摘要:

J O U R N A L H. E. AF~MBTRONG, Ph.D., F.R.S. E. ATKINBON, Ph.D. A. CRUM BROWN, D.Sc., F.R.S. WYNDHAM R. DUNSTAN. H. MCLEOD, F.R.S. R. MELDOLA, F.R.S. OF H. F. MOBLBY, M.A., D.Sc. W. RAMSAY, Ph.D., F.R.S. J. MILLAR THOMSON, F.R.S.E. T. E. THORPE, Ph.D., F.R.S. W. P. WYNNB, B.Sc. THE CHEMICAL SOCIETY. &bitor : C. E. QBOVES, F.R.S. Sub- &Mot : A. J. GBEENAWAY. 5. B. ASHEB ARON. D. BENDIX. A. Q.Bcoxa~. B. BRAUNER, P1i.D. B. H. BROUGH. H. (3. COLMAN, Ph.D. H. CBOMPTOX. L. DIE EONINQH. W. D. HALLIBUBTON, M.D., B.Sa., F. 9. KIPPINB, Ph.D., D.Sc. J. W. LEATHEB, Ph.D. A. R. LINQ. D. A. LOUIS. c. H. BOTIIALYLEY. F.R.S. N. H. J. MILLSB, Ph.D. G. T. MOODY, D.8c. J. M. H. MIJNRO, D.Sc. T. Gt. NIUEOLSON. E. W. PBEVOBT, Ph.D. E. C. ROSSITBB. R. ROUTLEDGE, B.Sc. M. J. SALTER. W.TATE. JAMES TAYLOR, B.Sc. J. B. TINQLE, Ph.D. J. WADE, B.Sc. (JN. W.) J. WALKEB, D.Sc., Ph.D. (J. W.) W. P. WYNNE, B.Sc. w. J. POPE. Vol. LX. 1 8 9 1. ABSTRACTS. L O N D O N : GURNEY & JACKSON, 1, PATERNOSTER ROW. 1891.LONDON : BARBISON AND 0 0 ~ ~ 4 , PBINTBRS IN ORDINANY TO HER MAJESTY, sr. MABTIN’S LANE.C O N T E N T S . ABSTRACTS OF PAPERS POBLISHED IN OTHER JOURNALS :- General and Physical CJLernist9-y, AMES (J. 23.). Some Gaseous Spectra : Hydrogen, Nitrogen . . . AYES (J. S.). Relations between the Lines of varioua Spectra . . . BOISBAUDRAN (L. DE). Spark Spectrum of Gadolinium Chloride . . ANDRES (A.). Spectroscopical Properties of Russian Oil of Peppermint . REQNARD (P.). Measurement of the Quantity of Light that enters Water . BUCHKREYER (L.). Change of Volume on Mixtiire of Two Liquids and its Influence on the Refractive Power .. . . . . . GLADSTONE (J. H.) and W. HIBBERT. Secondary Batteriee . . . MAGNANINI (G.). Electromotive Force of a Metal in a Series of Elecho- lytes . . . . . . . . . . . . . LE CHATELIEB (H,). Electrical Resistance of Metals . . . . . ARRHENIUS (S.). . KISTIAEOFFSEY (W.). Aqueous Solutiona of Double Salts . . . . TAMMAN (G.). Isomerism of the Metaphosphates . . . . . BROWN (J.). Electrification of Bffluvia from Chemical or Voltaic Reactions . . . . . . . . . . . . GORE ((3.). Changes of Property of Amalgams by Repeated Fusion . . ALLIHN (F.). Rise in the Zero Point of Thermometers of Jena Glass . . PICKERINQ (S. U.). Expansion of Water and Other 1,iquidR . . . BARUS (C.).Pressure Variation3 of Certain ITigh Temperature Boiling Points . . . . . . . . . . . . . LESPIEAU (R.) . Raoult’s Ebullioscope . . . . . . . STOHMANN (F.) and H. LANGBEIN. Thermochemistry of Pats and Fatty Acids . . . . . . . . . . . . . KLBINSTUCE (0.). Determination of Qpecific Gravity of Solids . . . RAMSAY (W.). Dissociation of Selenium Chloride . . . . . SUTHERLAND (W,). New Periodic Property of the Elements . . . CARNELLEY (T.). Approximate Algebraic Expression of the Periodic Law . PLANCK (M.). Osmotic Pressure . . . , . , . . . KAYSEE (H.) and C. RUNQE. Spectra of the Alkali Metals. . . . NASINI (R.). Dispersive Power of Organic Compounds . . . . KANONNIEOPF (I. I.). Relation between the Refractive and Rotatory Powers of Chemical Compounds. . . . .. . . . . GREEN (A. G.), C. F. CROSS, and E. J. BEVAN. New Photographic Method . . . . . . . . . . . . . MERCIER (P.). . WIEDEMANN (E.). Optical Notes . . . . . . . . PASCHEN (F.). Contact Difference of Potential of Metals . . . . TAMMANN ((3.). Electrical Conductivity of Precipitated Membranes . . TRGTSCH (J.). Influence of Water of Crystallisation on the Electrical Con- ductivity of Salt Solutions . . . . . . . . . CHROUSHTCHOPF (P.) and W. PASHEOFF. Electrical Conductivitr of Salt Solutions . . . . . . . . . . . . NOYES (A. A). Solubility of Mixtures of Electrolytically Dissociated Substances . . . . . . . . . . . . Electrical Conductivity of Salts in the Bunsen Flame Action of Borax in Developers for Photographic Plates a 2 PAQE 1 1 2 2 2 2 3 3 4 4 6 m 7 8 ’8 8 8 8 I I 11 11 1 2 13 14 137 138 138 138 139 139 139 140 141 141 142iv CONTKXTS.DRAGOUMIS (E. J.). Method of determining Thermal Expansion for Equal Quantities of Heat . . . . . . . . . . . GENIESER ( A . ) . . HOFMANN (A. W. T.). Dissociation Phenomena . . . . . . MAQNANINI (G.). Influence of Mineral Acids on the Velocity of the Re- action between Bromic and Hydriodic Acids . . . . . . WILDERMANN (M.). Velocity of the H alogenisation of Fatty Hjdrocarbons SABANBEFF (A.). Cryoscopic Investigation of Colloi’dal Substances . . WISLICENPS (H.). Apparatus for Distillation under Reduced Pressure . RETQERS (J. W.). Isomorphism . . . . . . . . . LONG (J. H.). Cimular Polarisation of certain Tartzate Soliitions . . BROOKS (E. E.). Phosphorescence of Lithium Compounds in Vacua, and Spectra of Coated Terminals .. . . . . . . . LEHMANN (0.). Crystalline Liquids . . . . . . . . ANDREwa (T.). Passive State of Iron and Steel . . . . . . BARUS (C.). Effect of Presmire on the Electrical Conductivity of Liquids . MAGNANINI ((3.). Electrical Conductivity of Boric Acid Solutions in Pre- sence of Dulcitol . . . . . . . . . . . GRIPPITHS (E. H.). Determination of Boiling and Freezing Points by means of the Platinum Thermometer . . . . . . . . STOHMANN (F.). Heat of Combustion of Organic Compounds . . . STOHXINN (F.). Relations of the Heats of Combustion of Solid Bibasic Acids tothose of Gaseous Hydrocarbons. . . . . . . LALA (U.). . PERMAN (E. P.). Experiments on Vapour Density . . . . . MACGBEGOR (J. G.). Variation of Density with Concentration cf Weak Aqueous Solutions of certain Salts .. . . . . . . TRAUBE (J.). Dissociation Hypothesis of Arrhenius . . . . . TRUSSEWITSCH (A. A.). Surface Tension of the Halogens . . . . KEHRMANN (F.). Influence of Mass on Chemical Processes. . . . BADER (R.). Affinity Constants of Organic Acids . . . . . AUNT (T. S.). Coefficient of Mineral Condensation in Chemistry . . HEYPEL (W.). Reactions at High Temperaturev and Pressares . . . SCHULZ (H.). Apparatus for Fractional Distillation in a Vacuum . . ITEMPEL ( W.). Error in the Principle of the Ordinary Exsiccstor . . CANERER (157.). Absorption Plates of Wood Wool . . . . . LOWENHERZ (8.). Molecular Refraction of Substances containing Nitrogen Du BOIS (H. E. J. (3.) and H. RUBENS. Refractiou and Dispersion in Certaiii Metals .. . . . . . . . . RtaoLLoT (H.). Absorption Spectrum of Iodine Solutions . . . JCHARF (P.). Gas Battery . . . . . . . . . . YASCHEN (F.). Development of E.M.F. between Mercury and an Electro- lyte . . . . . . . . . . . . . BERTHELOT (D.). Conductivities of Isomeric Organic Acids and their Salts BLUMKE (A). Connection between the Theoretical and Empirical Iso- thermals of Mixtures . . . . . . . . . . STOHXANN (F.) and C. KLEBER. . COL~ON (A.). Endothermic and ExotJimnic Reactions of Organic Bases , AMAGAT (E. H.). Compressibility of Gases : Results with Oxjgen, Hydro- gen, Nitrogen, and Air . . . . . . . . . . GALITZINE (B.). Dalton’s Law . . . . . . . . . JOLY (J.). Method for Determining the Absolute Density of a Gas . . !UASSON (0.). Relation between the Boiling Points, Molecular Volumes, mid Chemical Characters of Liquids .. . . . . . YOUEG (S.) . Relation between the Boiling Points, Molecular Volumes, and Chemical Characters of Liquids . . . . . . . IIEILBORN (E.). Coniaection between the Critical Data of Liquids and their Chemical Con st itutioii . . . . . . . . . . GALTERMEISTER (R.) . ViRcosity of Liquid Carbon Compounds and its Relation to Chemical Constii ution . . . . . . . . Estimation of the Specific Gravity of Frothy Syrups. Compressibility of Mixtures of Air and Carbonic Anhydride The Hydrogenation of Closed Chains EAQE 142 142 143 144 145 145 146 146 ’ 249 249 249 2 50 260 251 251 251 252 253 253 254 255 257 257 257 258 258 259 259 260 373 373 374 374 374 375 375 376 377 378 378 3’79 379 319 350 3SOv OONTENTS.PAWLRWSKI (B.). Influence of Pressure on Dissociation . . . . RIECKE (E.). Continued Dissociation and the Vapour Density of Sulphur . TIMOFBEFF (W.). Eflusion of Gases through a Narrow Aperture a t Different Tempmat urvs . . . . . . . . . . . VERNON (H . M.). Law of Diffusion of Liquids . . . . . . WIEDEBURQ (0.) . Hydrodiffusion . . . . . . . . STEFAN (J.). Ewporation and Dissolution Considered as Processes of Diffusion . . . . . . . . WINELER (L . W.?. Soiubi1;‘ty of‘Gases in Water . . . . . RAOULT (F . M.). Vapour Pressure of Solutions . . . . . . DOYEB (J . W.). Determination of Solubility Coefficients . . . . LE BLANC and A . A . NOYES . MAZZOTTO (D.). Cryohydrates of Mixtures of Salts . . . . . NEBNST (W.). New Application of the Crposcopic Method to the Deter- BECKMANN (E.).Determination of Molecular Weights by the Ebullition Method . . . . . . . . . . . . . BOLTZMANN (L.). Osmotic Pressure from the Etanilpoint of the Kinetic Theory of Qases . . . . . . . . . . . CIAMICIAN ((3.). The Molecular Theory and Elecbrolytic Dissocitttion . TRAUBE (J.). The Amocitltion Hypothesis in its Relation to the~l’heories of Clausius and Van’t Hoff . . . . . . . . . CLARKE (F . W.). Conoordance in Atomic Weight Ddterniinations . . BRUHL (J . W.). Measurement of Refractive Indices a t High Temperatures by means of tlhe Total Retlectometer . . . . . . . FOCK (A.). Explanatiun of Optid Aativity . . . . . . L~VAY (E.). Relatian between Electrical and Chemical Energy in Galvanic Cells . . . . . . . .. . . . BUBCH (G . J.) and V . H . VRLEY . Variation of E.M.F. of Cells of certain Metals, Platinum, and Nitric Acid . . . . . . . . OBERBECE (A.) and A . J . EDLER . Eleclromotive Force of Ualvanic Elenieuts ARBHENIUS (S.). Conduction of Nlectricity by the Vapours of Heated Salts . . . . . . . . . . . . . OSTWALD (W.). Conductivity of Ismeric Organic Acids and their Salts . . . . . . . . . . . . . BERTHELOT (D.). Conductivity of Isumeric Organic Acids and their Salts . . . . . . . . . . . . . OBERBECE (A.). Elect. rical Behaviaur of Precipitnted Membranes . . ERRERA (L.). Relation between Atomic Weight and Magnetim . . VICEXTJNI ((3.). Thermal Dilatation of Liquid Bismuth near its Melting Point . . . . . . . . . . . . . PICKERING (S . U.). Determinations of the Heat Capacity and Heat of Pusion of some Substances to test the Validity of Person’s Absolute Law .. . . . . . . . . . . . Use of the Cdorinietric Bomb for the Determination of the Heat of Combustion of Coal . . . . . . . . BRUHL (J . W.). Determination of the Specific Gravity of Viscid Sub- stances . . . . . . . . . . . . . SCHEIBLER (C.). Determination of the Specific Gravity of Viscid Sub- stances . . . . . . . . . . . . . ARRHENIUS (S.). Hypothesis of Electrolytic Dissociation . . . . NASINI ( R ) . Nature of Osmotic Pressure . . . . . . . MONTEMARTINI (C.). Velocity of Decomposition of Ilitrous Acid in Aqueous Solution . . . . . . . . PRUD’HOMME . Mordantsand the Periodic Law . . . . . . Augmented Solubility . . . . . mination of Molecnlar Weights . . . . .. . . FULDA (H.). Sulphonation of Quinoline and Phenol . . . . . CANTOR (33.). Chemistry of the Accmulator . . . . . . ZAHN (G . H.). Electrical Besistance of Bismuth . . . . . SCHEUHER.KESTNRR . MARGULES (M.). Dalton’s Law . . . . . . . . . NOYES (W . A.). Unit of A&rnic Weights . . . . . . . PAGE 381 381 381 883 383 384 384 386 387 388 385 389 389 389 390 390 390 391 513 613 513 514 514 514 515 515 517 517 517 61 8 518 619 520 520 520 520 521 522 522 523 523vi CONTENTS. PAQL GWGLIELMO ((3.). Modification of the Sprengel Pump . . . . 524 BRWHL (J. W.). Vapours. . . . . . . . . . . . . 629 BEUHL (J. W.). Refractive Indices of Water . . . . . . 629 BRUHL (J. W.). Relation between the Spectrometrical Constante and Chemical Constitution of Epichlorhpdrin, Acetaldehyde, Parwet- aldehyde, and Benzene .. . . . . . . . . 630 BEETHELOT (D.). Basicity of Acids deduced fram their Conductivity : Monobasic and Bibasic Acids . . . . . . . . 631 BERTHELOT (D.), Conductivities of Triba-sic Acid8 . . . . . 632 OSTWALD (W.). Conductivityof Organic Acids . . . . . . 632 BERTHELOT (D.). Conductivityof Organic Acids . . . . . 632 HEILBORN (E.). Specific Heat of Mercury . . . . . . . 632 THOMSEN (J.). Heat of Combustion and Constitution of Organio Com- pounds . . . . . . . . . . . . . 632 BPUHL (J. W.). Relatione between the Heats of Combustion and Structural E’ormulse of the Alkylene Oxides, Acetaldehyde, and its Polymerides, Trimetliylene and Benzene . . . . . . . . . 633 LALA (U.). Compressibility of Mixtures of Air and Hydrogen .. . 634 BARWS ((3.). Compressibility of Hot Water and ita Solvent Actian on Glass . . . . . . . . . , . . . 634 LVNQP (G.) and 0. NEUBERQ. Determination of Vapour Densitiee . . 633 LORENTZ (H. A.). Kinetic Molecular Theory of Dilute Solutions . . 637 BOLTZMANN (L.). Osmotic Pressure and the Kinetic Theory of Gases . 638 TRAWBE (J.). Dissociation Hypothesis . . . . . . . 638 LELLMANN (E.) and H. GROSS. A5nito-y of Bas- . . . . . 638 REFOPMATSKY (a). Velocity of Reaction in Gelatin . . . . . 639 STIJHL (M.). Self-action by Means of Water Pressure. . . . . . . 640 HARTLEY (W. N.). Relations between the Lines of Various Spectra . . 773 OLSZEWSKI (K.). Ab~orption Spectrum and Colonr of Liquid Osygen . 773 DESLANDRES (H ). of Hydrocarbons . . . . . . . . . . . 773 GLADSTONE (J.H.) and G. GLADSTONE. Fluorobenzeneand AlliedCompounds . . . . . . . 774 BARBIER (P.) aiid L. Rowx. Sdts . . . . . . . . . . . . . 774 BRUHL (J. W.). 774 WAT~TEP (B.). Optical Prqerties of a-Bromonaphthalene . . . . 376 BECQUEREL (H.). Light and Heat . . . . . . . . . . . 7’16 BIDWELL ( S . ) . Experiments with Selenium Cells . . . . . 777 GLADSTONE (J. H.) and W. HIBBERT. ’777 HAWSSKNECHT ((3.). Solid Carbonic Oxide . . . . . . . . . . 777 ROSA (E. B.). Specific lnductive Capacity of Electrolytes . . . . 778 BRAWN (F.). Observations on Electrdysis . . . . . . . 778 DRWDE (P.) and W. NERNBT. Aggregation on the Behaviour of Bismuth in t-he Magnetic Field. . 779 CAILLETET (L.) and H. COLARDEAW. ratures and Pressures, especially of Water . . . . . . 779 RICHAEDSON (A.E.). Point and Moleculas Weight. . . . . . . . . 780 SWART (A. J.). Lawsof Dissociating Gases , . . . . . 780 ANDREAE (J. L.). Constant Vapour Pressure . . . . . . 781 VRIENS (J. (3. C.). its Solut.ions . . . . . . . . . . . . 783 DIETEPICI (C.). Vapour Pressures of some Aqueous Salt Solutions at 0” . 783 BECKMANN (E.). Apparatus for Freozing Point Determinations . . 784 RIEKE (E.). Thermal Potential for Dilute Solutions . . . . . 786 Refrawtion and Chemical Constitution of Gases and New Automatic Mercury Air-pump, with Armngement for New Mlethod of Investigating Faint Baads in the Spectra Refraction and Dispersion of Dispersion of Organic Compounds : Ethereal Relations between Dispersion and Chemical Constitution , Phosphorescence of Minerals under the Influence of Chemistry of Secondary Batteries .Electrical YheiLornena developed in the Formation of Influence of Temperature and the State of Determination of the Critical Tempc- Specific Gravity of a Liquid, a Functiou of its Boiling Vapour Prcssuro of Copper Potassium Chloride andCONTENTS . vii Discussion on the Theory of Solution . . . . . . . . MASBON (0 ) . Deductions from the Gaseous Theory of Solut. ion . . PICKELINC) (S . U.). Deductions from the Gaseous Theory of Solution . RAMSAE (W.). Some Ideas about Solution . . . . . . . BODLANDEL (Gt.). Solubility of some Substances in Mixtures of Water and Alcohol . . . . . . . . . . . . . BODLANDER ((3.). Solubility of Mixed 13alts in Water . . . . CONRAD (M.) and C . BBWCKNER . . EVANS (W . P.). Rate of Decomposition and Stereochemistry of Chlor- COLSON (A.).Action of Water on Normal Salts of hmines of the Parathe SCHLEIELMACHEB (A.). Boiling Point Determinations with Small Amounts of Material . . . . . . . . . . . . WATSON (G.). Precipitation . . . . . . . . . WELLS (H . I,.). Automatic Mercury Pump . . . . . . KAYSER (EL) and C . RUNGE . Spectra of t h s Elements of the Second LEMOINE ((3.1. Chemical Effects of Light : Measurement of Physical Ab- SACE (P.). Determination of the Maximum Conductivity of very Dilute PIGEON (L.). Thermochemistry of Platinic Chloride and its Compounds . BERTHELOT . Calorimetric Data . . . . . . . . . MASSOL ((3.). Thermochemistry of Bibasic Organic Acids . . . . JAHN (H.) . Themhemistry of Dextrotartaric and Lsevotartaric Acids .SCHMIDT (GI . C.). Vapoiir Pressures of Homologous Compounds . . LEMOINE ((3.). Dissociation of Amylene Hydrobromide under Low Pres- THOULET (J.). Dkusion of Fresh Water into Sea Water . . . . TRAUBE (J.). Freezing Points of Dilute Aqueous Solutions Gf Non-Electro- EYKMAN (J . F.). Cryoscopic Behaviour of Aqueous Canesugar Solu- tions . . . . . . . . . . . . . PICKEBINO (5 . U.). Theory of Dissociation into Ions and its Conse- quences . . . . . . . . . . . . . PICKEBING (S . U.). Association z)emus Dissociation in Solutions . . . LUPTON (S.). Reduction of the Results of Experiments with Special PICEEEINO (S . U.). Reduction of the Results of Experimenta on the HAYES (E . H.). Reduction of the Results of Expzriments on the Hydrate PICKE~~INO (S . U.). Objections to the Work on Sulphuric Acid Solu- tions .. . . . . . . . . . . . BLAREZ (C.) . Influence of Inorganic Potassium Ss1t.s on the Solubility of BLAEEZ ((2.). Influence of Potassiuni Halides on the Solubility of Nbrmai ROSZKOWSKI (J.). Influence of Temperature on the Limits of the Explosion of hueous Mixtures . . . . . . . . . Determination of Affiity Coetticients hydrins . . . . . . . . . . . . . TRAUBB (J.). Theory of Dissociation . . . . . . . . CLARKE (F . W.). Atomic Weights . . . . . . . . Periodic Group . . . . . . . . . . . sorption . . . . . . . . . . . . . Copper Sulphate Solutions . . . . . . . . . EEILBORN (E.). Critical State of Liquids . . . . . . . WALD (F.). Adhesion at the Breezing Point . . . . . . PIOEERING (8 . U.). Cryoecopy of Dilute Solutions .- . . . lytes and Electrolytes . . . . . . . . . . TRATJBE (J.). Electrical Conductivity and Freezing Point . . . . sure8 . . . . . . . . . . . . Reference to the Hydrate Theory of Solution . . . . . . Hydrate Theory of Solution . . . . . . . . . Theory of Solution . . . . . . . . . . . . . . . . . . TREVOR (J . E.). Solutions of Double Salts Potassium Eydrogen Tartrate . . . . . . Potassium Sulphate . . . . . . . . . . BUDDE (E.). Dead Space in Chemical Reactions . . . . . . MEYERHOFFBB (W.). Factors of Energy . . . . . . . KUMMEL ((3.). Botatory Dispersion of Tartrates . . . . . PAC35 786 791 793 793 794 795 796 796 797 873 874 875 875 877 966 965 966 966 967 968 969 969 969 969 970 970 971 971 971 972 972 fly72 973 973 973 973 973 974 974 975 975 975 1145... \-Ill CONTENTS.PAOB HIWS (G.). Sensitisem for h y s of LOW Refmngibility . . . . 1145 LOEB (M.). Is Chemical Action Affected by Maqnetiem ? . . . . 1145 CALLENDAR (a. L.) and E. H. QEIFPITHS. mometers . , . . . . . . . . . . 1146 JONES (H. C.). of Material . . . . . . . . . . . . 1146 STOHMANN (F.) and 0. KLEEBER. Hydrogenation of Closed Chains . . 1146 BBUHL (J. W.). 1147 MULLER (J.). Dsuaion of Ammonia through Water and Alcohol . . 1147 AREHENIIJS (S.). Hypothesis of Electrolytic Dissociation . . . . 1148 NERNST (W.). Distribution of a Substance between Two Solvents . . 1148 AIJLICH (P.). miscible Solvents . . . . . . . . . . 1148 LELLMANN (E.) and H. GROSS. Affinity CoeCficients of Bases . . . 1149 SCHUKAEEFF (A.). Velooitv of Reaction between Metals and Halogens .1149 MA~NANINI (G.). Reaction’ between Ferric Salts and Soluble Thiocyanates. 1150 LIEBEEICH (0.). Dead-spacein ahemical Reactions . . . . . 1150 OBTWALD (W.). Autocatslysis . . . . . . . . . 1151 RETGERS (J. W.). Isomorphism . . . . . . . . . 1151 BRUHL (J. W.). perature . . . . . . . . . . . . 11 52 EDER (J. M.). Ammonia-Oxygen Flame . . . . . . . . . 1305 NASINI (R.) and 1’. COSTA. sulphine Derivatives . . . . . . . . . . 1305 ELLINGER (H. 0. U.). 1305 ROSENTHAL (J.). Electrical Conductivity of Solid Electrolytes . . . 1307 LE CHATELIEE (H.). trical Conductivity. . . . . . . . . . . 1308 HARTWIG (K.). Molecular Conductivity of Acids in Various Solvents . 1308 EXNEE (F.). Electrochemical Investigations . . . . . . 1309 VAN DER WAALS (J. D.).Formulse for Electrolytic Dissociat.ion . . 1309 TECLU (N.). The Nature of Flame . . . . . . . . 1309 BERTHELOT and MATIGINON. Thermochemietry of Organic Chlorine Com- pounds . . . . . . . . . . . . . 1311 DE FORCEAND. Constitution and Heat of Formation of Bibasic Erythr- oxides . . . . . . . . . . . . . 1312 MASSOL ((3.). Thermochemistry of Propionic Acids and of the Alkaline Propionates . . . . . . . . . . . . 1313 TIMOF~EFF (W.). Heat of Dissolution of Carbon Compounds in Various Alcohols. . . . . . . . . . . . . 1313 BEETHELOT and MATIQNON. Themochemistq of the Camphene Series . 131.3 MOIJLTN (A.). Atomic Weights and the Densities of Liquids . . . 1315 SCHALL (C.) and L. KOSSAKOWSKY. Study of Evaporation . . . 13i6 BECKMANN ((3.). Determination of Molecular Weights by the Boiling Point Method.. . . . . . . . . . . 1317 ENGEL. Influence of Alkaline Bases on the Solubility of Alkaline Salts , 1318 BLAEEZ (C.). Influence of Potassium Salts on the Solubility of Potassium Chlorate . . . . . . . . . . . . . 1319 VAN DEL WAALS (J. D.). Magnitude of the Pressure in Coexisting Phases of Mixtures, especially in s’alt and Acid Solutions . . . . . 1319 ISAACHSEN (D.). Change of Colour of Salt Solutions . . , . . 1319 BKRAUP (2. H.). Theory of Double Linkage . . . . . . 1320 DE LALANDE (F.). Copper Oxide Battery . . . . . . . 1405 LE BLANC (M.). Electromotive Forces of Polariaation . . . . 1405 TIMOF~EFF (W.). Specific Heats of some Solutions . . . . 1406 ARRHENIUS (S.). Heats of Neutralisation . . . . . . . 1406 HINRICHS ((3.).Pressure. . . . . . . . . . . . . l a 6 NEUBERQ (0.). Vapour Density of Ammonium Chloride . . . . 1407 Standardising Platinum Ther- Determination of the Boiling Point with Smdl Quantities Determination of the Specific Gravity of Viscid Siibstances Relation between Affinity and Partition Coefficients in Im- Vacuum Desiccator arranged for Evaporation at any Tem- New Bands and Lines in the Emission Spectrum of the Molecular Refractire Energy of some Methyl- Strengkh of Solutions estimated by their Refraction Molecular Changes in Metals as shown by their Elec- Calculation of the Boiling Point of a Liquid under anyOONTENTS. ix AYTOINR (C.). Vapoiir Pressure of Water up to 200 Atmospheres . . DUHEM (P.). A Theorem of Willard Gibbs. . . . . . . HINEICHS ((3.). Calculation of Molecular Volumes .. . . . TRAUBE (J.). Capillarity Constantee of Organic Substances in Aqueous Solution . . . . . . . . . . . . . GUYE (P. A.). Determination of Molocular Weight at the Critical Point . BAN BIJLERT ( A.). Cryoscopic Observations . . . . . . WANELYN (J. A,) and W. J. COOPER. Solution . . . . . . BARUS (C.) and E. A. SCHNBIDER. Nature of ColloYdal Solutions . . BEBSCH (W.). Interaction between Oxidea and Hjdroxides of Hoavy Metals and the Halogen Compounds of the Alkalis . . . . BUGAUSZKY (S.). Velocity Coefficients of Rases . . . . . . WALD (F.). Energy Content in Chemistry and Physics . . . . STUHL (M.). Glass Air Pump . . . . . . . . . E IC H H OBN. U ni versa1 Gasholder . . . . . . . . BLOCHMANN (R.) and R. BLOCHMANN. Lecture Experiment : Dissociation of Ammonium Chloride .. . . . . . . . . Iqrorganic Chemistry. ENIETBCH (R.). Properties of Liquid Chlorine . . . . . . BORNTRAGER (H.). Simple and Rtqpid Evolution of Pure Gases . . MOISSAN (EL.). Atomic Weight of Fluorine . . . . . . TIMOF~EFF (W.). Solubility of Oxygen and Hjdrogen in Water and in Alcohol . . . . . . . . . . . . . CURTIUS (l’.). Hydrogen Nitride (Azoimide) . . . . . . LOEW (0.). Catalytic Decomriositiolr of Ammoniiim Nitrite . . . BERTHELOT. Absorption of Carbonic Oxide tw Earth. . . . . BOCK (A.) and KLUSS. Double Chlolride and hthionate of Barium . . SCHNEIDER (R.). Action of Hydrogen on Potassium Thallium Sulyhide . BOISBAUDRAN (L. DE). Reseadies on the Gadolinium of Marignnc . . BOISBAUDRAN (L. DE). Equivalent of Terbia .. . . . . MAURO (F.). Ammonium Bluoroxginolybdate . . . . . . ROTHENBACH (F.). Datible Salts of Tungshc and Vanadic Acids . . ASTRE (C.). Bismuth Oxyiodide . . . . . . . . . SCHUTZENBRRQER (P.). Platinum Thiocaybide . . . . . . GAUTIER (H.) and G. CHARPY. Afinities of Iodine in Solution . . . BECQUEREL (H.) and H. MOISSAN. Fluorspar fmm Quinci6 . . . COSTA (T.). Molecular Weight and Refractive Energy of Sulphur Di- chloride . . . . . . . . . . . . LUNGE ((3.) and M. ISLER. Specific Giavity of Solphuric Acid . . . ROSENPELD (M.). Reduction of Oxygen Compounds with Hodium . . FOCK (A.) and K. KLGs. Ammonium Pyroeulphite . . . . . SESTINI (F.). Properties of some Beryllium Salts and of the Corresponding Aluminium Compounds . . . . . . . . . . OTTO (R.) and D. DREWES.Magnesium Lead CMoride . . . . MINET (A.). Electrolysis of Fused Aluminimn Chloride , . . . OLATZEL (E.). Preparlttion of Chromium from Potassium Chromium Chloride and Nagnesium . . . . . . . . . HERTZ (J.). Molecular Weights of Sulphur, Phosphorus, and Iodine in Solu- tion . . . . . . . . . . . . . DITTE (A.). Action of Sulphuric Acid on Metals . . . . . BOUTZOUREANO. Selenite8 . . . . . . . . . . MAWMEN& (E. J.). Preparation of the Nitroeen Hydride N2H2 . . . CURTIUS (T.) and H. SCHULZ. Hydrazine Hydrate and Haloid Salts (Halo- gen Diammonium Compounds) . . . . . . . . MOISSAN (IT.). Phosphorus Trifluoride . . . , . . . MOISSAN (H,). Preparation of Phosphorus Oxjfluoride . . . . PAOB 1407 1#7 1408 1408 1411 1411 1412 1412 1413 1413 1414 1414 1414 1415 14 14 15 15 66 16 16 16 16 17 17 18 18 19 19 148 148 149 150 1 50 151 15 L 151 152 152 260 260 262 262 263 264 264X CONTENTS .PAQB MOISSAN (H.). Arsenic Fluoride . . . . . . . . 265 MCCAY (L . W.). Action of Hydrogen Sulphide on the Ortharsenatm of the Alkali Metals . . . . . . . . . . . . 265 SCHUTZENBERQEE (P.) snd L . SOEIUTZENBEBQER . Certain Forms of Carbon . . . . . . . . . . . . . 265 PRANGE (A . J . A.). Allotropic Silver . . . . . . . . 266 WBIQHT (C . R . A.) and C . THOMPSON . Ternary Alloys . . . . 267 PESCI (L.). So-called Ammoniacal Mercury Compounde . . . . 268 GORQEU (A.). Manganese Oxides . . . . . . . . 270 FABRIS ((3.). Violet Chromium Fluoride . . . . . . . 271 GARNIER (J.). Artificial Production of a Chromium Blue . . . . 271 PICCINI (A.).Action of Ammonia on Solutions of Normal Ammonium Tit an0 fl uoride . . . . . . . . . . . . 271 SCHNEIDEB (R.). Atomic Weight of Bismuth . . . . . . 271 SMITH (E . F.) and H . F . EELLEE . Action of Hydrogen Sulphide on certain Metallamines . . . . . . . . . . . . 2t2 WANKLYN (J . A.) and W . J . COOPER . Hydrogm . . . . . 392 MUSSET (F.). Purification of Iodine from Chlorine . . . . . 392 EASSNER ((3.). Utilisation of Atmospheric Oxygen . . . . . 392 HINSBEEC) (0.). Selenium . . . . . . . . . . 393 MENDELBEPF (D.). The Discovery of Nitrogen Hydride . . . . 394 LWPKE (R .. ). Preparation of Hydrogen Phosphide . . . . . 397 BESSON (A.). Bromides . . . . . . . . . . . . 398 PARTRIDGE (E . A.). Atomic Weight of Cadmium . . . . . 399 RICHARDS (T . W.). Cuprammonium Compounde .. . . . 399 HAACK (K.). Mercury Arsenates and Phosphates . . . . . 400 HEINTZE (J.). Ultramarine . . . . . . . . . 900 LIVERSIDQE (A.). Reniovul of Gold froin Solution and Suspension by Fungoid Growths . . . . . . . . . . . 441 JOLY (A.). Ammoniacal Derivatives of Ruthenium Nitroeochloride . . 401 PALMAER ( W.). Iridioammonium Compounds . . . . . . 402 CURTIUS (T.) and R . RADENHAUSEN . Hydrogen Nitride (Azoimide) . . 524 VELEY (V . H.). Certain Mctals . . . . . . . . . . . 525 Combination of Ammonia with Phosphorus Chlorides and NICOLAS (M.). Preparation of Pure Phosphoric Acid . . . . . 398 Conditions of Chemical Change between Nitric Acid and MINET (A.). Electrometallurgy of Aluminium . . . . . . 525 CLASSEN (A.) . Atomic Weight of Bismuth . .. . . . . 525 ANTONY (V.) and A . LUC~HESI . Aaric Sulphide . . . . . 526 AMAT (L.). Phosphite . . . . . . . . . . . . 641 BESSON (A.) . Silicobromoforui . . . . . . . . . 642 JOANNIS . Sodamide and Disodanimonium Chloride . . . . . 642 JOANNIS . Combination o€ Ammonia with Chlorides . . . . . 643 MORSE (H . N.) and J . WHITE . of Metallic Magnesium . . . . . . . . . . 643 WELD (F . C.). 643 LUEDEKINQ ((2.). Hydrated Lead Oxide . . . . . . . 644 HIRSCH (A.). Copper Arsenates . . . . . . . . . 640 RATHKE (B.). The Carbon of Spiegeleisen . . . . . . . 646 RATHKE (B.) . Crystalline Ferroinanganese . . . . . . . 646 SEUBERT (K.) and K . K O B B ~ Atomic Weight of Rhodium . . . 646 WARDER (R . B.). 798 ILOSVAY (I.). a Flame? Ie there Ozone near a Flame? . . . . . . 798 AMAT (L.). Conversion of Sodium Pyropbosphite into Phosphite .. 799 WARREN (H . N.). New Form of Silicon . . . . . . . 799 BESSON (A.). Action of Hydrogen Iodide on Silicon Chloride . . . 800 BERTHELOT . Action of Heat on Carbonic Oxide . . . . . . 801 Conversion of Sodium Pyrogdiosphite into Sodium Hydrogen Dissociation of Magnesium Oxide by Means Melting Point of certain Alloya . . . . . . ROIJSSEAU (G.). Hydrated Sodium Manganites . . . . . . 645 Coefficients of Volatility for Aqueous Kydrochl.oric Acid Is it possible to form Ozone by Lowering the Temperature ofCONTENTS . BERTHELOT . Reaction of Carbonic Oxide . . . . . . WINKLER (C.). Reduction of Oxygen Compounds by Magnesium . . BODLANDEB ((3.). Rubidium Barium Dithionate . . . . . RICHARDS (T . W.) .Atomic Weight of Copper . . . . . . ASB~TH (A . v.). Artificial Cryolite and the Dissociation of Aluminium Fluoride . . . . . . . . . . . . . OSMOND (F.). Csrburation of Iron by the Diamond . . . . . V~ZES (M.). Bromo-nitro-compunds of Platinum . . . . . LIEIDIS (E.). Double Nitrites of Rhodium . . . . . . . VERNON (H . M.). Silent Discharge and Chlorine . . . . . LEA (M . (3.). Allotropic Silver . . . . . . . . . HALLOCK (W.). New Method of making Alloys . . . . . . VIQNON (L.). Formation of Coloured Lakes . . . . . . KNAPP (F.). Magnus’ “ Black Sulphur ” . . . . . . . FOCK (A.) and K . KLUSS . Tliiosulphates . . . . . . . KEuss (Q.) and H . MOPAHT . Beryllium . . . . . . . MEINEKE (C.). Atomic Weight of Chromium . . . . . . FRIEDEEIM (C.). Molybdovandates .. . . . . . . PETBESEN (E.). V a n a h m Fluorides . . . . . . . . SEUBEPT (K.). Atomic Weight of Osmium . . . . . . STOKLABA (J.) . The Soluble Phosphoric Acid Compounds of Super- phosphates . . . . . . . . . . . Behaviour of Preparations of Zinc Sulghide . . . . Atomic Weight of Leiithanum . . . . . . CAWLEY (J.}. BRAUNER (B.). SEUBEFLT (K.). Atomic Weights of the Platinum Metals . . MORLBY (E . W.). Volumetric Composition of Wtrter . . . . . FILETI (M.) and F . CROSA . Preparation of Hydrobromic Acid . . . ENGEL . Two New Modifications of Sulphur . . . . . . . FRIEDEL (C.). Crystalline Form and Optical Properties of Engel’s Crystal- COLEFAX (A.). Volatility of Sulphuric Acid a t Ordinary Temperatures . HOWT (A) and R . OTTO . Formation of Dithionic Acid from Sodium Sulpbite .. . . . . . . . . . . . line Modification of Sulphur . . . . . . . . . TRAUBE (M.). Sulphuryl Peroxide (Holoxide) . . . . . . SAB~TIER (P.). Boron Hydride . . . . . . . . . MoIsaAN (H.). Boron Triidide . . . . . . . . . SABATIER (P.). Boron Sulphide . . . . . . . . . SABATIER (P.). Boron Selenide . . . . . . . . . MARSHALL (EL) . Potassium Persulphate . . . . . . . ROSENFELD (M.). Sodium . . . . . . . . . . GUNTZ . Argentous Compounds . . . . . . . . BESSON (A.). Action of Hydriodic Acid on Boron Bromide . . . Action of Hydrogen Bromide on Silicon Chloride . . . BESEON (A.). WEEILEN (J . M.). MEYER (G.). Cause of the Slight Solubility of Chemically Pure Zinc in Acids . . . . . . . . . . . . . . . Deterniination of the Molecular Weight of some Metals OTTO (R.) and D .DREWES . Magnesium L e d Iodide . . . . . BETTENDORFF (A.). Earths of the Cerium and Yttrium Groups . . . SCKUMANN (J.). Amalgams . . . . . . . . . . ANDR~ ((3.). Ammoniacal Mercuric Chlorides . . . . . . P~CHARD (E.). New Oxygen Compound of Molybdenum . . . . PBCHARD (E.). New Oxjgen Compound of Tungsten . . . . . KRUBS ((3.) and K . OFrNMlara . Thiovanadates . . . . . KEISER (E . H.). Atomic Weight of Oxygen . . . . . . VIARD (G.). Basic Magnesium and Zinc Chromites and Normal Cadmium Chromite . . . . . . . . . . . KRAUSE (A.) and V . MEYEEL . . NOYES (W . A.). Atomic Weight of Oxygen . . . . . . MA~CHLEWSKI (L.). Reaction between Hydrogen Arsenide and Sjlrer Slow Combustion of Gaseous Mixtures . xi PAQE 801 801 80z 803 805 805 806 807 807 507 808 877 877 879 880 881 881 881 882 8844 884 8M 885 976 976 976 977 977 978 978 979 979 980 981 981 981 982 982 983 983 984 984 984 386 986 987 988 988 989 1153 1154 1154 Nitrate .. . . . . . . . . . . . 1154xii CONTEXTS . PAGE HITCHCOCK (R.). Action of Light on Silver Chloride . . . . . 1155 WINELER (C.). Reduct-ion of Oxides by Magnesium . . . . . 1155 SEIJBERT (K.). Basic Zinc Sulphite . . . . . . . . 1157 MOISSAN (H.). Prepamtion of Crystdine Barium and Calcium Flnor- chlorides . . . . . . . . . . . . 1155 KWASNIK (W.). Action of Ammonia on Zinc Chloride . . . . 1157 VAN LESSEN . 1157 WRIGHT (C . R . A.) and C . THOMPSON . Ternary Alloys . . . . 1158 WEIGHT (C . R . A.), C . THOMPSON. and J . T . LEON . Ternary Alloys: Method of Graphic Representation .. . . . . . 1158 RBTQEES (J . W.). Decomposition of Potassium Manganate by Ammonium Salts . . . . . . . . . . . . . 1159 KEHRMANN (F.) and M . FREINPEI, . Complex Inorganic Acide : Phospho- tungstic Acids . . . . . . . . . . . 1150 MOREL (J.). Hpdrate of Potassium Stannicliloride . . . . . 1160 HENSGEN (C.). Subliiiiation of Antimony Tricliloride . . . . . 1160 MATTHEY (N.). Metallurgy of Bismuth . . . . . . . 1161 MEYER (V.). Bismuth Bromide . . . . . . . . . 1161 ROBERTS-AUSTEN (W . C.). Certain Properties of Metds considered in re- Iation to the Periodic Law . . . . . . 1161 SCHNEIDEB (E . A.). Colloidal Suiphides of Uold . . . . . . 1162 MYLIUS (F.) and F . I'OERSTER . Derivatives of Carbonyl Cliloropla ti- nite . . . . . . . . . . . . . 1162 PALMAER (W.).Iridioammonium Compounds . . . . . . 1165 FEIT ( W . ) and K . KUBIERBCHKY . . 1320 CIJRTIUS ('J?.). Diammonium Bemieulphate . . . . . . . 1321 MINET (A.). Electroly& of Fused Cornpounds of Boron and Silicoii . 1321 WARREN (H . W.). Sodium and Potassium Niirites . . . . . 1321 ~ I J N T Z . Silver Subchloride . . . . . . . . . . 132Z MOND (L.) and R . NASINI . Some Physical Properties of Nickel Carbon Oxide and of other Nickel Compound8 . . . . . . . 1322 ROSENHEIM ( A.). Action of Platinic Hydroxide on Tiingstates . . . 1323 SCHNEIVEB (R.). Atomic Weight of Bismuth . C'onipoaition of Commcr- cia1 Bismuth and of Commerciully Pure Bismuth . . . . . 1324 PIGEON (L.) Compounds of Platinio Chloride with Hydrogen Chloride . 1325 J~PGRK~EN (S . M.). Luteorhodium Salts .. . . . . . 1325 J~RGENSEN (S . M.). Acid Luteorhodium and Roseorhodium Nitrates . 1327 LEDIJC (A.). Gravimetric Composition of the Air . . . . . 1416 LEDIJC (A.). Specitic Gravities of Oxygen, Hydrogen, and Nitrogen . . 1416 LVP~ERRE ((2.). A Property of Sulphur . . . . . . . 1417 CHENEVIER (A.). Purification of Carbon Bisulphide . . . . . 1417 MUTHMANN (W.). Isomorphism of Sulpliur. Selenium. and Tellurium . 14.17 POIJLENC ((2.). Phosphorua'l'rifluorodichloride . . . . . . 1417 CLAYION (E . G.). Arsenious Oxide Solutions . . . . . . 1418 BERSON (A.). Boron Phosphide . . . . . . . . . 1418 BESSON (A.). Silicon Chloriodidee . . . . . . . . 1418 BESBON (A.). Silicon Bromiodides . . . . . . . . 1419 SABATIEB (P.). Silicon delenido . . . . . . . . . 3419 MOISBAN (H.).Carbon Tetriodide . . . . . . . . 1420 UUNTZ . Action of Light on Silver Chloride . . . . . . 1420 MOISSAN (H.). Silver Fluoride . . . . . . . . . 3421 LIMB ((3.). Electrolysis of Barium Chloride . . . . . . 1421 DENNSTEDT (M.). Hardening of Plast. er Casts . . . . . . 1421 POTNTET (G.). Preparation of Crptallme Monocalcium Phosphate . . 1421 CAUSSE (H.). Action of Acetstes on Monocalcium Pliosp'iate . . . 1422 LEPIERRE (C.) and M . LACHAUD . Thallium Conipounds . . . . 1422 LEDUC (A.). Copper Hydrides . . . . . . . . . 1422 ROUSSEAIJ ((3.) and Gt . TITE . . 1423 STEINSCHNEIDER (J.). Copper Phosphates . . . . . . . 1423 hBuds (G.). Erbium and lhdjuium . . . . . . . . 1424 Nitrite of Potassium. Lead. and Copper . . . . . Prepbration of Hydrobromic Acid .Action of Water on Basic Copper Salts .CONTENTS. SEUBEUT (K.) and W. POLLARD. Melting Point and Crystalline Form of Aluminium Chloride . . . . . . . . . . GAUTIER (H.) and G. CHARPY. BERTHELOT. A Volatile Compound of Iron and Carbonic Oxide. Nickel: cmbon-oxide . . . . . . . . . . . . GARNIER (J.). Volatilissbion of Nickel and Iron in Presence of Carbonic Oxide . . . . . . . . . . . . . SCHUTZENBEBQEB (P.). Volatility of Nickel in Presence of Hjdrogen Chloride . . . . . . . . . . . . . VORTMANN ((3.). Cobalt Dioxide. . . . . . . . . RECOVRA (A.). Action of Heat on Solutions of Chromic Sdb. Green Salta of Chromium . . . . . . . . . . . MASSIQNON (J.) and E. VATEL. New Process for the Manufacture of Chromates . . . . . . . . . . . . PBCIXARD (E.). Reaction of Chromic Acid with Barium Hydroxide in Presence of Oxygen .. . . . . . . . . OUVRARD (L.). Zirconatm of the Alkalis . . . . . . . OUVFLAED (L.). Zirconatfee of the Alkaline Earths . . . . . V’ILM (I?.). Antimony Pentasulphide . . . . . . . . MOISSAN (H.L Action of Phowhorus Pentaauoride on Heated Spongy Action of Nitric Acid on Iron . Platinbm ‘ . . . .. . . . . . . JOLY (A.), Osmium, Osmitimic Acid, and Osmismates . . Mineralogical Chemistry. LINDSTP~M (G.). Birmuth Minerals from Gladhammar HIDDEN (W. E.) and S. L. PENFIELD. Hamlinite . SCHULTEN (A. v.). HAMBERQ (A.). HATLE (E.) and H. TAUSS. Minerals from Styria . MEUNIER (S.). Fluorine and’ the Synthesis of Minerals RAMMELBBERQ (C.). Sigterite, 8 New Felspar . . SCACCHI (E.). Miuarah from Vesuvius . . . DATHE (E.).Amphibolite from Habendorf, in Sileeia . RAMMELSBERQ (C.). Chemical Nature of Tourmaline . KALB (G. W.). Composition of Tourmaline. . . KOCH (M.1. Peridotite from the Harz . . . Preparation of Artificial Molybdenite Flinkite and Heliophpllite from Sn eden . . . . . . . . . . . . . . . . . . . . . . . . BBOQC~ER (W. C.) and H. BACKSTR~M. Mineralsof the Garnet Group KNOP (A.). SICKENBERQER (E.). Natural Cement from Cairo . . . . IDDINCIS (J. P.). Obsidian Cliff. Yellowstone Park . . . . Minerals and Rocks in the Diamond Fields of South Africa OSANN (,(.). Eruptive Rocks of the Cabo de Gttta . . . WEINSCHENE (E.). Meteoric Iron frorn Magure, Arva, Hungary DANA (E. S.) and H. L. WELLS. Selenium and Tellurium Minerals from Honduras . . . . . . . . . . . . BRCQEEEEL (H.) and H.MOISSAN. Fluorspar from Quinci6 . . . ROBERTSON (J. D.). New Variety of Zinc Sulphide . . . . . GmTrf (F. A.). Tetmdymite, I-ron Pyrites, Quartz Pseudomorphs, Scapo. 1it.e) Alhnite, &c. . . . . . . . . . . . FREMY (E.) and A. VERNEUIL. Synthesis of Rubies . . . . . I)ODLEY (W. L.). Curious Occurrence of Vivianite . . . . . MARKOVNIKOPF (V,). Dihydrothenardite . . . . . . . YENFIELD (8. L.). Connellite from Cornwall . . . . . . ~ ~ O O R E (‘l‘.). Nickel Ore from New Caledonia . . . . . . KEMP (J. F.). Minerals from Port Henry, New York. . . . . IDDINQS (J. P.) and S. L. PENFIELD. Fayalite in the Obsidian of Lipari . VENABLE (F. P.). TwoNew Meteoric Irons . . . . . . JOHNSTON-LAYIS (H. J.). Celestine containing Free Sulphur . . . ... xu1 PAQE 1426 1426 1427 1429 1429 1329 1430 1430 1431 1431 1431 1432 1433 1433 20 20 20 20 21 21 22 22 23 24 24 % 26 25 26 a6 26 27 153 188 154 164 156 156 156 157 157 158 158 1.59 272MOPBISON (W.).Elaterite from Ross-shire . . . . . MACADAM (I.). Analyses of Vmious Minerals . . . . HEDDCE (M. F.). Identity of Bruiachite and Fluorapar . . MIEBS (H. A.). Pyrargyrite and Proustite . . . . . PENFIELD (5. L.). Crystals of Copper Pyrites . . . . MELVILLE (W. H.). Metacinnabarite from California. . . CHESTEB (A. H.). Mangano-magnesian Magnetite . . . KINCH (E.). Dufrenite from Cornwall. . . . . . GENTH (F. A.) and S. L. PENFIELD. Ferric Sulphates from Chili UENTH (F. A.). Picropharmacolite, Pit,ticite, and Gibbsite . . HEDDLE (M. F.). Dudgeonite, Hydroplumbite, and Plumbonacrite JACQUEMIN (E.).Silicate containing Copper and Silver . . TEALL (J. J. H.). Minerals from the Lizard . . . . PIBESON (L. V.). Mordenite . . . . . . HOLLAND (T. H.). Large Borphvritic Crvstals of Felspar . . JUDD (J. W.). Conversion of a Felspar into a Scapolite . . MALLET (J. W.). Occurrence of Silver i n Volcanic Dust . . HOWELT. (E. E.). Two new Iron Meteorites. . . . . KUNZ (U. F.). Five new American Meteorites . . . . LIVE~BIDQE (A.). Australian Meteorites . . . . . L'H~TE (L.). . LIVERBIDQE ( A.). Hot Spring Waters. . . . . . FLINK ((3.). Pinakiolite and Trimerite, new Swedish Minerals . DE SCHULTEN (A.). Synthesis of Kttinite and Tachhydrite . . DABAPSICY (L.). Castanite . . . . . . . . TRAUBE (H.). The Proportion of Molybdenum in Scheelite . WILTJAMB (J.F.). Mangahopectolite. . . . . . IGELSTRON (L. J.). Identity of Violan and Anthocroite . . GOGUEL (H.). Chrvmtile from the Pvrenees . . . . GONNARD (F.). Offr&ite, a new Minim1 . . . . . LACROIX (A.). French Minerals . . . . . . . WWLFINQ (E. A.). Kryokonite . . . . . . . SELLA (A). Kative Nickel in River Sand . . . . . STPUEVEB ((3.). Brookite from Beura (Ossola) . . . . Mineral Water of Penon de 10s Banos, Mexico BROWNING'(P: E.). OEBBEKE. Kreittonite from Bodenmais . . . . . . HILIEBBAND (W. F.). Occurrence of Nitrogen in Uraninite . . LUEDECKE (0.). New Borate from Stassfurt . . . . . MILCH (L.). New Borate from Stassfurt . . . . . . KLEMENT (C.). Apatite, Chlorite, and Mica from Belgian Localities . MAB (F. W.), So-called Perofskite from Magnet, Cove, Arkansas .Rhodochrosite frob Franklin Furnace, New Jersey CLAR~E (F. 'W.) and E. A. SCHNEIDER. WILLIAMB (J. F.). PENFIELD (S. L.). Anthophyllite from Franklin, North Carolina . PIPSSON (L. V.). Fowlerite, Variety of Rhodonite from New Jersey . PENFIELD (5. L.). Beryllium Minerals from Chlorado . . . SCHWPFER (R.). Composition of Mica and Chlorite . . . . RAMSAY (W.). Nepheline-syenite of the Kola Peninsala . , . RUNTIN~TON (0. We). New Meteoric Iron from North Dakota. . SIEMASCRKO (J. v.1. Meteorite of Ochanek . . . . . . Conkitution of Natural Silicates. Eudialyte and Eucolite from Magnet Cove, Arkansas . LEDOW (A. R.). Pipe Creek Meteorite . . . . . . TROTTABELLI ((3.). Meteorite from Collescipoli . . . . . JANNE~AZ (E.). Native Silver and Dioptase from the French Congo.HABBINQTON (B. J.). Uoethite, Serpentine, and Qarnet from Canacla KOZOVSKI (N.). Manganese Ores of Transcaucaeia . . . . EOZOVSEI (N.). Manganese Ore in Ekaterinoslav . . . . FOIJLLON (H. v.). Breunnerite and Bloedite from Hall, in the Tyrol , FHIEDEL (U.). Melanophlogite . . . . . . . . ABZEUNI (A.) and A. FRENZEL. Ferron&rite . . . . . WBNJTKOFF (P.). Eutaxitic Glasses of the Lipnrites . . . . PAGE 272 272 273 273 273 273 274 274 274 275 275 276 276 276 276 277 277 277 278 279 279 280 4434 405 405 406 p07 4( r7 407 mi 405 a 8 526 527 527 527 527 528 528 528 529 529 529 529 530 530 530 531 531 532 532 533 647 647 647 648 648 648 649 . 64.9CONTENTS . xv SCHNEIDER (C.). Basaltic Hornblondes . . . . . . . KNOP (A.). Undetermined Silicates from the Kaiserstulil .. . . KEKNGOTT (A.). Composition cd Idocrase . . . . . . . TOUT (J . H . I,.). Composition of Slags . . . . . . . SAKDBERGER (B'. v.). Lithionite-granites . . . . . . . JOHN (C . v.). . . . . LATTEBMANN ((3.). The Lautenthal Brine Spring . . . . . PENPIELD (8 . L.). Aurichalcite . . . . . . . . . MELVILLE (W . H.). .Powellite, a New Mineral Speciee HEADDEN (W . P.). Columhite and Tantalite from the Black Hiils of South Dacota . . . . . . . . . . . . . CHROUSTCHOPP (K.). Artificial Formation of Amphibole . . . . BECK (R.) and W . LUZI . Formation of Graphite by Contact Meta- morphosis . . . . . . . . . . . LORENZ ((3.). Action of Dry Hydrogen Sulphide on Metals : Synthesis oi Minerals . . . . . . . . . . . . . MEUNIER (S.). Artificial Formation of Daubreelite .. . . . MEUNIEB (S.). Artificial Production of Hplite at the Ordinary Tempera- ture . . . . . . . OTTO (R.) and J . H . KLOOS . Artkcial Periclm, a Produc't of h e Magne: sium Chloride Industry . . . . . . . . . . PEMBERTON (H., Jim.). Chromite . . . . . . . . FARRINGTON (0 . C.). Cryetalhsed Aznrite from Arizona . . . . WHEELER (H . A.}. Ferrogoslarite. a New Variety of Zinc Sulphato . . BAILEY (E . H . S.). Halotrichite from Colorado . . . . . . WELLS (H . L.). Occurrence of Pollucite a t Hebron, Maine . . . DE LANDEBO (C . F.). Pink Groesularite from Mexico . . . . DERBY (0 . A.). Occurrence of Xenotime as an Accessory Constituent of Rock8 . . . . . . . . . . . . . DERBY (0 . A.). Magnetite Ore Districts in Brazil . . . . . BUCHANAN (J .Y.). Occurrence of Sulphur in Marine Mud8 and Nodules, and its B~ariiig on their Mode of Formation . . . . . . IRVINE (R.) nd W . S . ANDERBON . Action of Metallic and other Salts on Calcium Car'>onate . . . . . . . . . . . IRV~NE (R.) I nd J . GtILBON . Manganese Deposits in Marine Muds . . BTJCHANAN (J . Y.). Composition of some Deep Sea Deposits from the Medi- terranean . . . . . . . . . . . . MURRAY (J.) and R . IRVINE . Silica and the Siliceous Remains of Organ- ismsin Modern Seaa . . . . . . . . LASPBYREB (H.). Sychnodymite: A New Gobalt Ore . . . . . LABPEYRES (H.). Eorynite from Silesia . . . . . . . SANDBERGER (F . v.). Falkenhynite from Joachimsthal . . . . GEXTH (F . A.). (3ahnite and Columbite from Delaware Co., Pennsylvania . BLOMBTRAND (C . W.).Monazite from Sweden . . . . . . FLINK ((3.). Ochrolite from Pajsberg . . . . . . . . KENNGOTT (A.). Formula of Axinite . . . . . . . . PETERSSON (W.). GadoLinita and Holmite . . . . . . . MULLER (W.}. Garnet from Kedabek, in Caucasia . . . . . HYLAND (J . S.). Mesolite from Co . Antrim . . . . . . SCHMIDT (A.). Zircon . . . . . . . . . . . HYLAND (J.,S.). Spherulitic Rocks from Co . Down . . . . . GENTH (F . 8.) Bguilarite, a New Species . . . . . . . CROSS (W.). Alunite and Diaspore from Colorado . . . . . BLAKE (W . P.). Columbite of the Black Hills, Dakota SOLTMANN (R.). Melanite from the Ktliserstuhl . . . . . . Rocks of the Eruptive Mass of Jablonica LASPEYRES (H.). Kallilite : A New Nickel Ore . . . . . . (XENTR (F. A.). Seleniferous Bisumthinite and Gusnaiuatite .. . HEADDBN (W . P.). . . . HIDDEN (W . E.) and J . B . MACKINTOSH . Polycrase of North and South Cruolina . . . . . . . . . . . . . Griphite, a New Phosphate from Dakota . . . PAGE 649 650 651 651 651 662 652 652 886 886 886 887 989 990 990 991 991 992 992 992 993 993 993 993 994 994 995 995 995 995 1167 1167 1167 1167 1168 1168 1168 1168 1168 1169 1169 1169 1169 1327 1328 1328 1328 1329 1329xvi OONTENTS . GEKTH (F . A.). S . N . PRNFIELD. and L . V . PIBSSON . Axinite. Eudialyte. Titanite. and Monticellite . . . . . . . . . DAUBRSE and S . MEUNIEB . Native Iron oE Terrestrial Origin from Berezowsk . . . . . . . . . . . . CAUARD (E.). Fornintion of Natural Sulphides . . . . . . NEUBERT (E . W.) and F . KOLLBECK . Iron Pyrites containing Nickel and Cobalt .. . . . . . . . . . . . ELOCKMANN (F.). Eukairite. Umangite. and Luzonite from the Argentine . IQELSTROM (L . J.). Plumboferrite. a New Swediah Mineral . . . HILLEBRAND (W . F.). Mineralogical Notes . Autlerite . . . . CESARO (G.). Barytes from Rumelange . . . . . . . SCHULZE (H.). Minerals from Tarapack . . . . . . . BACESTROM (H.). Place of LLngbanite in the Mineral System . . . DE GRAMONT (A.). Artificial Datholite . . . . . . . HOLST (N . 0.). Rhyolites from Sweden . . . . . . . GOLLEB (E.). Oligoclase and Biotite from Gailbach . . . . . JANNETAZ (E.). Wernerite from Chili . . . . . . . . TENNE (C . A.). Sigterite and Albite from Sigtera . . . . . MATTIROLO (E.). Natrolite of Montecatini . . . . . . . NEQEI (G . B.). Natrolite . . . . . . . . .. KOCR (F.). Amorphous Minerals from Budapest . . . . . CHROUBTCHOFF (K . v.). Artificial Hornblende . . . . . . BAUER (M.). The Basalt of the Stempel, near Marburg . . . . WOLFP (H.) Basaltic Rocks of €lessen . . . . . . . RUPPRECHT ((3.). Rocks and Minerals from Corsica . . . . KELLER (H . F.) and A . C . LANE . Chlorit. oid from Champion. Michigan . WILLM (E.). Chalybeate Waters containing Free Sulphuric Acid . . Organic Chemistry . BERTHELOT . VABET (R.). Combination of Mercuric Cyanide with Litluum Salts . . SEMMLER (F . W.). Indian Geranium Oil: Oxidation of Geraniol . . SWOBODA (E.) aud W . FOSSEK . Dihyclric Alcohols derived from Isobut- aldeh de . . . . . . . . . . . . S r m a m (E.) and E . ScHuLzE . Arabinose derived from Wheat Bran and Rye Bran . . .. . . . . . . . . HANTZSCH (A.) and A . WERNER . Stercochemical Isomerides of Nitrogen Compounds . . . . . . . . . . . . HANTZSCH (A.). Attempts to Prepare Stereochemical Isomerides of Condensation of Acetylene by the Silent Discharge . . . . PABENTI (C.). Ethylene Dithiocyanate . . . . . . . CoMBEs (A.). Diacetylcarbinyl Acetate . . . . . . . FISCF~EB YE.) and 0 . PILOTY . Sugars Derived from Rhamnose . . . SCHEIBLEB (C.) and H . MITTELMEIER . Starch . . . . . . Nitrogen Compounds . . . . . . . . . . SFELIG (E.). Displacement. of Hdogens by the Amido-group . . . MALBOT (H . ). Isobutylsmine . . . . . . . . . YINNER (A.). Action of Secondary Amines on Imido-Ethers . . . LEDERRR (L.). fbBromopropaldehgde and B-Bromopropionic Acid . . JORANNY ((3.). Action of Hydrocyanic Acid on Unsaturated Aldehydes . CUBTIUS (T.) and H .SCHULZ . Molecular Weight of Glyuocine and ite Anhydride . . . . . . . . . . . . MAUTHNER (J.) and W . SUIDA . Glycocine . . . . . . . CURTIUB (T.). Constitution of Diazo-fatty Acids . . . . . KRAFT (F.). Synthesis with Ethyl Sodiocarbanmte . . . . . BARTHE (L.). Ethyl Allylcyanosuccinrlte . . . . . . . FITTIQ (R.). Action of Bromine on Angelic and Malek Acids . . . BOUVEAULT (L.). Syntheses of Pu’itriles and of the /%Ketonic Ethers . . BARTHE (L.). Methyl Cpnosucciiiate and Cynnotricarballylate . . . PAQB 1329 14!34 143 1. 1435 1435 1435 1455 1436 1436 1436 1437 1437 1437 1438 1438 1438 1438 1438 14.39 1439 1440 14-40 14 10 1440 28 25 29 29 30 31 31 33 33 34 35 36 36 37 37 37 38 38 39 39 41 42 42 43CONTENTS .xvii PAQB WELD (F.), J . B . LINDSAY. W . SCHNELLE. and B . TOLLENS . The so-caIled Sulphite Liquor. and the Rotation of Gluconic. Glalactonic. and Rhamn- onic Acids . . . . . . . . . . . . CLAUS (A.). Constitution of Benzene and Naphthalene . . . . SBPEK (0.). Substitution in Aromatic Hydrocarbons . . . . SCELIFY (F.). Derivatives of Orthodibromobenzene . . . . . Hydroeiilphides . . . . . . . . . . . WIDUN (0.). . FUCES (J?.). Behaviour of Phenols and Hydroxy-acids towards the Alkali MAZZARA (G.). Constitution of Thymol and Cymene Derivatives . . MAZZABA ((3.). Constitution of Thymoquinone and Carvacrol Derivatives . CAUSSE (H.) Action of Chloral on Redorcinol and of Aldehyde on Yyro- gallol . . . . . . . . . . . . . HINSBEBQ (0.). Formation of Ethereal Salts and Amidea in Presence of Water and Alkali .. . . . . . . . . . REBUPFAT (0.). Action of Aniline on Chloracetic Acid . . . . HANTZSCH (A.). Condensation Products of Aromatic Aldehydes with Aromatic Amines . . . . . . . . . . . TIEMAXN (F.). Orthohydroxybenzjlamine . . . . . . . KBAFT (F.). Possibility of Existence of an Asymmetrical Nitrogen Atom . HOUVEAULT (L.). Action of Amineaof the Benzene Series and of Phenyl- hydrazine on Ketonic Nitriles . . . . . . . . CHELMICKI (S.) . Carbonylorthamidophenol and Thioavborthamidophenol . SIEIDEL ( P.) . Derivatives of Carbonylorthamidophenol and of Thiocarborth- amidopnenol . . . . . . . . . . . . CURTIUS (T.). Action of Alkalis on Acid Salts of Diazobenzene: Ethyl Diazobenzoate . . . . . . . . . . . Change of.Propyl into Isopropyl in the Cumene Series KNOEVENAQEL (E.). Prepmtion of Anhydrous Diazo-salts .. . CURTIUS (T.). Hydrogen Nitride (Azoimide) . . . . . . PICTET (A.). Action of Acid Chlorides on Acid Amides . . . . CURTIUS (l’.). Action of Sodium on Acid Amides . . . . . PINNEB (A.) . Uiphenjloxycyauidine . . . . . . . . PUBGOTTI A.). a-l’oluamideand ib Derivatives . . . . . PINNEB (A!) . Conyersion of Nifriles into Imido-ethers . . . . PINNER (A.). Amidines . . . . . . . . . . PINNER (A.). Action of Benzamidiue on the Ethereal Salte of Aromatic Orthohydroxy -acids . . . . . . . . . . HOLLEYANN (A . F.). Compounds containing the Group C2N20, . . OSTERSETZEB (0.). Compounds of Phthalimide with Phenols . . . EICHENG~EUN (A.) and A . EINHOBN . Dihydrobenzaldehyde .. . HANTZSCH (A.). Stereochemical Isomerides of Pamtolyl Phengl Ketone . WIDMAN (0.). Constitution of Cumenylpropionic Acid . . . . QUENDA (E.). Metliy1resorc:inolphthaloylic Acid . . . . . . BOTTINQEB (C.). Gallic Acid. Tannin. and Oak Tennic Acids . . . BOTTINGEB ((2.). Actionof Phenylhgdrazine on Tannin Extracts . . VILLON (A.), ManufLtcture of Decoloriaed Tannins . . . . . ANSCAWTZ (R.) and P . BEIDIX . Diphenylsuccinic Acids . . . . ANSCHUTZ (R.). Identity of Pyranilpyrok&dxme and Citraconanil . . HAUSSEB (J.). Paranitro-orthotoluenesulphonic Acid . . . . . WISCHIN (R.). Metaxylenedisulphonic Acid . . . . . . MICHAELIS (A.) and E . GODCHAUX . Action of Thionpl Chloride on Secondary Aromatic Amines . . . . . . . . . LEDEBEB (L.). New Synthesis of Indigo .. . . . . . HEUMBNN (K.). Synthesis of Indigo and Allied Dyes . . . . . HERZLG (J.) and S . ZEISEL . Dearnotropy in Phenols . . . . . REBUFFAT (0.). Diphenyldiethjlene Derivatives . . . . . OQLI~LORO (A) . Synthesis of Benzylcinnamic Acid . . . . . PINNRR (A.). Imido-ethers . . . . . . . . . REBUFFAT (0.) . Perkin’a Reaction . . . . . . . . BAUCEJ (C.). Iodometaxylenesulyhonic Acid . . . . . . VOL . LX . I 48 44 44 44 -45 46 443 47 48 49 to 60 60 61 61 62 63 5.E 66 66 67 68 59 59 69 t10 60 61 64 65 65 68 69 69 70 70 510 70 71 78 73 73 73 74 75 75 75 76 76x ~ i i CONTENTS . ERAFFT (F.) and E . BOUBWEOIS . Naphthyl Sulphides . . . . HIRSCH (R.) and F . KALCKHOFF . Action of Aromatic Bases on Naphthol- Violet . . . . . . . . . . AMTHOR (C.) and G . MULLER . Dry Distillation of Terpenylic Acid .. EKSTRAND (i . (3.). Naphthoic A'cids . . . . . . . . HEUSER (A.) and C . STOEHR . Methyldipyridyls . . . . . 8TOEHR (c.). u-picoline and a-Isobutyleneyyridine . . . . . LOCHEBT (H.). Diethylmuscarinepyridine . . . . . . . C u u s (A.) and P . HEERMANN . Tribromoquinolines . . . . . CARLIER (E.) and A . EINHORN . 2'-Quinolylacetaldehyde . . . . EBauss (K.) . Papaveroline . . . . . . . . . . STOEHR (0.). Strychnine . . . . . . . . . . BEREND (L.) and C . STOERB . Brucine . . . . . . . PEHKSCHEN (C.). Alkaloi'ds of Vemtmm album . . . . . hjdro uinoline, and Pyridine . . . . . . . . LUBBE (A.). Aconitine . . . . . . . . . . FBEIJND (M.) and M . HEIM . Hydrnstine . . . . . . . FREIJND (M.) and A . PHILIPS . Hgdrastine . . . .. . . JAHNS (E.). Alkalo'ids of the Areca Nut . . . . . . . Action of Sulphurous Anhydride on Flour . . . . . DHECHSEL (E.). Formation of Carbamide from Albumin . . . . DEHOFF (t . H.). Nitro- and Chloro-derivatives of @-Methy1-8-oxyquinazo- line . . . . . . . . . . . . . LELLMANN (E.) and H . PEKRUN . Benzyl Derivatives of Piperidine, Tetra- EINHORN TA.) . Tropidine . . . . . . . . . . EICHENBUN (A.) and A . EINHOBN . Hydrobromanhydroecgonine . . BALLAND . GnsTAvsoN (G.). Action of Chlorine on Trimethylene . . . . EBMYANOFF (N.). Hexylene Dibromide obtained from Diallyl . . . VOLHARD (J.). Oxidation of Potassium Cyanide with Potassium Perman- ganate . . . . . . . . . . . . . 'VARET (R.). . HELL (C.) and 51 . WILDEBMANN . Action of Alcoholic Potassium Cyanide . .. . . . . ICRUQER (R.). Derivatives of Melidoacetic Acid . . . . . . EIJNER (S . N.). Action of Hydrogen Chloride and Bromide on Ethyl Ally1 Ether . . . . . . . . . . . . DEKKERS (P . J.). Tetramethylene Glycol . . . . . . . MALBOT (H.) and A . MALBOT . Isopropylaminee . . . . . . SIMON-THOMAS (J . C . A.). Propylnitramine and Isopropylnitramiue . . HOFMANN (A . W . v.). Diethylenediamine . . . . . . . REPORMATSKY (S.). Action of Zinc and Ethyl Chloracetste on Ketones and Aldeh des . . . . . . . . . . . BOTHAMLEY (8 . H.) and G . R . THOMPSON . Action of Phosphorud Tri- chloride on Organic Acids and Water . . . . . . . KLIMBNKO (E.). Paracrylic and Hyttracrylic Acids . . . . . AUTENRIETH (W.). fl-Chlorocrotonic Acids . . . . . . ELION (H.). Preparation and Properties of Ethyl Sodacetoacetate and Ethyl Sodethylacetaacetate .. . . . . . . . HALLER (A.) and A . HELD . y-Cyanoacetoacetates . . . . . ANSCHUTZ (R.), P . BENDIX, and W . KERP . Meaitene Lactone and IEO- TANATAB (S.). Action of Methylen;! Iockrie and Chlorine on Ethyi Malonate . . . . . . . . . . . . TANATAB @.\. Reaction between Methvlene Iodide and Ethvl Malonate . Combination of Mercuric Cyanide with Cadmium Salts . on Halogen Derivatives of Amylene EERTONI (G.). Two New Butyl Nitrates . . . . . . . ZIJLKOWSEI (K.). Starch . . . . . . . . . . VESTERBERQ (A.). 4- and fl-dmyrin . . . . . . . . BERG (A.). Amylamines . . . . . . . . . . dehydracetic Acid . . . . . . EZBDA (R.) ahd J . WIEDEMANN . Succi&mic Acid . . . . . . YIGTTI (A.). Spthesie of Asparagine .. . . . . . . 175 76 77 77 79 80 81 82 82 83 84 t15 86 87 87 88 90 91 92 93 94 94 95 93 159 160 160 161 161 162 163 164 164 166 165 166 167 169 169 169 170 170 170 171 172 174 175 175COXTENTS. Xi x PAGE 171; 177 1 i 7 178 178 178 179 180 181 182 183 184 1s4 185 1P6 186 I F 6 I R E lb9 189 190 192 193 193 195 193 196 198 198 200 200 200 202 202 203 203 204 205 206 206 206 207 208 2u8 209 2 10 211 AYSCHUTZ (R.). TAKAT.AR (S.) and C. TCHELETIEFF. RALLER (A,) and A. HELD. Synthesis of Citric Acid. , KLIXPNXO (E.) and BLTCHSTAB. Amic and Anilic Acids of Fumaric Acid and Male'ic Acid. Dikactylic Acids . . . . . Action of Phosphoric Chloride on 'Citric A s s c ~ ti TZ (R.) . Dig1 ycollic Anh Sdride . . . . . . . and Aconitic Acids . . . . G~THZEIT (M.) and 0. DRESSEL.A l k ~ l Deriraiives bf Eihgl Dicarbony: glutaconate : Kew Spt,hesis of aa-Dialkylglutaric Acids . . , KLBSOS (P.). Thiocarbimidoacetic Bcid and Thiohrdantoh . . . STCFFER'(E.). Hydrolysis of Yulplioues . . " . . . . Meta- and Para-ethilisopropylbenzene . . . . &IARCKWALD (W.). GT-STATSON (G.). AcLion of Acid Chlorides on B a s e im Presence of Alkalis . . . . . . . . . . Ratibnale'of Reactions in the Presence of Alnminium Chloride and Bromide . . . . . . . . . UHLHORX (E.). Diisopropylbenzene . . . . . . . Kosova~ors (I,), Nononaphthane and its Deriratires . . . . MARKOVNIKOFF (V.). Caucasian Petroleum . . . . . TASSINAEI [G.), Action of Thionyl Chloride on the Phenols . . . STLTFFER ( E , ) , Condensation Products of Glposal and some Mercaptans . MAZZARA ((3,).Constitution of Thymol and Carracrol Deriratires . . XIETZKI (R.). Constitution of Rhodizonic Acid . . . . . WALLACK (0.). Replacement of the Hydrogen Atoms in the Methylene BECKE (P. v. D.). STAEDEL (W.) and A. KOLB. Xitronietacresols . . . . . . Group . . . . . . . . I . . MISEXXI (G,). Action of Paratoluidine and Aniiine on Phloroglucinol . KIETLKI (R.) and R. ROSEL. Tetramidotoluene . . . . . . GOLDSCRXIDT (H.) . Diazo-compounds . . . . . . . BECKMASX (E,). Aldoximes . . . . . . . . . TRA~TMANN (E.). Dyes of the Primuline Group . . . . . ECEENROTH (H.) and 8. DOKNER. Parachloracetotolu'idide and Metapara- nitrochloracetotoluidide . . . . . . . . . . Action of Potassium Hvpobromite HOOGEWEREF (S.) and W. A. PAX DORP. .- on Phenylsuccinimide . . .. . . . . . . ROTRSCHILD (F. W.). Carbamide Deriratires of dmidocinnamic Acid . CLACS ( A , ) . Alkyl Aromatic Ketones . . . . . . . . ERLEXNEYER (E,). ConverRion of Cinnamic into Isocinnainic Acid . . HEILXASN (E,). Metax~.lalphthalide . . . . . . . . HEDIX (S. (3.). Condensation Products of Amido-acids with Benzene- sulphonic Chloride . . . . . . . . . . . AUTENHIETH (W.). Benzenesulphinic Acid and Ethrlsulphinic Acid . . AUTENRIETR ( W , ) . Sulphone Derivatires of the Crdtonic Acids . . . AUTESRIETH (W.). Sulphur Deriratire s of Ethyl Auetoacetate, Ethyl linAElrIER (G.) and A. SPILEER. . HEUMINK (K.). Synthesis of Indigo with Phenylglycocine. . . . BIEDERMANX (A.) and R. LEPETIT. Synthesis of Indigo from Anilidoacetic Acid . . . . . . . . . . . . XRAEMER (G:) and A SPILKER.Condensation of Cinnamene with Methyl- benzene Derivatives . . . . . . . . . . XRAEMER (G.), A. SPILKER, and P. EBERHARDT. Cinnamene Derivatives of Sromatic Hydrocarbons and their Conversion into Anthracene . . REYSE (P.). Condensation Products of Paranitrobenzyl Cyanide. . . KOENIGS ( W.), Condensation of Cns<iturated Hydrocarbons with Phenols . KOELTIKQ (E.) and P. WERNER. Diphenyl Derivatives from Alkylh>-droqtiin- GCENEZ (R,). Benzoic Fluoride . . . . . . . . . BOTTINGER ((3,). Isogallic Acid Phenvlhydrazide . . . . . Methylacetoacetate, and Ethyl Ethylacetoacetate . . . . Indene and Cinnamene in Coai Tar , . . - oncs . . . . . . . . . . . . . HIRSCH (R,). Ortliomethylbenzidine . . . . . . . . NOELT'IBG (E.) and P. WEHA-ER. Diphenyl Bases .. . . . b 2xx COXTENTS. PAGB OGLIAL~~O (A.) and E. RO~SINI. Phenylhydrocarbostyril . . . . . . . 214 CLAWS (A.) and H. TEBSTEEGEN. Naphthyi Meihyl Ketones . . . 214 BEBNTHSEN (A.). amidosulphonic Acids . . . . . . . . . . 216 WEBSCHEIDER (R.). Dinaphthyl Picrates . . . . . . . 216 PICTET (A.) and t3. ERLICII. Chrysidines . . . . . . . 216 DUNWODY (R. G.). Turpentine . . . . . . . . . 217 WALLACH (0.). Terpenes and Ethereal Oils . . . . . . 217 WALLACH (0.) and F. HARTMANN. Fenchole, an Isomeride of Camphor . 218 MARKOVNIKOFF (V.). Rose Oil . . . . . . . . . 219 STOERP (C.). 15-Methylpyridine . . . . . . . . . 219 BIZZAPBI (D.). New Class of Acridines : Phenylearbazaci4dine . . . 219 HUBACHRB (K.). Thiazoles . . . . . . . . . . 220 ROUBLEPF (T.). Trimethylthiazole, Methylethglthiazole, and Thitrzolecarb- oxylic Acids .. . . . . . . . . . . 223 WORMANN (M,). Diazo-compounds of the Thiazole Series . . . . 225 TAUBEE (E,). Synthesis of a Diamidocarbazole from Benzidine . . . 227 EAUDER (E.). Tritopine and other rare Opium Bases . . . , . 227 HESSE (0.). Atropamim . . . . . . . . . . 228 SCHMIDT {E.). Root Constit.uenta of Scopolia atropoldes . . . . 228 ~ S L L E (F.). Alkalo’ids of Chelidoniurn majus . . . . . . 229 ~ALZBERGER ((3.). Alkaloids of the Rhizome of reratrum album . . 230 PARTEIEIL (A.). Cytisine . . . . . . . . . 231 KLUG (F.). Products of the Artificial’Digestion of Glue . . . . 238 OUPE (P. A.). Active Amy1 DerivatiTes . . . . . . . 281 CHABRI~ ((2.). Hydrolj sis of Halogen Carbon Compounds . . . . 28L COUTURIER (F.).8-Dipropylene . . . . . . . . . 282 SCHOL’L (R.). Constitutio; of Fulminic Acid . . . . . . 282 FARNSTEINEB (K.). tory Power of Cane-sugar . . . . . . . . . 283 SCHE~BLER (C.) and H. M ITTELYEIER. Starch . . . . . . 284 LIPPMANN (E. 0. v.). Gummy Exudation from the Sugar Beet. . . 284 MALBOT (€I.). Diisobutylainine Ethyl Oxalate . . . . . . 284 NEWBTJPY (5. 3.) and M. W. BAPNUM. Action of Propaldehyde on Alcohols. . . . . . . . . . . . . 284 NEWBURY (S. B.) and E. M. CHAMOT. Action of Alcohols on Acralde- hyde . . . . . . . . . . . 285 NEWDUNY (S. B.) and W. 5 . CALKIK. Action of Alcohul on Crotonaldehyde 285 DODGE (17. D.). The Indian Grass Oils . . . . . 285 NEWBURY (S. B.) and W. R. ORNDORFF. Action of Dilu& Nitric Acid on Acetone. . .. . . . . . . . . , 287 ~ C H O L L (R.). Action of Hydroxylamine on Isonitrosoketones . . . 287 SCHMITT (R.). Formation of Zinc Propionate by thc Action of Carboriic Anhydride on Zinc Ethide . . . . . . . . , 288 MARIE (T.). Preparation of Cerofic Acid . . . . . . . 288 OTTO (R.) and W. OTTO. ’ Formation of Ethereal Salts bs means of Ethyl Ch lorocarbonate . . . . . . . . . . . 288 BISCHOFF (c. A.) and K. JAUNGNJCEER. Piinelk Acids . . . . 289 BISCHOFF (C. A.) and N. MIN’TZ. Ethgldimethjlsuccinic Acid . . . 290 Anwms (K.) and J. A. GARDNEP. Tetramethylsuccinic Acid . . . 290 BISCHOFF (C. A ). Homologues of Male’ic Acid . . . . . 291 GEBNEZ (D.). Combinations of Mulic Acid with Alkali Moiybdates . . 291 BISCHOFF (C. A.). Etliyl ~sobutenylt,ricarhoxylate . . . . .292 KLOBBIE (E. A.). Action of Nitrous Acid on Amido-derivatives . . 292 THIEPFELDEE (H.). 294 ZEKONI (M.). Action of Methyl Iodide on Furfuryllimine . . . . 294 SCHOTTHN (C.). 295 ZENONI (M.). Ppomucic and Dehjdromucic Acids . . . . . B.5 SC~OPFP (M.). Broniobenzonitriles . . . . . , . . 295 Ortlionitrophenylcinnamic Acid and Naphthasultonsulphonic Acids and a-Naphtholsulphnn- Actioh of certain Inorganic Salts on the Specific Rota- Reduction of Glycuronic Acid by Sodium Amalgam . Action of Acid Chlorides on Bases in Presence of Alkalis .CONTENTS . xxi PAGB BIC~INELLI (P.). Action of Methylchlomfm on Phenol in PreRence of Potash and Soda . . . . . . . . . . . MAZZARA ((3.). Constitution of Thymoquinones and B-Hydroxythymoquin- one Derivatives . . . . . . .. . . KEHRMANN (F.) and J . MESSINQER . Thymoquinonedioxime . . . Action of Phosphorus Pentschloride on Hydroxys zobenzene . . . . . . . . . . KRAUSE (A . ). Isomeric Forms of Ortllonitrophenylglyoxylic Hydrazone . SCH~PFF (M.). Substitution of the Anilido-group for Halogen Atoms in the Benzene Nucleus . . . . . . . . . . GROHNANN (A.). Derivatives of Parabromometanitrobenzoic Acid . . BEIDENSLEBEN (E.). Toluidonitrobenzoic Acid and Naphthykmidonitro- benzoic Acid . . . . . . . . . . . . DENINGER (A.). Nitration of Hydroxybenzoic Acids . . . . . NIBTZEI (R.) and F . RUPPERT . Ortho- and Meta-crcsotic Acid . . . BIGINELLI (P.). Saligeninoryacetic acid . . . . . . . MICHAELIS (A. ) and R . HERZ . Thionjhmines . . . . . . DELISLE (A.) and 0 . IIAGAr . MetetboxyphenylsuIphonic Acid .. . HEUMANN (K.). Synthesis of Indigo and Allied Dyes . . . . . LEDEHER (L.). Synthesis of Indigo from Phenylglycocine . . . . ZATTI (C.) and A . FERBATINI . Action of Methyl Iodide on Hydro-a- WITT (0 . N.1, E . NOLTING, and E . GBANDMOWGIN . Indazole Derivatives . ~ ~ H R A (A.). Derivatives of Benzidinemetasulphonio Acid . . . . DEYUTH (R.) and M . DITTRICH . . SOHOLL (R.). Action of Nitrogen Tetroxide on Aromatic Ketoximes and on HUGOUNENQ (L.) . Tetrachlorophenol . . . . . . . OBEBMULLER (K.). Cholesterol . . . . . . . . . ERNST (0.). Derivatiires of Diphenylamine . . . . . . . RUHL (J.). Thiophenylhydrazine . . . . . . . . . GRIMALDI (S.). Diarnylphenylbydrazone . . . . . . . TAFEL (J.) and A . MAUNITZ . PhenRcyl Sulphide . . . . . . ZEHRA (A.).Metaparadbmidobenzoic Acid . . . . . . . HEUMANN (K.) and R . PAQANINI . rn ethyl indole . . . . . . . . . . . . GUYE (P . A.). Fluorene Hydrides . . . . . . . . Glyoximes . . . . . . . . . . . . DITTRICR (M.). Ethers of Benziloximes . . . . . . . DE NEUPVILLE (R.) and H . v . PECHMANN . Dipbenpltriketone . . . glycollic Acid . . . . . . . . . . . Oximes of Haloid Benzophenones . OGLIALORO (A.) and 0 . E’ORTE . Cresolcinnamic Acid and Metacresol- ONVFROWICZ (S.). Sulphides of &Naphthol . . . . . . SEMMLEE (F . W.). Ethereal Oils of Asafetida . . . . . . SFMMLER (F . W.). Indian Geranium Oil : Geranaldehyde : Geranio Acid . POLECK (T.). and C . ECXART . German and Turkish Rose Oil CAZENEUVE (P.). Phenolic Acid from Camphor . . . . . . BIYRCKER (E.). Action of Camphoric Anhydride on Benzene . .. SCHLEIF (W.). Crystalhe Principle from the Bark of Diospyros vir- giaiam . . . . . . . . . . . . . LADENBURG (A.). 8-Picoline . . . . . . . . . NOELTINQ (E.) and E . TRAUTXAIW . Derivatives of Toluquinoline and Met axy loquinoline . . . . . . . . . . . Condenaation of Metanitrobenzaldehyde with Quin- aldine . . . . . . . . . . . . . . . . RIST (E.). 2-Methglquinaldine . . . . . . . . . RICHARD (B.). ConstiLntion of &Quinaldinesulphonic Acid . . . MAQUENNE . B-Pyrazoledicarboxylic Acid . . . . . . . SCHMIDT (E.) and M . WERNECKB . Caffeidine . . . . . WARTANIAN (W.), DANCKWOETT (W.). Derivatives of Morphine . . . . . . ARNAUD . Cinchonamine . . . . . . . . . . GAZE (R.). Berberine and Hydroberberine . . . . . . . MUSSI (U.).Ecgonine . . . . . . . . . . . 296 297 297 297 298 2w 301 301 502 302 302 303 304 305 306 307 308 309 310 310 311 311 311 312 313 314 314 315 317 3 18 320 320 322 323 323 324 324 324 325 325 329 329 329 330 331 332 332 332 333xxii COXU'TENTS, PAffB MARINO-ZUOO (F.). New Alkalo'id from Chrysanthemum cineruriefoliltm . GRRRARD (A . W.) and W . H . SYMONS . Ulexine and Cytisine . . . GRESHOPF {M.). Alkalo'ids and other Active Principles from Planta grow- B~CHAMP (A.). Coagulation : Preparation of Soluble Case'in . . . Prote'ids of Milk . . . . . . . . Action of Lime on Case'in and on Milk . . . . . CHITTENDEN (R . H.) and E . E . SMITH . Digeetion Products of Gluten- case'in . _. . . . . . . . . . . . CHITTENDEN (R . H.) and J . A . HARTWELL . Crystalline Vitellin and Vitelloees .. . . . . . . . . . . COPEMANN (8 . M.). Crystallieation of HEemoglobin . . . . . BOER (C.). Compounds of Hemoglobin with Carbonic Anhydride . . MESLANS (H.). Ally1 Fluoride . . . . . . . . . COLBP (C . E.) and F . D . DODGE . . PRUD'HOMME . Reactions of Potassium Ferricyanide . . . . . EOLLEMAN (A . F.). Constitution of Fulminic Acid . . . . . SCHOLVIEN (L.). Behaviour of Ethyl Ether with Sulphiiric Acid : Separation . . . . . . . LINDET (L.). Production of Higher Alcohols in Fermentation . . . STONE (W . E.). Penttiglumses (Pentoses) . . . . . . . WILEY (H . W.). Pine-tree Honey-dew and Pine-tree Honey . . . FISCHER (E.). Reduction of Fruit-sugar . . . . . . . FISCHER (E.). Synthesis of a New Gtlucobiose . . . . . . BAIJEE (R . W.).Sugm from the Pectin of Pluins . . . . . MALBOT (H.). Action of Aqueous Ammonia on Isopropyl Iodide and Chloride . . . . . . . . . . . . . SCHULZE (E.) and A . LIKIEBNIK . Preparation of Lecithin from Pltrnt Seeds . . . . . . . . . . . . . HOPVANN (A . W . v.). Ethylene Bases . . . . . . . MA JERT (W.) and A . SCHMIDT . Piperazine . . . . . . HOBMANN (A . W . v.). The Action of Heat on the Hydrochlorides of Ethylene Bases . . . . . . . . . . . LADENBURG (A.). Diethylenediimine (Piperazine) . . . . . CTAISEN (L.) and E . HORI . Action of Hydroxylamine on Acetoacet- aldehyde . . . . . . . . . . . . . WOLFF (L.). Glyoxylpropionic Acid and its Derivatives . . . . EMERY (W . 0.). Actionof Ammonia, Isobutylamine, and Aniline on Ethyl CIAISEN (L.). Coloured Compounds derived from Ethyl Acetonoxalate .EMEBY (W . 0.). Ethyl B- Acetjltricarballylate . . . . . . EMERY (W . 0.). New Synthesis of Tricarballylic Acid and of certain Ethereal Salts . . . . . . . . . . . CLAISEN (L.) and E . HORI . . . . . CLAISEN (L.). Hydrolyeiv of Ethereal Salts of Orgauic Acids by Potassium Acetate . . . . . . . . . . . . CIAISEN (L.). Synthesis of Chelidonic Acid . . . . . . TIEMAN (W.). Oxidation of Gtluconic Acid with Fehling's Solution . . FEANCEIMONT .(A . P . N.) and E . A . KLOBBIE . Actiou of Nitric Acid on Ethyl Methenyltricarboxylate . . . . . . . . FBANCH~MONT (A . P . N.) and E . A . KLOBBIE . Action of Nitric Acid on Methane Di- and Tri-sulphonic Acids . . . . . . . CLAISEN (L.). . ANGELI (A.) and 0 . CIAMICIAN . Oxidation Products of Brominated Thiophens .. . . . . . . . . . . . Conversion of Orthocliloronitrobenzene and Orthobromonitrobenzene into Orthonitranisoil and Orthonit ropbenetoil . ing in the Dutch Indies . . . . . . . . . . HALLIBURTON (TI'.). R~NUER (S.). Action of Nitriles on Organic Acids of Ethyl Ether fmm Ethyl Bromide HAAF (C.). Guanaminee . . . . . . . . . . Acetonedicarboxylate . . . . . . . . . . Synthesis of Aconitic Acid Preparation of Ethereal Salts of Furfurylacrylic Acid . RENAXD (A.). Trithignyl . . . . . . . . . . LOBRY DE BBUYN (C . A.). LOBRY DE BRUYN (C . A . ). Direct Substitution in the Aromatic Series 333 334 334 338 339 34!Q 342 342 343 343 409 409 410 410 410 41 1 411 412 413 412 413 413 413 414 415 415 416 416 416 416 422 422 423 423 424 425 425 426 426 426 427 427 427 420 429CONTENTS .Xxiii LOBRY DE BEIJYN (C . A) . UnsTmmetrical Trinit.robeneene . . . LOBRY DE BRUYN (C . A.). Symhetrical Dinitrophenol . . . . HAHLE (H.). Metanitroparamidophenol and its Derivatives . . . ELss (K.). Quantitative Investigation of Reduction Processes . . . PFRENQEE (M.). Phenol of Birchwood Tar . . . . . . KEERMANN (It.). Constitution of Quinone . . . . . . . LAUTH (C.). Colour Reactions of Aromatic Amines . . . . . MICHAELIS (A.) and A . SCHENK . Action of Phosphorous Chloride on Ter- tiary Aminee . . . . . . . . . . . . HIRSCH (R.). New Synthesis by means of Diazo-compounds . . . REIBSERT (A.) and W . KAYBEB . Action of Phenylhydrazine on a-Hydroxy- acids and their Ethereal Salts . . . . . . . . HANTZSCH (A.). Determination of the Spacial Configuration of Stereo- isomeric Oximes .. . . . . . . . . . HANTZSCH (A.). Configuration of Asymmetrical Oximes which do not form S tereome t ric Isomerides . . . . . . . . . . HANTZSCH (A.). Oximes of Aldehydes and a-Ketonic Acids . . . HOLLEMANN (A . F.) . Constitution of Fulminic Acid : nibenzoylcarbsmide GOLDZWEIG (A.) and A . KAISER . Hydroxyketones from Fatty Acids and Phenols . . . . . . . . . . . . . EEDMANN (H.) and E . SCHWECETEK . Chloro-derivative6 of Benzaldehyde . CLAISEN (L.) and R . STOCK . Action of Hydroxylamine on Benzoylacet- aldehyde . . . . . . . . . . . . . FITTIQ (R.). Intramolecular Change in Uneaturnted Acids . . . . FIBCHER (0.) and L . SIEDER . Orthamidoparditolylamine . . . . HANTZSCH (A.). Stereo-isomeric Ketoximes .. . . . . DIJNSTAN (W . R.) arid 0 . F . C . BLOCH . Artificial Salicylic Acid . . . DOHME (A . R . L.). Cot.tmarone . . . . . . . . . STIEQLITZ (A.). Quinonecarboxylic Acids . . . . . . . HEUMANN (K.). Indigo from Phenylglycocine . . . . . . UELACRE (M.). Constitution of Benzopinacoliae . . . . . . LAWTH (C.). Derivatives of Dimethylaniline . . . . . . XEIST (F.). Dehydrobenzoylacetic Acid . . . . . . . BEIST (F.). Ethyl Diphenylpyronedicarboxylate . . . . . . GAESS (F.). Nitro- and Amido-derivatives of p-Naphthyl Ethyl Ethers . EBEILT (R.) and E . KI,EINER . Naphthylene Dibydrosulphide and Dithio- cyanate . . . . . . . . . . . . . CLAUS (A.) and 0 . PHILIPSON . Halogen Derivatives of Naphthplamine . MINQUIN (J.). Action of Sodium Benzyloxide on Cyanocamphor .. MINQUIN (J.). Action of Cyanocamphor on Sodium Phenoxide and Sodium Nap hthoxide . . . . . . . . . . . . MARKOVNIKOFF (V.). Presence of Ethylene Linkages in Terpenee . . KWASNICK (W.). Kuro-moji Oil . . . . . . . . . WOY (R.). Massoyene . . . . . . . . . . . SEMMLER (F . W.). Ethereal Oils contained in Asafcetida . . . . FLUCKIQER (B . A.) and GISISON . Suberin and Cork Cells . . . . ABCHAN (W.). Derivatives of Homopiperidinic Acid . . . . CLAISEN (L.) m d W . ZEDEL . Phenylisoxazolme . . . . . PINNER (A.). Imido-ethers and their Derivatires . . . . . EICKEE (K.). Phenazines . . . . . . . . . . GRAEBE (C.). Formation of Quinalizarin from Alizarin . . . . BLADIN (J . A.). Oxidation of Phenylmethyltritlzolecltrboxylic Acid : Phanyltriazoledicarboxylic Acid and the Constitution of Pheayltriazole- carboxylic Acid .. . . . . . . . . . PINNER (A.) and R . WOLFFENSTEIN . Nicotine . . . . . . JORISSEN (A.) and L . GEOSJEAN . Solanidine of Potato Sprouts . . . OUDEMANS (A . C.). 1c1 etallic Ueriratives of Cupre'ine. . . . . DECKERS (A.) Hnd A . EINHOBN . Dextrococa'ines . . . . . . Ptomriines formed in the Cultivation of Swine Fever Bacillus . . . . . . . . . . . SCHWEINITZ (E . A . v.). PAa E 429 430 430 431 432 432 433 434 436 437 438 439 442 443 445 446 4.47 448 431 452 454 456 455 456 456 457 458 459 459 4d30 461 463 463 466 464l 464 464 464 465 466 468 468 470 472 473 4-75 474 475 476xxiv CONTENTS . PAGE HARNACK (E.). Egg-albumin free from Ash . . . . . . 476 LORENZ (R.). Compound of Gelatin and Metaphosphoric Acid .. . 477 LIEBEEMANN (L.). Metaphosphoric Acid in the Nucleh of Yeast . . 477 EPFBONT (J.). Action of Hydrofluoric Acid on Diastase . . . . 477 EILOAUT (A.). Relative Motion of Singly Boundcardon Atoms . . . 633 HELL (C.) and M . WILDERMANN . Halogen Derivatives of Amylene (Tri- methylethylene) . . . . . . . . 633 CLAU~ (A.) and F . v . DREDEN . Cetyl hcoh’ol . . . . . . 535 BORNTR~QEB (A.). Inversion of Saccharose by Hydrochloric Acid . . 53s SCHEIBLEB (0.j. Solubility of Sugar in Mixtures of Alcohol and Water . 536 SCFlEIBI.ER (c.) and H . MITTELMEIER . Gtahin . . . . . . 536 LINTNER (C . J.). Action of Potassium Pcrmanganate on Starch . . . 637 MAJERT (W.) and A: SCHMIDT . Spermine . . . . . . . 538 POEHL (A.). Spermme . . . . . . . . . . 538 TIEMANN (F.).Amidoximes and Azorimes . . . . . . . 538 539 AUTENRIETH (W.). Derivatives of Acetal and Acetone . . . . 540 SCHEUBEB.~ESTNER . Turkey Red Oil . . . . . . . . 542 WILL (W.). lose . . . . . . . . . . . . . . 542 EMERY (W . 0.). 544, GERNEZ (D.). dates . . . . . . . . . . . . . 6415 AUWER~ (K.). EMERY (W . 0.). COPEMAN (Y . M.). Myohematin . . . . . . 478 CURATOLO (T.). Methylquanicil and Trimethylguanicil . . . . 539 SEMMLER (F . W.). CLAUS (A.) and 0 . PFEIPPEH . Ieonitrostearic Acid . . . . . 541 Olefinic Constituents of Ethereal Oils . . . . Hydroxypyruric Acid. a Product of Decomposition of Cellu- Action of Ammonia and of Ainines on Ethyl Aceto- Combination of Malic Acid with Alkaline Phosphomolyb- Synthesis of Alkyltricarballglic Acids and other Polycarb- Action of Ethyl p-Bromopropionate on Ethyl Malonate succinate and .its Homologues . . . . . . . . . WIBLICENUS (W.) and M . SCHRLDT . Ethyl Ethoxyoxolacetate . . . 545 and Ethyl Acetoacetate . . . . . . . . . . 547 DULL ((3.). Derivatives of Levuloeecarboxglic Acid . . . . . 547 STORCB (L.). Constitution of Thiocarbamide . . . . . . 648 oxylic Fatty Acids . . . . . . . . . . . 546 AVENABIUS (C.) . carbazidee into Isomeric Bases . . . . . . . . 548 ANSGIELI (A.). Action of Ethyl Oxalate on Acetothibnoiie . . . . 559 LEVI (L . E.). Biophen . . . . . . . . . . 551 NASINI .(I+. ) . by means of their Dispersive Powers . . . . . . . 551 LIEIEBNIK (A.). Lupeol- . . . . . . . . . . 651 SCHREIBER (R.) . Phenoxyethylamine and Paracresoxyethylamine . . E52 HIRSCH (R.). Stability of Diazo-compounds in Aqueous Solution .. 554 HEUSLBR (I!.). Dry Decomposition of Diazoamido-compoands . . . 555 PAGANINI (R.). tives . . . . . . . . . . . . . 556 TIEMANN (F.). Sulphur Derivatives of Amidoximes . . . . . 557 VOLTMER (L.). &mine on Thimrbamides . . . . . . . . . 558 CBAYEN ((3.). Parabromobenzenylamidoxime . . . . . . . . 559 ROCH (H.). Condensation Products from Thiouramidoximea . . . 560 HUTCHINSON (A.). Reduction of Aromatic.Amides . . . . . 561 PUBGOTTI (A.). Nitro- and Amido-derivatives of Phenylacetamide . . 562 NAAR (A.). Derivatives of Cinnamaldehyde . . . . . . . 5f32 CLAUS (A.). Aromatic Alkyl Ketones and their Oxidation . . . . 5641 CLAUS (A.) and W . SCHEULEN . Bromonit. robenzoic Acids . . . . 664 MINUNNI ((3.) and L . CABERTI .New Mode of Formation of Benzoic anhydride . . . . . . . . . . . . 565 Conversion of Alkylthiosinamines and Alkylallylsemithio- Distinction of Ulylbenzene from Propylbenzene Derivatives ODDO ((3.). Diazo-derivatives of the Aromatic Series . . . . . 553 Action of Phosphorus Pentachloride on Oxyazo-deriw- Action of Hydroxylamine. Ethoxylamine, and Benzyloxyl- Action of Carbon Bisulphide on Benzenylamidoxime andCOKTEKTS. XXV PAOB PREY (H.) m d M. HOROWITZ. New Method for obtaining Aromatic Carboxylic Acids . . . . . . . . . . . BIZZARRI (D.). Coumamne . . . . . . . . . . REISSERT (A.). Condensation Products of Anilidoglutaric Acid . . . EKBOM (A.). Metsdinitrodiphenyldisulpliine . . . . . . AUTENRIETH ( W .). Substituted Sulphones . . . . . . . OTTO (R.) and A.mSS1NQ. Phenylsulphonearetonemermptole . . . GBOEQESCU (M.). Benzenesnlphonates of Aromatic hdicles . . . OTTO (R.). Benzenesillphonates of Aromatic Radicle8 . . . . TUAUBB (W.). Aromtttic 9dphonamie Acids . . . . . . TAUBPR (E.). Ortbodinitrodiphenyl and Orthodiamidodiphenyl . . . MAZZARA ((3.). Carbazole . . . . . . . . . . BLANK (A.). Cwbazole Sjnthesie . . . . . . . . KOENIGS (W.). Condensation of Unsaturated Hydrocarbons with Phenols : Tetrahydronaphthylphenol . . . . . . . . . WILLQERODT (C.) and F. Scnnzz. Picryl-a- and B-naphthylhydmzinee, EKBOM. (A.). Action of Hydriodic Acid on 1 : 3’-Nitronaphthalsnesulphon- amide . . . . . . . . . . . . . . CLAISEW (L.). Action of Ethyl Formate on Camphor. . . . . HALLER (A.). Influence of Solvents on the Rotatory Powers of CampLols and Tsocamphols .. . . . . . . . . . KILIANI (H.). Digitonin and Digitogenin . . . . . . . CIAMICIAN ((3.) and P. SILRER. Hydrocotoln, s Con&nent of Cot0 Bark. LAFAR (F.). Cochineal-carmine . . . . . . . . . STOEHB (C.). Synthetical Pyridine Bases of the &Series . . . . KOSTANECKL (S. v.). Tinctorial Properties of Nitrosoxyquinolinee . . KOSTANECKI (S. v.) and M. REICHER. Quinolinedihydroximes . . . EDINQER (A.) and E. BOSSWNG. Substitution Products of Isoquinoline . STOBHB (c.). New Class of organic Bases . . . . . . . GBEHARD (F.). new Base, CgtT,2Na0, from Epichlorhydrin and Phenyl- hydrazine . . . . . . . . . . . . BLAU (P.). Constitution of Nicotine . . . . . . . . HBSSE (0.). Isocinchonine . . . . . . . . . . STRANSKY (8.). Veratrine .. . . . . . . . MULLBR (W.). Double Salt of C&aYne . . . . . . . MULLER (W.). Cocfiine Chromate . . . . - . . - LIEBERMANN (c.) and 0. KURLINB. Oxidation Of Hygrine . . . BUCHKA (K.) and A. MAQALHAfs. Cytisine . . . . . . GRANDIS (V.). Crystals Occurring in the Nuclei of Liver Cells. . . (JCEUTZENBEBQEB (P.). Synthesis of Protdds . . . . . . GRANDIS (V.). Action of Glycerol on Egg Albumin . . . . . SIEGFRIED (M.). Decomposition Products of Protdds . . . . FREDYBICQ (L.). Preservation of Oxyhoemoglobin . . . . . FBEDERICQ (L.). Preservation of Hsemocyanin . . . . . . 8TEWART ((3. N.). Electrolysis of, and Putrefaction of Bile . . . BEWAD (I.). Tertiary Nitro-hydrocarbons of the Aliphatic Series . . PAT ERN^ (E.) and A. PERATOKER. Supposed Isomeride of Acetylene Di- iodide .. . . . . . . . . . . . ~ E M M L E R (F. W.). Anhydmgeraniol, Olefinic Terpenes, and the Formation of the Clo,ued Carbon Chain . . . I . . . . . . VARET (R.). Ammonincal Derivatives of Mercuric Cyanide . . . TRAUBE (J.) sncl0. NEWBEXG. Action of Iodine on the Alcohole of the C,H2.+aOSeries . . . . . . . . . . BRUHL. (J. W.) and H. BILTZ. Metallic Derivatives of Alcohole : . . DR FORCRAND. Alkaline Derivatives of Erythritol . . . . . FREUND (A). Formation of Sorbose from the Juice of Mountain Ash Berries . . . . . . . . ALLEN (E. W.) and B. TOLLEBS. Wood Sugsr’(Xyiose) and Wood Glum (Xjlan) . . . . . . . . . . . . and a-Dinitrophenp1-a- and B-naphthyihydrazines . . * . . 665 566 567 567 567 568 56% 569 569 570 570 57 1 671 571 673 574 575 576 558 578 579 579 580 580 581 682 583 583 585 685 685 586 587 5N7 588 589 590 59 1 69 1 691 653 655 655 G55 656 656 657 658 659xxvi CONTENTS.PAGE VILLIERB (A.). Conversion of Starch into Dextrin by the Butyric Ferment VILLIEBB (A.). Fermentation of Starch by the Butyric Ferment . . TANBRT (C.). Levosin : A New Carbohydrate from Cereals . . . VIQNON (L.). Cotton Dyeing . . , . . . . . . BEBQ (A.). Normal Butglamines . . . . . . . . MO~CHATOS (H.) and B. TOLLENS. Additive Products uf Hexumethplene . SCHOLL (R.). The Simplest Normal Oxime and its Polymerides . . . OTTO (R.) and J. TBOQER. Ethylsulphoneacetone and Diethylsulphone- acetone . . . . . . . . . . . . . SCHEUREB-KESTNEB. Turkey-red Oil . . . . . . . . SCHABDINQER (F.). A New Optically Active Modification of Lactic Acid obtained by the Bacterial Decomposition of Cane-sugar.. . . FISC~EB (E.) and R. STAHEL. Xylose. . . . . . . . ALLEN (E. W.) and B. TOLLENS. Xylonic Acid . . . . . . ZEL~NSKY (N.) and A. BE~REDKA. Relative Properties of Dimethgl- glutaric and Trimethylsuccinic Acids : Stereoisomeric Trimethylsucciiiic Acids . . . . . . . . . . . . . PECHMANN (H. v.). Acetonedicarboxylic Acid . . . . . . WNSCHMANN (M.) and H. v. PECHMANN. Synthesis of Citric! Acid from Acetouedicarboxy lic Acid . . . . . . . . . BURTON (B. S.) and k€. v. PECHMANN. Condensation of Acetonedicarboxylic Acid with Phenol8 . . . . , . . . . . . DUNSCEMANN (M.) and H. v. PECHMANN. Alkyl Derivatives of Acetonedi- carboxylic Acid . . . . . . . . . . . NIEME (A. 1 and H. v. PECHMANN.Citracumalic Acid, a New Condensation JACOBI (H.). Oximes of Sugars . . . . . . . . Prdduit of Acetonedicarboxylic Acid . . '. . . . SCHIFF (H.). Preparation of Pyromucic Acid . . . . . BLABEZ ((3.). Solubi1it.y of Potassium Hydrogen Tartrate . . . Yiscesa (E.) and 0. PILOTY. Reduction of Saccharic Acid . . FISCHIRR (E.). d- and i-Mannosaccharic Acids . . . . . EMERY (W. 0.). Tricarballylic Acid . . . . . . . SOHULZO (E.) and A. LIKIEPNIK. Constitution of Leucine . . . VAPET (R.). Isopurpurates. . . . . . . . . UHB (Y.). Alkyl Compounds of Cadmium and Magnesium . . LIEBEBMAPN (C.) and A. SEYEWITZ. Purity of Benzene . . . SCRWEITZER (R.). Acetylation of Aromatic Substitution Products . JANOVIKY (J. V.). New Reaction for Dinitro-coriipounds . . . HEI~E (R.). Synthesis of Hydrocarbons .. . . . . WIDMAN (0.). The Constitution of Cymene . . . . . MEYBB (R.). Cgmene. . . . . . . . - . W IDMAN (0.). Et,hylpropylbenzene . . . . . . . WILLGEBODT (C.). Preparation of Nitroso-compounds . . . ZINCICE (?.) and 8. RABINOWIT~CH. Action of Chlorine on Resorcinol NOELTINQ (E.) and L. STOECKLIN. Nitration of Aromatic Amines . GEIMAUX (8.). Reactions of Oxg-alkyl Derivatives of Dimethylaniline . BIs~azYcK1 (A.) and (3. CYBULSKI. Action of Acid Chlorides on Ortho- diamines . . . . . . . . . . . . . FISCBEB (0.) and Gt. FISCHER. Yaramidocarbinols . . . . . MINIJNNI ((3.). Sodium Compounds of Aromatic Anilides and Amines . QODCHA~X (E,). Action of Selenyl Chloride on Aromatic Tertiary Amines . . . . . . . . . . . . . ODDO ((3.). Triazobonzene .. . . . . . . . . MINUNNI ((3.). Coiistitution of the Amido-derivatives of Hydroxylamine . TIEYANN (F.). Amidoximes . . . . . . . . . VORLANDEB (0.); Constitution of Disubstituted Oxalenediamidines . . CLEMM (A.). Derivatives of Metahydroxgbenzaldehyde . . . . KXONE (W.). Parahydroxybenzer.ylamidoxime . . . . . . C+ABRIEL (S.) and P. HEYMANN. Action of Alkylene Bromides on Thi- 659 660 661 662 662 663 663 664 665 665 666 667 668 669 670 672 673 673 675 676 676 67'7 678 680 681 681 682 684 654, 685 685 686 688 688 688 689 698 693 694 695 696 696 696 697 697 697 699 700 amides -. . . . . . . . . . . . . 501CONTENTS. XXI-ii ~ C H I F F (H.) and A. VANNI. Isomeric Ethyl Amidotolylcarbamates . . ABBL (J. J.). Benzilidenebiuret and. Chlorobenzylidenethiobiuret .. TIEMANN (F.). Production of Orthochloranisaldehyde from Paranitro- toluene . . . . . . . . . . . . . HABEB (F.). Piperonal Derivatives . . . . . . . . GBAEBE (C.) and A. EICHENGRUN. Hydroxyketone Dyes: A New Di- GOTTIG (C.). Ethereal Salts of Cblorhydrins . . . . . . FBITsCH (P.) . Salts of Dichlorhydriil with Aromatic Acids . . . FBITSCH (P.). Triglycerides of Aromatic Acids . . . . . . Z~NCEB (T.) and H. WALBAUM. Action of Chlorine on Hydroxybenzoic Acids . . . . . . . . . . . . . GARELLI (F.). Action of Phenylhydrazine and Hydroxylamine on some Ketonic Acids . . . . . . . . . . . OTTO (R.) and A. R~SSING. Action of Sodium Phenylmercaptide on Ethyl Chloracetoacet ate . . . . . . . . . . . BREDT (J.). Action of Ethyl Sodacetoacetate on Ethyl Benzalmalonate .WEQSCHEIDEB (R.). Ethyl Hydrogen Hemipinate . . . . . BOETTINQEB (C.). Oxidation of Gallic Acid . . . . . . MICHAELIS (A,) and E. GODCHAUX. Aromatic Sulphines . . . . MICHAELIS (A.}. Thionylamines . . . . . . . . . OTTO (R.) and J. TBBGER. Aromatic Sulphonic Iodides . . . . OTTO (R.) and J. TBOQER. Action of Zinc Ethyl on Aromatic Sulphonic Iodides . . . . . . . . . . . . OTTO (R.) and J, TROGER. Aromatic Thiosulphonic Acids . . . . OTTO (R.) . Behaviour of Sulphonic Chlorides towards Thiophenols and Thioalcohols in Presence of Alkttlie. . . . . . . . KAFEA (E.) . Benzaldehydesulphonic Acid . . . . . . . MORQAN (T. M.). Extraction of lndigotin from Commercial Indigo . . ECEENBOTH (H.). Synthesis of Dimethylindigo from Parachloraceto- SCHOTTEN (C.). Oxidatibn of Hydrated Pyridine Bases : Conversion of Tetrahydroquinoline into Isatin .. . . . . . . PAAL (C.). A hew Synthesis of Indazole Derivatives . . . . . ANSCFI~~TZ (R.) and H. GELDEUMANN. Action of Carhamide and Thiocarb- amide on Dihydroxytartaric Acid, Benzile, and Benzdin . . . ARGELI (A.). Action of Carbamide on Benzile . . . . . . ZANETTI (C. U.). Action of Naacent Hydrogen on t9-BeDzilemonoxime . LELLMANN (E.) . Reduction of Acetylo~thonitrobenzylpamtoluidine and of Benxoy lorthonitrobenzylaniline . . . . . . . . SCHWEITZER (R.). Naphthylglycollic Acid and p-Naphthyl Methyl Ketone ODDO ((3.) and E. BARABINI. ,9-lsoamylnaphthalcne . . . . . ABEQQ (R.). Derivatives of Chrysene . . . . . . . . HIRBCHBOHN (E.). Formation of an Asphalt-like Substance from Oil of Cassia .. . . . . . . . . . . . FABET (R.). Pyridine Compounds . . . . . . . . WEIDEL (H.) . Non-nitrogenous Acids derived from Pyridinecarboxylic A c i d s . . . . . . . . . . . . . BAMBEBQEE (E.). Piperylbiguanide . . . . . . . . LADENBURG (A.). Piperidinecarboxylic Acids . . . . . . BISCHLEB (A.). Piperazine . . . . . . . . . . KLINGCEMANN (F.). 1- Methyl-3-diphenyl-4-5-diphenglpyrrolone . . . DECKER (H.). Substituted Ammonium Compounds . . . . . REISSERT (A.). Juloles . . . . . . . . . . PECHMANN (H. v.). Action of Nitrous Acid on Ethyl Acetonedicarboxylate HANTZSCH (A.). Action of Hydroxylamine on @-Ketonic Acids and 8-Di- ketones . . . . . . . . . . . . . ANSCHWTZ (R.). So-called Phenylketohydroxydimethylanilidotetrahyclro- pyridinectrrboxylic Lactone : B-Anilidoglutaranil .. . . . hydroxyxanthone . . . . . . . . . . toluidide and Paratolylglycin . . . . . . NOET~TING (JL). Dyee of the Triphenylmethane Group . . . PAQB 702 702 703 704 706 707 707 708 708 711 712 712 712 713 714 715 718 719 719 720 720 722 722 722 723 725 726 726 728 727 729 730 730 732 732 733 736 735 735 736 736 736 738 739 741xxviii CONTENTS . PAOB STEUDE . (M.). Ethyl Bromacetoacetate . . . . . . . . . . 742 SCHATZMANN (P.). Attempts to prepare Hydrokhiazole Derivatives . . 744 BISTRZYCK~ (A.). Action of Orthodiamines on Orthaldehydobenxoic Acid 746 EEHRMANN (F.) m d J . UESSINQER . Indulines and Saff rnninea . . . . . . . . . 746 FISCHER (0.). oxaline Series . . . . . . . . . . . 747 HESSE (0.). Alkslo’ids of Bklladonna . . . . . . . . 748 LIEBERMANN (C.).Leevo-ecgonine and of Tropine . . . . . . . . 749 PARTHEIL (A.). Cytisine . . . . . . . . . . 750 BUCHKA (K.) and A . MAQALHAES . Cytisine . . . . . . 750 LINO~SIER (G.). Aspergillin. a Vegetable Hematin . . . . . 751 KONDAKOFF (J.). Halogen Derivatives of Amylene . . . . . 809 HAETMANN (E.). cular Weight . . . . . . . . . . . . 811 HELL (C.) and C . KITROSKY . Nitric h i d . . . . . . . . . . . . b12 LINDET (L.). Spirits . . . . . . . . . . . . . 813 WOHL (A.). Glucosoxime and Levulosoxime . . . . . . 833 WIECHMANN (F . (3.). Red Sediment formed in a Raffinose Solution . . 813 LIFSCHWTZ (J.). 814 S roKEs (H . N.). and their Chloro-derivatives . . . . . . . . . 814 COBLENTZ (W.) and S . GABRIEL . Dithioethylamine . . . . . 817 MALBOT (H.). Action of Aqueous Ammonia on Isobutyl Chloride in closed vessels at 100” .. . . . . . . . . . 817 BLPKENWALD (P.). Essential oil of Mnstard . . . . . . 818 WOLFEB (L.). Investigation of Crude Acetone . . . . . . 819 ZINCKE (T.) and F . KUBTER . Heating. and towards Phosphorus Pentachloride . . . . . 819 HELL (C.) and C . JORDANOFF . Derivatives of Palmitic Acid . . . 820 HELL (C.) and C . JORDANOFF . Cyanopalmitic Acid. Tetradecylmalonamic Acid. and Tetradecylmalonic Acid . . . . . . . . 821 ZrNcKE (T.) and F . KUSTEB . Propylideneecetic Acid . . . . . 821 HJBLT (E.). Velocity of Lactone-formation in the case of various Hydroxy- Acids . . . . . . . . . . . . . 882 HANTZSCH (A.). Isomerism of Oximes . . . . . . . . 823 CRAMER (C.). MonoxinieR of Succinic Acid . . . .. . . 823 SODEBBAUM (H . G.). Dioximidosuccinic Acids . . . . . . 825 BISCHOPF (C . A.). Trimethyleuccinic Acid . . . . . . . 828 BISCROFF (C . A.). Substituted Dimethylsuccinie Acid . . . . 829 MULDER (E.). 830 SCHWEITZER (R.). Acetyliodobenzene and Iodomandelic Acid . . . 830 EPHRAIM (J.). Action of Aldehydes onThioamides . . . . . 831 VIQNON (L.). Theory of Dyeing . . . . . . . . . 832 LIEBERMANN (C.). Allocinnamic Acid . . . . . . . . 832 SCHIFF (H.) and A . VANNI . Alnidotolyloxamic Acid . . . . . 833 TAUBER (E.) and R . LOWENHEBZ . Synthesis of Carbaaole Derivatives . . 834 HOOGEWERFF (5.) and W . A . VAN DORP . Transformation of a-Diketones in Alkaline Solution . . . . . 835 HEUMANN (K.). Diethplindrgo add Oihotoiylindigo . . . . . 837 P~CTET (A.) and H .J . ANICERSMIT . Pbenanthridine . . . . . 837 VAEET (R) . P ridine Compounds . . . . . . . . 838 BAMBEEQER (E.fand L . SEEBEPQEB . Dicyandiamide . . . . . 838 Thiazole Derivatives from Bromopyruvic Acids and horn BISOHLEB . Pheno-2’-methylrnet~adiazine (2’.Methylq, unazoline) . . . 745 Relations of the Eurhodines to the New Class of Fluorescent Colouring Matters of the Quin- Tropinic Acid and Oxidation Products of Dextro- and Complete Chlorination of Fatty Compounds of High Mole- Formation of Nitriles on Oxidation with Origin of the Higher Alcohols contained in Commercial Action of Nitric and dulphuric Acids on Vegetable Fibre . Action of Phosphorw Oxychloride on Ethereal Silicates GABRIEL (S.J. Derivatives of Ethylamine . . . . . . . 815 SCHWABTZ (Y.) . Hexamethylenamine .. . . . . . 818 Behaviour of Hexachlororthodiketexene on Transformation of Ethyl Disodiotrtrtrate by Ethyl Chloride .CONTENTS. xyk PAGE GOLDBCHMTDT (H.) and 8. POLTZEB. Derivatives of Orthamidoazo-com- pounds . . . . . . . . . . . . . AHREHS (F. B.). Sparteine. . . . . . . . . . CHARALAMPI. Alkalolds from the Swds of Delphhium staphisagria . . KONIG ((3.). Alkalolds of the Roots of Sanguilaaria canaden& and Cheli- donium majw. . . . . . . . . . . . MERCE (E.). Alkalolds of Sabadilla Seeds . . . . . . . COXINCK (0. DE). Ptomaines . . . . . . . . . YHIPsoN (T. L.). Vegetable Hsematin. . . . . . . . GUSTATSON (G.). Reaction Capacity of Chlorotrimethylene and some Allied Compounds . . . . . . . . . . . BURNS (P. S.). Dimolecular Ethyl Cyanide .. . . . . POLETAEFF ((3.). Boiling Point of Di-isopropylcarbinol . . . . ANQELI (A.). Eulyte . . . . . . . . . . . CROSS (C. F.) and E..J. BETAN. Solvent for Cellulose . . . . ANQELI (A.). Action of Nitric Acid on Acetylacetone . . , . ELIWEB (H.) and IJ. SCAMITZ. Dibut,yryl and Di-isovaleryl . . . YCHMIDT (E.). Angelic Acid . . . . . . . . . BISCROFP (C. A,). Substitution Derivatives of Succinic Acid . . . BISCHOFF (C. A.). Theoretical Results of Btudies in the Succinic Acid Series . . . . . . . . . . . . . BISCHOFF (C. A.). Dynamical Hypothesis in its Application to the Succinic Acid Series . . . . . . . . . . . . CJAMICIAN ((3.) and A. .ANQELI. . Oxidation Products of Brominated Thiophene . . . . . . . . . . . . . MIOLATI (A.). So-called Tsothiocyanoethylsulphine .. . . . VOLHARD (J.). Prepiation of Pyromucic Acid from Furfuraldehyde . WOLFF (L.) and P. F. GtANs. Furazancarboxylic Acid . . . . CLAWS (A.). Constitution of Benzene . . . . . . . . WIDMAN (0.). C p e n e . . . . . . . . . . MILLER (W. v,) and ROHDE. Oxidation of Cymene and hopropylbenzene with Chromyl Chloride . . . . . . . . . . . SCHRAMX (J.). Action of Halogens on Aromatic Compounds in Prebence KLINGEB (H.) and 0. STANDEE. Action of Sunlight on Organic Compounds . . . . . . . . . . . . . ANSCHUTZ (R.) and H. WEPER. Action of Aniline on Chloride and Bromide of Arsenic . . . . . . . . . . . WISLIOENWS (W.) and W. SATTLER. Corndination of Ethyl Oxalate with Anilides. . . . . . . . . . . . . KEHRMANN (F.). Action of Alkalis and Amines on Halogen Subetitufed Quinones .. . . . . . . . . . , WILLGERODT (C.). Symmetrical Trinitrosophenylparabromazobenzene . WILLQERODT (C.) and A. BOHM. Picrylchlorophenylhydrazine and SCHIFF (H.) and A. VANNI. Amidotolploxamethtrne . . . . . B~QINELLI (P.). Ethyl Acetoacetate Aldeliydeuramide . . . . & T A P E (E.). Formgl und Oxalyl Derivatives of Orthamidobenzamide . CLAWS (A.). Alkyl Ketones from Halogen derivatives of Aromatic: Hydro- carbons . . . . . . . . . . . . . ZACHARIAS (E.). Action of Ammonia on Derivatives of the Ethjl and Methyl Salts of Ortharnidobenzoic Acid . . . . . . ANSCHWTZ (R.) and W. BEPNS. Diethylcarbobenzonic Acid . . . MICHAEL (A.) and I?. C. FREER. Additive Products of Et.hvl Sodoaceto- acetate and Sodiomalonate with Ethereal Salts of Uneatur&d Acids .KNEBEL (W.). Derivatives of Phenyl Salicylate . . . . . . THIBME (P.). Action of Ammonia and Metliylamine on Deriratives of the Ethyl and Methyl Salts of' Nitrohydroxybenzoic Acids . . . . TAEGE (C.). Metanitrocoumarin . . . . . . . . . of Light. . . . . . . . . . . . CMCS (A.) andE. KBAUSE. Tliymol . . . . . . Related Componnds . . . . . . . . . 839 842 842 843 844J 846 846 888 888 889 889 890 890 890 891 891 892 893 893 896 696 897 897 898 898 899 900 901 902 903 905 !105 907 808 908 91 1 912 913 914 913 915 918sxs CONTENTS. ZOLFFEL ((3.). Tannins of Algarobilla and Myrobalans . . . . EYEMAN (J. F.). Shikimic Acid . . . . . . . . . CLAUS (8.) and C. GBONEWEG. 4 : 5-Dichlorophthalic Acid : Derivatives of Ortho-xylene . . . . . . . . . . . MEYER (R.). Benzeneazomalonic Acid .. . . . . . WISLTCENUS (W.) . Ethyl Benzamidoxalacetate and Benzamidopjruvic Acid . . . . . . . . . . . . . OTTO (R.) and J. TROOER. Action of Iodine on Sodium Benzenesulpliinate OTTO (R.) and J. TROOER. Thioanhydrides of Aromatic Thiosulphonic Acids and Polpthiosulpllonic Acids . . . . , . . OTTO (R.) and A. ROSSINO. Aromatic and Aliphatic Thiosulphonic Acids . LEDERER (L.). Spnthesis of Indigo from Phenylglycocine . , . . HEUMANN (K.). Non-formation of an Indigo Derivative by fusing Para- tolylglycocine with Alkalis . . . . . . . . . SCHOTTEN (C.). Isatin-blue . . . . . . . . . . LIMPR~CHT (H.). Benzidinedisulphonic Acid . . . . . . KLINOER (H.) and 0. STANDKE. lsobenzile . . . . . . KLINBER (H.) and L. SCHMITZ. New Syntbesis of Isobenzile .. . EESTRAND (A. (3.). Naphthoic Acids. . . . . . . . SCHMIDT (R. E.). Alizarinsulphonio Acids : Conversion of Anthraquinone- a- and -6-disulphonic Acids into Blmopurpurin and Anthropurpurin . SCHMIDT (R. E.) and L. GATTERMANN. New Dyes of the Anthraquinone Series . . . . . . . . . . . . BECKMANN (E.) and M. PLEISSNEB. Oil of ‘Pole; . . . . . HESSE (0.). Saponin . . . . . . . . .. . . YFAFF (F.). Poisonous Constituents of “Timbo” . . . . . GUTHZEIT (M.) and 0. DRESSEL. Synthesis of Pyridine Derivatives from Derivatives of a-Pyrone . . . . . . . . . . KRUOER (M.). Beta’ines of Pyridine Bases . . . . . . . MIOLATI (A.). Constitution of Rhodanic Acid , . . . . . PAAL (C.) and A. BODEWIQ. Quinazoliiies . . . . . . , NIETZKI JR.) and 8. HASTERLIK. Action of Dioxyquinones on Ortho- diamines .. . . . . . . . . . . . XEHRMANN (F.) and J. MESSINGER. Azonium Compounds . PINNER (8.) and R. WOLFFENSTEIN. Nicotine . . . . . . MOER (J. v, D.) and P. C. PL~GGE. Cystisine and Ulexine. . . . BBUNTON (T. L.) and S. MARTIN. Action of Alcohols and Aldehydes on Protei’ds . . . . . . . . . . . . . GABRIEL (S.) and W. ASCHAN. A Product of the Putrefaction of Protei’ds VAUBEL (W.). Formation of Ethers in the Preparation of Isoallylcne and its Homologues from the Corresponding Halogen Derivatives and Alcoholic Potash . . . . . . . . . . . MOH ;ER (E.). Purification of Crude Alcohol . . . . . . TISSIER (L.). The Fourth Primary Amy1 Alcohol . . . . . ZALOZIECKI (R.). Constitution of the Oxygen Compounds in Petroleum . DE FORCBAND. Preparation of Disodium Erythroxide. .. . . OST (H.). Refractive Power of Levulose and Invert Sugar . . . . MAQUENNE. Trehalose. . . . . . . . . . . STONE (W. E.) and D. LOTZ. Xylose from Maize Cobs . . . . CROSS (C. F.) and E. J. BEVAN. Action of Nitric Acid on Vegetable Fibres . . . . . . . . . . LE BEL (J. A.). Dissymmetry and Optical Activity of Alkyl Derivatives of Ammonium Chloride . . . . . . . . , TIDAL (R.) . Action of Hydroxyhydrocarbon Derivatives on Nitrides and Hydronitrides . . . . . . . . . . . . MOSCHELES (R.). Chloralimido-compounds . . . . . . FORSSELL (GI,). Action of Ethylenediamine on Thiamides . . . . in the Presence of Mercapt.ans . . . . . . . WALLACH (0;). Massoyene . . . . . . . PAGE 918 9 19 92 1 922 922 934 924 926 928 928 928 929 931 932 932 934 935 93 5 936 938 938 939 941 943 943 944 945 945 946 947 948 996 997 998 999 999 1000 1000 1001 1001 1002 1003 1003 1003 FOBSSELL (G.).Action of Ethylenediamine on Ethyl Dibromosuccinate . 1~04,CONTEXTS. xxsi WALLACE (0.) and J. WAHL. Derivative8 of Amylene Nitrosate . . WALLACH (0.) and P. ENQELS. Decomposition of Amylene Nitrosate with Sodium Etlioxide . . . . . . . . . . JAWER (J.). Condensation of Guanidine with Ethereal S&e of @-Ketonic Acids . . . . . . . . . . WALLACH (0:) and G. REINHABDT. Rubeanic Acid . . . . . BAIJMANN (E.) and E. FROMM. Isomerism of Thioaldehydee . . . BAUMANK (E.) and E. FROMM. Trithio-derivatives of Acetaldehyde . . DIJVILLIER (E.). Dimethylacrylic Acid from Tsovaleric Acid . . . WISBAR ((3.). Distillation of the Potassium Hydrogen Salts of some Acids of the Oxalic Series.. . . . . . . . . . MASSOL (Gt.j. Ethyl Hydrogen Malonate and Ethyl Potassium Malonclt,e . WIssaR ((3.). Decomposition of Gtlutaric Acid and Succhic Acid by Stin- light in Presence of an Uranium Salt . . . . . Lossm (W.) and A. KOHLEB. Hydrolysis of Ethereal Salts of Polibasic Acids . . . . . . . . . . . . . AUWEW (K.) and E. E~BNEB. Symmetrical Dimethylglutaric Acid and Trimethylsuccinic Acid . . . . . . . . . . BABTHE (L.) . Methyl Methylcyanosuccinate : Methyl Methylethenyltri- carboxylate . . . . . . . . . . . . HELL (C.), Isomeric Pimelic Acid from Amylene Bromide . . . . BOTTINGER (C.). Preparation of Gtlyceryl Pyrurate . . . . . AIGNAN. Constitution of Aqueous Solutions of Tartaric Acid . . . AIQNAN. Combinations of Tartaric Acid aud Potash or Soda in Solutions .DOEBNEP (0.). Formutioii of Inactive Tartaric Acid by the Oxidation of Phenol with Potassium Permanganate . . . . . . . ERRERA ((3.). Substitution of Hslogens in Aromatic: Hydrocarbons . * ERBERA ((3.). Action of Chromyl Chloride on Cymene . . . . TOHL (A.). Synthesis of Parapropyltoluene and Paraisopropyltoluene. . FILETI (M.). Paradipropylbenzcne . . . . . . . . FILETI (M.). Parapropylisopropylbenzene . . . , . . . JACKSOX (C. L.) and W. H. WARRRN. Reactions of Sodium Alkyloxides and Phenoxides with Tribromodinitrobenzene and Tribromotrinitm- benzene . . . . . . . . . . . . . GBAEBE (C.). Chloranil . . . . . . . . . . GRAEBE ((7.). Bromanil . . . . . . . . . . DIENIQ~S (Gt.). Compounds of Metallic Sulphites with A n i k .. . ANDR~ ((3.). Some Compounds formed by Mercuric Chloride . . . BADEE (R.). Symmetricai Trisubstitution Derivatives of Benzene . . DENIQBS (G.). Combination of Metallic Sulphitea with Amines of the Ben- zene Series . . . . . . . . . . . GBIMAIJX (E.) and L. LEF~VBE. Nitro-deriratives of Dimethylortha- anisidine . . . . . . . . . . . . BAMBERQER (E.). 1 : 4 : 6-Trimethylparaphenylenediamine . . . BRHBEND (R.) and E. KONIG. Alkyl Derivatives of Hydroxylamine . . I JMPBICHT (H.) . Azo-derivatives . . . . . . . . EosTdNEcKI (8. v.) and J. D. ZIBELL. Orthohydroxyazo-dyes . . . Lossm (W.). Tetrazotic Acids, Oxy- and Dioxy-tetrazotic Acids . . LOSSEN (W.) and F. MIEBAU. Benzenpldioxytetrazotic Acid . . . Lossm (W.) and M. NEUBEBT. Metanitrobenzenyldioxytetrazotic Acid .LOSSEN (W.) and C. LOSSEN. Phenethenyldioxytetrazotic Acid . . . Lossm (W.) and C. LOSSEX. Reduction of Benzenyldioxytetrazotic Acid . WILLQERODT ((2.). Orthochlorophenylhydrazine. . . . . . SODERBAIJM (H. G.). Configuration of w-Ieonitrosoacetophenone (Benzoyl- FISOHBR (0.) and E. HEPP. Induline kroup . . . . . . ANSCHUTZ (R.) and C. BEAVIS. Dichloromaleinanil Chloride . . . JACOBSEN (P.) and A. FRANKENBACHEB. Formation of Thionnhydro-corn- pounds. . . . . . . . . . . . . MEYER (R.). Phthaleins . . . . . . . . . formoxime) . . . . . . . . . . . PAQB 1004, 1005 1007 1008 1005 1010 1011 1011 1012 1013 1013 101 5 1017 1017 1018 1019 ioia 1020 1020 1020 1022 10.22 1023 1024 1027 1028 1029 1030 1030 1030 1031 1031 1032 1032 1036 1038 1038 1040 1040 10g1 1041 1043 1043 1044, 1047 1048xsxii OOhXENTS .BARBAQLTA (G . A.) and A . MARQUARDT . Action of Sulphur om Benz- BAUMANN (E.) and It . FROMM . Thio-derivatives of Benzaldehyde . . HEUSLEU (F.) . Behaviour of Cinnamaldehyde towards Alkali Hydrogen aldehyde . . . . . . . . . . . . BAUMANN (E.) and E . FBOMM . Aromatic Thioaldehydes . . . . S ulph i tes . . . . . . . . . . . . EBRERA ((3.). Some Ketones . . . . . . . . . ASCHAN (0.). Hydrogenation of Benzoic Acid . . . . . . B~TTINQER (C.). Anilpyruvic Acid . . . . . . . . FILETr (M.) and F . CROSA . GBAEBE cC. ) and 0 . SCEULTESS . Thioxanthone . . . . . . REISSERT (A.) and W . KAYSEB . Asymmetrical Phenylbydrazidoacetic Acid . . . . . . . . . . . . . KINNICUTT (L . P.) and (3 . D . MOORE . Action of an Alcoholic Solution .. . . FILETI (M.) and Gt . BASSO . . FILETI (M.) and Gt . AMORETTI . Isopropylphenylglycollic Acid and its Deriva- tives . . . . . . . . . . . . . KOSTANECEI (S . v.) and B . NESSLER . . Bo~~rzva~ar (C.). Tannic Acid of Oak Wood . . . . . . MOULTON (A2 . W.). Some Derivatives of Phthalic Sulphinide . . . DOEBNEB (0.). Symmetrical Alk+ophthalic Acids . . . . . V I m E (4.). Action of Urea on Sulphanilic Acid . . . . . . E~LBEBA ((3.). Nitrocymenesulphonic Acids . . . . . . OTTO (R.) . Unsaturated Sulphones . . . . . . . . of Silver Nitrate on Ethylphenyldibromoprpionate Derivatives of Cumic Acid Homocumic and Homoterephthalic Acids . . . . Synthesis of Hydroxyxanthones ZELINSKY (N.) and L . BIJCHSTAB . Stereoisomeric Methylphenylsuccinic Acids .. . . . . . . . . . . . AUTENRIETH (W.) . Certain Sulphone Derivatives and their Hpdrolysis in Alkaline Solution . . . . . . . . . . BUBMEISTER (R.) and A . MICHPELIS . Action of Phenylhydrazine on Ethyl Chloromdonate . . . . . . . . . . . HEYMANN (B.). Synthesis of Tndigotindisulphonic Acid (Indigocarmine) . RAMBEKQER (E.) and IV . LODTER . A Closed Chain. Analogue of Ethylene . ORNDORFF (W . It.) and F . L . KOBTRIGHT . Decomposition of some Diazo- NOELTINQ (E.) and E . GBANDMOUQIN . Orthonzo-compounds of tr-Naphthol NOELTING (E.) and E . GKANDMOUGTN . Molecular Change in the Forma- NOELTINQ (E.) and E . GRANDMOUGIN . Constitution of the Kydrazoms of /3- Naphthaquinone . . . . . . . . . . BRAS- (E) . Nitro-derivat.ive8 of Alizarin and Purpurin . . . .WALLACH (0.). Terpenes and Camphors . . . . . . . WAQNEJ~ ((3.). Presence of Ethylene Linkings in Terpenes . . . . VARET (R.). Terebenthene . . . . . . . . . . BTARD (A.) and P . LAMBERT . Terpene i n the Oil from Compressed Gas . PESCI (L.). Action of Phthalic Anhydride on Amidoterebenthene . . WALLACH (0.). New Compounds of the Camphor Series and a New Ter- pene . . . . . . . . . . . . . UAZENEUVH (P.). Pymgenic Conversion of Camphosulphophenols in to Ordinary Phenols . . . . . . . . . . . ARATA (P.) and C . GELZEB . Morrenole . . . . . . . LINOSSIEB (G.). Aspergillin, a Vegetable Hematin . . . . . J~ERTHELOZ! and G . ANDRB . Humic Compounds . . . . . . BAMBE~QEE (E.). Constitutioii of Rings containing Five Atoms . . . BEYEU (C.). Hantzsch s Pyridine Syntlreais .. . . . . ~ ( ~ T T I N G E R (c.1. Oxidation of Aniluvitonic Acid . . . . . SCHWAEZ (P.). &Picoliue . . . . . . . . . . AuwsRs (K.). Hydrobenwins and their Anhydrides . . . . . MILLER (W . v.). and J . PL~CHL . Aldehyde-green . . . . . . compoundsof Xaphthalene with Alcohol . . . . . . (P-Xaph thaquinone Hydrazones) . . . . . . . . tion of Disazo-compounds of a-Naphthol . . . . . . PAQE 1049 1050 1050 1052 10h2 1053 1064 1054 1055 1055 1087 1058 1059 1060 1061 1063 1064 1065 1066 1066 1067 1067 1068 1069 1089 1070 1072 1073 1074 1075 1076 1077 1078 1084 1084 1085 1086 1086 1n58 1088 1089 1089 1090 1090 1092 1092(YONTENTS . xxxiii PAQlf LADENBURG (A.). Synthesis of Oxypyridine and Piperidine Bases . . 1092 AHRENB (F . B.). y-Dipyridyl and y-Dipiperidyl .. . . . . 1093 MILLER (W . v.). Oxidation of Quinoline Derivatives . . . . . 1094 BAMBERGER (E.). Alicylic Homology . . . . . . . . 1097 EICHENQRUN (A.) and A . EINHORN . Methoxydihydroxydihydroquinoline . 1098 MILLER (W . v.) Synthesis of Quinaldine . . . . . . . 1101 MILLER (W . v.) and J . PLOCRL . 1102 MILLER (W . v.). Fluorescent Derivatives of Aromatic Diamines . . 1103 NOELTINQ (E.) and C . SCHWARTZ . Triquinylmetlicme . . . . . 1106 CLAISEN (L.) and P . ROOSEN . Derivatives of Pyrazole . . . . 1106 HANBIOT . Amidoisoxazole . . . . . . . . . 1108 WITT (0 . N.). Azonium Bases . . . . . . . . . 1108 KEHRMANN (F.) and J . MESSINGER . Azonium Bases . . . . . 1109 FISCHEB (0 ) and M . BUSCH . New Claee of Fluorescent Colouring Matters of the Quinoxaline Series .. . . . . . . . 1109 PECHMANN (H . v.). Formation, Properties, and Constitution of Osotri- azoles . . . . . . . . . . . . . 1110 JONAS (A.) and H . v . PECHYANN . Methyl-+Phenylosotriazole and its Derivatives . . . . . . . . . . . 1111 BALTZBR (0.) and H . v . PECHYANN . Homologues of n-Phenylosotriazole . 1115 BALTZER (0.) and H . v . PECHMANK . Osotriazole . . . . . 1116 PABBON (M.). Alkylisation of Secondary and Primary Bases by Potassium Alkyl Sdphates . . . . . . . . . . . 1118 LADENBURG and Gt . ADAM . New Alkalo'id from Coniam maculatum . . 1119 SAI.A MON ((3.). Paraxanthine . . . . . . . . . 1120 CAZENETJVE (P.) . Violet Colouring Matter derived from Morphine . . 1120 M ERCK (E.). Pseudocodeine . . . . . . . . . 1121 GRIMAUX (E.) and A . ANNATJD .Conversion of Cupreine into Quinine . 1121 JUSGFLEISCH (E.) and E . LEGER . Isocinchonine . . . . . 1121 LADENBTJRQ (A.). Tropine . . . . . . . . . . 1121 FRAGNER (K.). Amarylline and Bellamarine, two New Alkaloids . . 1122 ARATA (P.) and 0 . GELZER . Morrenine . . . . . . . 1122 GABRIEL (S.). CYpt. alline Egg Albumin . . . . . . . 1122 POUCRET (@.). Artificial Melanin . . . . . . . . 1123 FBANKEL (L: K ) . 1170 FREUND (M.) and P . LENZE . Polymeride of Trimethylacetonitrile . 1170 UEMONT (L.). Compound of Alcohol and Sodium Bisulphide . . . 11'70 STOKES (H . JY.). Action of Phosphorus Oxychloride on Ethyl Silicates and Silicon ISthoxychlorides . . . . . . . . . . 1171 FREUND (M.) and F . LENZE . Attempt ta Prepare Tertiary Butylcarbinol . 1172 MABERY (C . F.) and A .W . SMITH . Sulphur Compounds in Ohio Petroleum . . . . . . . . . . . . 1372 FISCIIEB (E.). Configuration of Grape Sugar and its Isomorides . . . 1173 WENDER (N) . Influence of Inactive Substances on the Rotatory Power of Very Dilute Sulutionsof Grape Sugar . . . . . . . 1178 TOLLENS (B.). Rotatory Power of Leviilose and Invert Sugar . . . 1178 SCHULTZE (E.). Chemical Composition of the Membrane of Plant Cells . 1178 EMICH (F.), Biguanide . . . . . . . . . . 1180 EYICH (F.), Guanidine . . . . . . . . . . 1180 MEYER (V.). Oximes . . . . . . . . . . . 1181 FREER (P . C.). Constitution of Aliphatic Ketones and the Action of Sodium on Acetone . . . . . . . . . . . 1181 FREER (P . C.) and S . 0 . HIQLEY . Action of Ethyl Chlorocarbonate on Acetone Sodium . . .. . . . . . . . 1182 VATJBEL (W.). '' Acetone-potaph" and " Acetone-soda" . . . . 1183 VLADESCO (D.). Action of Chlorine on Methyl Ethyl Ether . . . 1183 Colouring Matters from Hydroquinaldine . Hlectrolvsis of Metallic Thiocyanates and the Decompo- sition of Alkali ThiocytlAates . . . . . . . . . FISCHER (E.) and R . STAHEL . 1.-Sorbitol . . . . . . . 1173 HARTTJNQ (L.) . Hexamethylenamine . . . . . . . . 1179 BOTTINQER (C.). Preparation of Triacetin . . . . . . . 1183 VOL . LX . Cxxxiv UONTENTS. PACE S~DBRBAUY (H. G.). Cyanisonitrosoacetic Acid . . . . . . 1184 MICHAEL (A.) and 0. SCHULTHESS. Ethyl Salts of ufl-Hdogenised Acids . . . . . . . 11841 HAMONET (J.). Preparation of Ethereal Halts of @Ketonic Acids . . 1185 WOLFF (L.). Hydroxylevulinio Acid and Acet,yl~crylic Asid .. . 1185 EMERY (W. 0.). Action of Ammonia and Aniline on Ethyl Acetoglut- arat.e . . . . . . . . . . . . 1187 WALDEN (P.j. Tetric Acid, Oxytetric Acid, and their Homologiies . 1187 KEHRMANN (F,) and N. PICEEESGILL. Electrolysis of Cobalt Salts of Oxalic Acid . . . . . . . . . . . . 1.189 AUWERS (K.) and R. BERNRASDI. Determination of the Structure of Ftltty Acids by Bromination . . . . . . . . . 1189 AUWERS (K.) and A. IMHAUSER. Bromination of Succinic Acid and its Alkyl Derivatives . . . . . . . . . . . 1191 PIUTTI ( A.). Monoximes of Succinic Acid . . . . . . . 1191 CRUM BROWN (A.) and J. WALKER. Acids . . . . . . . . . . . . . 1192 CRUM BROWN (A.) and J. WALKER. Succinic Acid . . . . . . . . . . . . 1193 FISCHER (E ). Acid . . . . . . . .. . . . 1193 REOUSSOPOULOS (0.). Ethyl Ethylenedicarbamate . . . . . 1395 CIAMICIAN ((3.). Constitution of the Tetrole Rings . . . . . 1195 BRUHL (J. W.). Pjrone . . . . . . . . . . 1195 JSTRATI and P~TRICOU. Action of Chlorine on Beiizene in Presence of Sulphuric Acid . . . . . . . . . . . 1196 FRIEDEL (C.). Benzene Hexrtchloride . . . . . . . . 1196 ISTRATI. New Method of Iodation in the Aromatic Series . . . . 1197 ISTILATI. Iodopentachlorobenzene . . . . . . . . 1197 BTRENQ (F.). Ortbonitrotoluene . . . . . . . . . 1197 NOELTING (E.) and G. A. PALMAR. mercial Xylene . . . . . . . . . . . 1197 FABINI (E.). Colouring Matter of Red Carbolic Acid. . . . . 1198 LINDEMANN (T. v.). Action of Epichlorhydrin on Phenols. . . . 1198 KLERBERQ (W.). Act.ion of Formaldehyde on Phenols .. . . 1199 CLAUS (A.) and others. tives into Quiiiones . . . . . . . . . . 1199 EDBLEANO (L.). Action of Sulphur Chloride on Aniline . . . . 1202 BAXBERQEB (E.) and P. WULZ. Methylparatoluidine. . . . . 1202 MENTON (E.). Adjacent Ortho-xylidine . . . . . . . 1203 BOE DDINQHAUS ( W .) . Paranitrosobenzylaniline and Paranitrosobenxyl- toluidine . . . . . . . . . . . 1205 NEWMAN (H. E.j. Deriratives of Ethylene Phenyldiamine and its Homologuee . . . . . . . . . . . . 1206 GOLDSCHMIDT (H.) and R. BRUBACHER. Rydroxyozo-compounds . . 1209 HELLEB ((3.). Action of Carbonyl Chloride, Carboiiyl Sulpliide, and Alkyl Chlorocarbouates on Phenvlhydrazine . . . . . . . 1212 EEHRMANN (F.) and J. MESSINGER. Relations between Eurhodines, Indulines, and Safranines .. . . . . . . . 1213 MEYER (V.). Benzylthiocarbimide . . . . . . . . 1214 LELLMANN (E.) and E. BENZ. Compounde Prepared from Methylphenyl- chloroformamide and Diphenylchloroformamide . . . . . 1814 COBLENTZ (V.). Seleno- and Thio-derivatives of Ethylamine and Propyl- amine . . . . . . . . . . . . . 1216 HOOGEWERFF (5.) and W. A. VAN DORP. Action of Alkali Hypochloritee and Hypobrornites on some Imides and on Phthnlodiamide . . . 1216 MASX (M.). Reduction 6f Trimet,hylgallamide ; Acetylgallamide . . 1218 BrscHoFF (C. A.). Acids of the Fumaric Series . . . . . . 1220 ~ L L (H. v. D.). Action of Thiocarbimides on Hydroxylsmine . . . 1822 Alloisomeriem : Dehalogenisation of . Electrolytic Synthesis of Bibasic Synthesis of Alkyl Derivatives of New Isomeride of Mucic Acid and the so-called Paramucic Occurrence of Et.hylbenzene in Com- Orientation by Conversion of Paradinitro-deriva- GOLDSCHMIDT (H.).Cryoscopic Experiments . . . . . 1211CONTENTS. XXXV CLADS (A.), Aromatic Alkyl Ketones : their Oxidation by Potassium Per- manganate . . . . . . . . . . . . TAHAHA (Y,). Synthesis of Peonol. Application of Perkin's Reaction to Aromatic Ketones . . . . . . . . . . . DITTRICH (M.) and V. MEYEB. Derivatives of Ethyl Dinitrophenyl Acetate , . . . . . . . . . , . . EDELEANO (L.1. Preparation of Unsaturated Aromatic Acidu . . . GRAEBE (C.) and A. LANDRISET. Action of Potaesium Cyanide on GATTERMANN (L ). Method for the Isolation of Aromatic Sulphonic Acids ISTRATI and GEORQESCO. Action of Sulphuric Acid on Iodine in Preaence of Calcium Benzenesulphonate .. . . . . . . DE ROODE (R.). Derivatives of Benzoic Snlphinide . . . . RANDAT~L (W. W.). Orthosulphoparatoluic Acid and its Derivatives . . OTTO (R.). Hydrolysis of Sulphones . . . . . . . . BAUMAKN (E.). Hydrolysis of Sulphones and Ethereal Salts of Benzene- KNIETSCH (R.). Synthesis of TndigobindiRuIphonic Acid (Indigocarmine) . ~CBULEOFER (L.). Action of Stannous Chloride on Nitrophenyliredazole- carboxylic Acid . . . . . . . . . . . BRASCH (R.) and G. FREYSS. Benzidine Colouring Matters . . . BESTHORN (E.) and W. CUETMAN. Anilidoacridines and Hydroxyacridines. GALEWSKY (P.). Diphenylene Oxide . . . . . . . . RUEANOFF (A.), Condensation of Benzaldehyde with Phenols . . . SCEIAFER (A.), Oximes of Asymmetrical Ketones. . . , . . HOFFMANN (E.).Oximes of Halogenated Benzophenorres . . . . EOTTENHAHN (W.), Metabromobenzophenoue and its Oximes . . . ~ I T T R I C H (M.), Svmrnetrical Parsrliuhlorobenzophenone and its Oximes . DODQE (F. D.). Diphenylfurazan and some Derivatives of Oximes . , BOURGEOIS (E.). Tolvl Naphthvl Sulphides . . . . . . BAMBERQRR (E.) and C. GtOLDSCRMIDT. Ethyl-a-naphthylamine . . KOLL (A.). n8-Benzenylnapht,hylenediamine . . . . . . HOOKER (S. C ). Derivatives of Lapachic Acid . . . . . . SCHWEITZEB (R.), Boiling Points of some Compounds of High Molecular Weight . . . . . . . . . . . . GRAEBE (C.) and A. PHILIPS. Oxidation of Alizarin Green and Alizar- indigo Blue . . . . . . . . . . . WALLACH (0.). Terpenes and Ethereal Oils. . . . . . . WAQNER ((3.). Constitution of Pinene.. . . . . . ANDERLINI (F.). Derivatives of Cantharidin . . . . . . EOSTANECKI ($3. v.). Gentiain . . . . . . . . . LELLMANN (E.) and R. JUST. Derivatives of Piperidine . . . . LELLMANN (E.) nnd R. JUST. ' Behaviour of Piperidine Bases towards Aromatic Halogen Cornpounds . . . . . . . . RUGHEIMEB (L.). Introduation of Bivalent Radicles into Piperidine . . ASCHAN (W,). Derivatives of Homopiperidic Acid . . . . . DECKER (H.). Substituted Ammonium Compounds . . . . . WELTER (A.). Action of Hypochlcrous Acid on Bromoqiiinolines . . ZINCKE (T.). Action of Chlorine on Hydroxyquinoline . . . . CLAWS (A.) and H. HOWITZ. Halogen Alkyl Compounds of Parahydroxy- quinoline and the Derived Quaternary Ammonium Bases . . . BAMBERQER (E.) and P. Wncz. Homolopes of Tetrah ydroquinoline.. BAMBBRQER (E.) and P. Wur,z. Tetrahydro-1-amidoquinaldine . . . LELLMANN (E.) and H. ZIEMSSER. Derivatives of 1-Methylquinoline and 3-Meth ylquinoline . . . . . . . . . . . SCHIFP (K.). Cocstitution of Phenanthroline Bases . . . . . BAMBERQER (E.). Reduction of Tricyclic Syaterns . . . . . BAMBERGEB (E.) and L. STETTERHEIMER. Tetrahydro-a-naphthaquinoline. BAMBERGCER (E.) and L. STETTENHEIMEB. " Aromatic " Octohydro-a- naph thaquinoline . . . . . . . . . . . Phthaldehvdic Acid . . . . . . . . . sulphinic Acid . . . . . . . . . . 0 2 PAQB 1222 i223 1224 1225 1225 1226 3 226 1226 1228 1229 1229 1231 3231 3 231 1232 1234 1234 1235 1236 1236 1237 1237 1238 1238 1239 1239 1244) 124Q 1240 1242 1243 1244 1244 1245 1246 1246 1247 1248 12419 1262 1253 1256 1257 1258 1258 1258 1260xxxvi CONTENTS.PAOB TAFEL (J.). Strychnine . . . . . . . . . 1262 FJLEHNE (W.). Constitution of Pseridoephedrine . . . . . 32641 LIEBERMANN (C.). Benzoylpseudotrope'ine, an Alkaloid of Java Coca Leaves 1265 ADEEMANN (F.). Alknlolds of Cor*qdal/s cuva . . . . . . 1266 HOOPEP (D,), New Alkaldid in Tylophora asthmatica. . . . . 1266 HUNTER (W.). Influence of Oxygen on the Formation of Ptomaine8 . . 1267 $ALKOWSEI (E.). Peptotoxin . . . . . . . . . 1267 WEEIQO (B.). Harnack's Ash-free Albumin . . . . . . 1268 DENAEYER (A.). Behavionr of Albumin when Subjected to Pressure . . 1269 HINRICES ((3.). Paraffins . . . . . . . . . . . . 1330 FAVORSKY (A.). Isomeric Change in Unsaturated Hydrocarbons . . 1330 TSCHEBWEN-IVANOFF (N.). Polymeride of Trichloracetonitrile .. . 1332 HEMMELMAYR (F. v.). Oxygen . . , . . . . . . . . . . 1332 LADENBURG (A.). Diethylenediamine (Piperazine) . . . . . 1333 PERATONEE (A.) and B. STRAZZERI. Synthesis of Pyrone . , . . 1333 HELL (C.) and J. SADOMSKY. New Derivatives of Stearic Acid . . . 1335 MULLER (P. T.), acetate . . . . . . . . . . . . . 1337 MTCHAPL (A.). Levulinic Acid, Acetonediacetic Acid Dilactone . . . 1337 CLAWS (A.). Action of Zinc on Ethyl Dibromosuccinate . . . . 1338 SKEAWP (2. H.). Conversion of Malei'c Acid into Fumaric Acid . . . 1338 HEMMELMAYE (F. v.). carhami de . . . . . . . . . . . . 1539 HORBACZEWSEI (J.). the Pro iuction of Leucocytosis in Mammals . . . . . . 1340 XUHLIKG (0.). Azines of the Uric Acid Group . . . . . . 1341 MINUNKI ((3.). Thiophen .. . . . . . . . . 1342 VAUBBL (W.). Ring and Nucleus Structure of Aromatic Hydrocarbons . 1343 FILETI (M.). Constitution of Cymenc. . . . . . . . 1344 REINQLASS (P.) . Metacyanbbenzul Chloride and Metacyanobenzaldehyde . 1344 DE VARDA ((3.) and M. ZENONI. benzaldehyde with Phenol and Reeorc*inol . . . . . . 1346 RRAUS (A.). Methylation of Spmmetricnl Orcinol . . . . . 1347 DE VARDA ((3). ' Action of Light on Anethoil . . . . . . 1347 NEF (J. U.). Constitution of Quinone. . . . . . . . 1348 HERZIQ (J.). Euxanthone . . . . . . . . . . 1349 Lrs1%1c+ ((3.). Synthesis of Aromatic Mercaptans. . . . . . 1350 CUBTIUS (T.). Nitrogen linked together . . . . . . . . . 1350 GOLDSCHMIEDT ((3.) and R. JAHODA. Chlorhydrin . . . . . . . . . . . . 1351 KROMER (H.). Commercittl Yseudocumidine .. . . . . 1351 SCHOLTZ (M.). Action of Ammonia on Ortho-xylylene Bromide. . . 1353 MAZZARA (G.) and A. LEONARDI. Ladenburg's Method for Distinguishing Orthodiamines . . . . . . . . . . . 1354 MINUNNI ((3.). Constitution of Isomeric Oximes. . . . . . 1354 Cumus (T.) and K. THUN. Action of Hydrazine Hydrate on Ketones and Orthodiketones . . . . . . . . . . . 1355 CURTIUS (T.) and F. RAUTEBBEBQ. Action of Hydrazine Hydrate on Benzophenone . . . . . . . . . . . 1358 CUBTIUS (T.) and K. THUN. Action of Hydrazine Hydrate on Isatin and Phenols. . . . . . . . . . . . . 1360 MINUNNI ((3.) and L. CABERTI. Action of Phenylhydrazine on the Benzald- oximes . . . . . . . . . . . . . 1361 WILLGIERODT (C.) snd L. ELLON. Nitrohalogenhydrazo- and Nitrosohalogen- rtzo-compounds .. . . . . . . . . . 1361 KLAUBER (A.). a-Metaxylylhydrazine. . . . . . . . 1362 RHOUSSOPOULOS (0.). Methanetriquinol or Triquinylmethane . . 1261 Calculation of the Melting and Boiling Points of Normal Oxidation of Sodium Alkyloxldes by Atmospheric Action of Bibasic Acid Chlorides on Ethyl Sodiocyan- Methylene Derivatives of Carbaniide and of Thio- Formation of Uric Acid and of Xanthine Bases and Products of Condensation of Metanitro- Nomenclature of Compounds containing Two Atoms of Action of Benzylamine on GlycolCONTENTS . xxxvii MAZZARA ((3.) and A . LEONARDI . Behaviour of Aldehydes with Ortliamido- phenols . . . . . . . . . . . . . CLAUS (A.) and W . NEUKRANZ . Oxidation of Mixed Fatty Aromatic Ketones by Pot aseium Permunpanate . . .. . . . CLAUS (A.1 and R . WBHR . Pmatolylacetic Acid . . . . . . SCHMITT (R.) and H . HAHLE . Catecholcarboxyljc Acids . . . . HAHLE (H.). Preparation of Phenoldicarboxylic Acids . . . . ALLENDOBFF (0.). Phthalaldehpdic Acid . . . . . . . QOLUSCHMIEDT ((3.) and L . EWER . Action of Potaasium Cyanide on Ethyl OTTO (P.) . Action of Carbonic Chloride on Glycol Clilorhydrin . . . AUWERS (E.) and F . v . MEYENBUHB . New Synthesis of Isindtlzole Derira- tivea . . . . . . . . . . . . BEBTONI ((3.) . A New aeries of Oxynitro-derivatives of Tripheoyl- niethaue . . . . . . . . . . . . . HEEBMANN (P.). Nitro-derivatives of a-Ethoxpnaplithalene . . . SOWINSKI (W . v.). Hydrogenation of the Naphthoic Acids . . . . ODDO (G.). a- and B-Napht hylazoacetoacetic Acids and their Derivatives .SCHMIDT (R . E.) and L . GATTERMANN . Hydroxy-derivatives of Alizarin- blue . . . . . . . . . . . . COESELLI ((3.). Terebic Acid . . . . . . . . . VALENTA (E.). Resin obtaiued from Thwites’ Doma zqylanica . . . KOSTANECKI (S . v.) and E . SCHNIDT . Gentiein . . . . . . HERZIQ (J.) . Quercetin and its Derivatives . . . . . . . XANETTI (C . U.). Synthesis of Ethylpyrroline . . . . . . BEORBIEVICS (G . ;.). Oxidation of Quinoline Derivatives . . . . OSBOPNE (T . B.). The Proteiids or AlbuminoPds of the Oat Kernel . . MALEBBA (P.). The Viscous Materitll formed by . the Bacterium gliscrogenuna HINRICHS ((3.). Mechanical Determination of the Arrangement of the Carbon Atoms in Organic Compounds . . . . . . . PATEIN (G.). Action of Boron Fluoride on Nitriles .. . . . VARET (R.). Action of Ammouia on some Compounds of the Halond Salts of Mercury . . . . . . . . . . . . VARET (R.1. Cyanogen Compounds of Magnesium . . . . . WARREN (H . N.). Fulminates . . . . . . . . . TORNOE (H.). Ally1 Alcohol and its Formrction from Dichlorhydrin and Sodium . . . . . . . . . . . . . GERNEZ (D.). Rotatory Power of Compounds of Mannitol with Acid Moly bdatcs . . . . . . . . . . . . FISCHEB (E.). Configuration of Grape Sugar and its Isomerides . . PLAKTA (A . v.) and E . SCHULZB . Stachpose . . . . . . LIKIEBNIK (A.). Lupeol . . . . . . . . . . VILLIEBS (A.). Conversion of Starch into Dextrin by the Butyric Ferment . PPUD’HOMME . Bleaching of Cottoll by Hydrogen Peroxide . . . . MATIQNON (C.). Ureides from Normal Acids . . . . . . MATIGNON (C.). Products of Oxidation of Uric Acid .. . . . MATIBNON (C.). Parabanic and Oxaluric Acids . . . . . . BAMBERQER (E.) and P . WULZ . Action of Diazobenzene Chloride on Acetone . . . . . . . . . . . . . MULLEB (P . T.). Ethereal Nitrosocyanacetates . . . . . . Cyanostearic Acid, Hexadecjlmalonic Acid, Hexadecylmalonamic Acid . . . . . . . . . ASCHAN (0 ) . Acids fmm Baku Petroleum . . . . . . . CAUSSE (H.). Bismuth Salicylate . . . . . . . . Opianate . . . . . . . . . . . . HOLMES (J . H.). Paraxylenedisulphonic Acid . . . . . . BARTOLOTTI (P.). Eseence of Myrtle . . . . . . . . KOBTANECKI (S . v.). Gentisin . . . . . . . . . CARBARA ((3.). The Bark of Gonolobus conduiango . . . . . KRUQEB (M.). Pvridinebetai’nes . . . . . . . . . WALTER (G.). Tchthulin .. . . . . . . . . HELL (C.) and J . SADOMSKY . PAQB 1363 1364, 1365 1386 1366 1367 1369 1371 1373 1374 1375 1578 1379 1380 1381 1302 13’341 1384 1385 1386 1386 1386 1387 1387 1388 1389 1389 1390 1391 141 1441 1441 1442 1442 1442 14.43 1444 1446 1446 14443 1447 1445 1448 1440 1449 1450 1451 1462XXXViii CONTENTS . PAGE OTT (P.). Propylideneacetic Acid . . . . . . . . . 1453 SCHEURER.KESTNEE . Polyinerides of Ricinolelc Acid . . . . . 1454 LIYACHE (A.). Solid Product of the Oxidation of Drying Oils . . . 1454 JACQUEMIN ((3.). Preparationof Lactic Acid . . . . . . 1454 TIVOLI (D.). Dehydracetic Acid . . . . . . . . . 1455 MICHAEL (A.) and G . TISSOT . Homologues of Malic Acid . . . . LUDWIQ (A.) and E . A . KEHRER . A Furfurallevulinic Acid . . . 1456 1455 BEHTHELOT and ANDR~ .Thermochernistry of Humic Acid from Sugar . 1458 PECHMANN (H . v.). Decomposition Products of a-Hydroxy-acids . . 1457 DEORY (A.). Orthocyanobenzyl Chloride and Orthocpnobenzal Chloride . 1460 ERDMANN (H.). Preparation of 1 : 2 : 4- and 1 : 3 : 4-Dichlorotoli~ene . . 1462 I~RAEMER (G.) and A . SPILKER . Artificial Mineral Lubricating Oil ; the Condensation Products of Ally1 Alcohol with Methylbenzenes . . 1462 E~UMANN (H.), Action of Chlorine on Acetoparatoluidide . Preparation of Products of the Action of Aromatic Carbodiimides on Ortho- BAUR (A.). Artificial Musk . . . . . . . . . . 1464 Metachloroparatoluens . . . . . . . . . . 14436 LOECMANN (J.). y-Phenoxypropylnmine . . . . . . . 1467 PELLIZZARI ((3.). Anilguanidine . . . . . . . . . 1471 SEITZ (0.).Halogenated Amines of the Fatty Series . . . . . 1472 ZIBELL ( J . D.). Orthohydroxyazo-dyes . . . . . . . 1473 SALKOWSEI (H.). Thiocarbaniidcs . . . . . . . . 1474 OELEER (A.). Derivatives of Bromopiperonal . . . . . . 1474 GOLDSCEMIDT (H.) a d C . KJELLIN . Isomeric Paranitrobenzaldoxirnes . 1476 GOLDSCEMIDT (H.) and C . li JELLIN . oximes . . . . . . . . . . . . . 1477 GtOLDsCHMIDT (H.) and H . STOCKER . Homologues of Benzhydrylamine . 1479 GUIGIHET (C . E.). 1481 ASCHAN (0.). Hydrogenation of Beiizoic Acid . . . . . . 1481 GOTTIB (C.). p-Dichlorhydrin Metahydroxybenzoate . . . . . 1482 ERLENMEYER (E., Jun.). Optically Active Phenylbromolactic Acids . . 1482 L~EBERMANN (C.) and H . SACHSE . Diiodocinnaniic Acid . . . . 1483 ERDMANN (H.). Nitration of Cinnumic Ahd and Phenylmelhacrylic Acid in the Side Chain .. . . . . . . . . 1483 LIEBERMANN (C.) and A . HARTMANN . Condensation of Allocinnamic Acid with Phenols . . . . . . . . . . . . 1484 PELLIZZARI ((3.). Amidobenzoic Derivative& of Ethyl Acetoacetate . . 1484 METER (R.). Action ot Phtbulic Chloride on Phenols . . . . . 1485 BAEYER (A . v.). Relationship between Ethyl Succinosuccinate and Phloro- BAEYER (A . v.), R . JAY, and L . JACKSON . Phenylhydrazine Derivatives BAEYEB (A . v.) and G . v . BRUNINGI . Constitution of the Phenylhydrazine Cuus (A.) and C . MANN . Sulphonation of Parachloronitzobenzene and Paracbloraniline . . . . . . . . . . . 14238 CLAUS (A.) and H . BOPP . 8ulphonation of Metachloronitrobenzene and Metwhloraniliiie . . . . . . .. . . . 1489 CLAUS (A.) and F . IMIMEL . Snlphonation of Orthotolnidine . . . . 1490 SCHOTTEN (C.) . Bromisatin.blue . Compounds of Mono- and Di-bromisatin with Piperidine . . . . . . . . . . . 1491 TAUBER (E.) and R . LOEWENHERZ . Dimethylcarbazole . . . . 1491 JUILLARD (P.) and G . TrssoT . Preparation of Hydrobenzoln and of Deoxy- benzoSn . . . . . . . . . . . . . 1492 EPHEAIM (J.). Derivatives of DeoxjbenzoYn . . . . . . 1492 NESSLER (B.). Synthesis of Rydroxyxanthones . . . . . . 149$ PAT ERN^ (E.) and L . CABERTI . Derivatives of Lapachic Acid . . . 1494 V~GNON (L.). Melting Points of Binary Systems of Hydrocarbons . . 1495 KELLER (A.). dittmines . . . . . . . . . . . . 1468 NOELTINQ (E.) and E . GRANDMOUQIN . Azoimide . . . . . 1473 Additive Compounds of Alkylisoald- Conversion of Gallic Acid and Tannin into Benzoic Acid glucinol .. . . . . . . . . . . . 1485 of Ethyl Succinosuccinate . . . . . . . . . 1486 Derivatives of Ethyl Succinosuccinate . . . . . . 1486CONTENTS. 2txxix HOMANS (J.), R. STELTZNEE, and A. SOEOW. Truxillic Acids . . . OLIVERI (V.). Essence of Lemons . . . . . . . . CLAurBIAU ((3.). Hygroscopic Behaviour of Camphor and Thymol . . HALLEE (A. . Compounds of Camphors with Aldehydes . . . . HALLER (A]. Derivatives of Cyanocamplior . . . . . . MIXQUIN (J.). Methyl and Ethyl Methylcltmphocarboxylates : Preparation of Methylcamphor . . . . . . . . . . . CIAYICIAN ((3.) and P. SILBEB. Reduction of Apione. . . . . TAHARA (Ye). Adonin, a Glucoside from Adonis amurensis. . . . DENNSTEDT (M.). Action of Methyl Alcohol on Pyrroline .. . . CIAMICIAN ((3.) and C. U. ZANETTI. Action of Hydroxylaminei on the ENGLEB (C.) and P. ROSUMOFF. Metiyl a-Pyridyl Ketone. . . . ENOLEP (C.) and F. W. BAUEE. Ethyl a-Pyridyl Ketoneand it8 Conversion into Pseudoconliydrine . . . . . . . . . . ENQLER (C.) and H. MAJMON. Propyl a-Pyridyl Ketone . . . . ENGLEB (C.). &Ketone Derivatives of Pyridine . . . . ME~~LING ((3.). Behaviour of “ Diwethylpiperidine” and Allied Base; towards Hydrogen Chloride . . . . . . . . . LELLMANN (E.) and W. LTPPEET. Formation of Bases of the Quinoline Series . . . . . . . . . . . . . EPHRAIM (J.). Preparation of Amidoquinoline . . . . . . BAMBEEQER (E.) and R. MULLER. Tetrahydro-derivatives of @-Naphtha- quinoline nnd @-Napbthaquinaldine . . . .. . . BAMBEEQEB (E.) and R. MULLER. Octohydro-derivatives of @-Naphtha- quinoline . . . . . . . . . . . . BAMBERQEE (E.) and L. STEASSER. Octohydro-derivatives of &Naphtha- quinaldine . . . . . . . . . . . . FISCHEE (0.) and M. BUSUH. New Class of Fluoresccnt Colouring Matters of the Quinoxaline Series . . . . . . . . . NAF (E.). Nitroso-derivatives of the Thiazoles . . . . . . LIPPMANN (E.) and F. FLEISSNEE. Action of Hydriodic Acid on Quinine and Cinchonine . . . . . . . . . . . GRIMAUX (E.) and A. AENAUD. Quinethylene . . . . . . FEEIJND (M.) and C. DOBMEPER. Hydrastine . . . . . . LIEBBRMANN (C.). Pseudotropine . . . . . . . . JAELNS (E.). Alkalo’ids of the A r m Nut . . . . . . . CAMPANI ((3.) and S. ORIMALDI. Lupinidine from White Lupines . . SCHULZF, (E.) and A.LIKIEENTK. Formation of Carbamide and the Decom- position of Arginine . . . . . . . . . . CORIPT (J.) and Q. AUSIAUX. Heat Coagulation of Proteids . . . HUQOUNENQ an? EEAUD. Toxalbumin secreted by the Microbe of Blen- norhagic Pus . . . . . . . . . . . . BEBTIN-SANS (H.) and Gt. MOITESSIEE. Conversion of Carboxy-bremoglobin into Methremoglobin, and Detection of Carbonic Oxide in the Blood . Pyrrolines . . . . . . . . . . . ENGLEE (C.). Pyridpl Ketones . . . . . . . . P?tysiological Chemistry. MARTIN (9.) and D. WILLIAMS. Influence of Bile on Pancreatic Digestion COLAS (E.). Action of Nicotine on the Heart and Blood Vessels . . SAINT-LOUP (K.). Pigments of the Aplpis . . . . . . ROESER. Liquids from Hydatid Cysts . . . . . . . . LIEBEEICH (0.). Lanolin and the Detection of the Cholssterin Fats in Man KUHN (M.).Composition of the Milkof Cows in the Early and Late Periods of Lactation . . . . . . . . . . . DOREMUS (C. -4.). Elephant’s Milk . . . . . . . . DESESQUELLE (E.). Passage of Naphthol into the Urine . . . . GAUBE. Ure-phosphates and Hippuro-phosphates . . . . PAGB 1495 1496 1497 1498 1499 1500 1500 15u1 1501 1502 1503 1503 15041 1506 1506 1506 1509 1509 1510 1511 1513 1514 1516 1517 1518 1518 1520 1520 1521 1521 1521 1521 1522 96 96 96 97 37 97 98 98 98XI coxmws . PA BE DUBOIS (R.). Carrotene . . . . . . . . . . . . 98 GBEHANT (N.). theEye . . . . . . . . . . . . . 99 COMBEMALE and DWIQUET . LABORDE (J . V.). 99 MARFORI (P.). Physiologicd Action of Ouaiacol . . . . . 99 ROGER (G . H.). Substances which Favour Infection .. . . . 100 NEUMEISTBB (R.). Yroteid Absorption . . . . . . . 233 EWLZ (E.). Cyetin in Pancreatic Digestion . . . . . . . 236 ENGIEL (W.). Organic Basis of various Shells . . . . . . 236 MALIJ~RE (A.). Effect of Acetic Acid on Respiratory Changes . . . 344 BOER (C.). The Specific Quantities of Oxygen in Blood . . . . 344 ROSENHEIM (T.). Influence of Proteid on the Digeetion of Foods free from Nitrogen . . . . . . . . . . . . 341 MUNE (I.). Influence of Ulycerol and Fatty Acids on Gaeeous Metabolism 345 MABSHALL (J.). Trarisfuoion of Mixtures of Blood and Salt Solution . . 347 ROHMANN (F.) and J . MUHSAM . Amouut of Dry Residue and Fat in Arterial and Venous Blood . . . . . . . . 347 SWIATECEI (J.). Alkalinity of the Blood after Large Dosee of Sodium DEOUIN (R.).New M e t h i of Hsemato-uikalimetry : Reiative'A.lk&nity of the Blood of Vertebrates . . . . . . . . . 348 WEBTHEB (M.). Formation of Lactic Acid in Muscles . . . . 348 B ~ H M (R.). Formationof Lactic Acid in Muscles . . . . . 3.18 SCHO~VDOBFF (B.). Influence of Drinking large quantities of Water on the Excretion of Uric Acid . . . . . . . . . . 348 SMITH (F.). Sweat of the Horse . . . . . . . . . 349 ABGUTINSEY (P.). Excretion of Nitrogen in Sweat . . . . . 350 BLEIBTEEU (L.). Influence of Muscular Work on the Output of Urea . 350 SCHENP (F.). 350 UDRANSZKY (L . v.) and E . BAUMANN . liiamines and Cystinuria . . 350 BOEM (L.). Absorption of Mercury Salicylate . . . . . . 351 SWIN (C . A.). 478 ERUMMACEEB (0.). Influence of Muscular Work on Proterd Metabolisui .470 TAUBEB (E.). Fate of Morphine in the Animal Organism . . . . 479 SKORE (L . E.). Fate of Pepbone . . . . . . . . . 479 DEL-~PINB (S.). Cutaneous Pigment as an Antecedent of Hsemoglobin . 480 SHORE (L . E.). 481 DICKINSON (W . L.). Action of Leech Extract on Blood . . . . 482 FILEHNE (W.). Transformation of Hemoglobin in the Bile . . . . 482 BENDEBSKI (I.). Excretion of the Digestive Ferments from the Animal . 483 BOHLAND (C.) and H . SCHUBZ . Cams of Leucsemia . . . . . . . . . . . 483 HOPPE-SBYLEB ((3.). Calcium Salts in Urine . . . . . . 484 HOPPE-QBYLER (F.). Urine and Blood in Cases of Melanotic Sarcoma . 484 LANOLEY (J . N.) and W . L . DLCKINSON . Action of Poisons on Nerve-fibres and Peripheral Nerve-cells . . . . . . . . .4-85 QBEENWOOD (M.). Action of Nicotine on Invertebrates . . . . 485 QUINABD (L.). Effect of Morphine on Cats . . . . . . . 486 SOHLICE (IK.). Action of Strychnine . . . . . . . . 496 Mosso (TJ.). Physiological Action of Cocaine . . . . . . 486 NIXOLSEI (W.) and J . DOGIEL . Physiological Action of Curare . . . 487 CHAPMAN (H . C.) and A . P . BBUBAKER . Respiratory Exchanges in Animals . . . . . . . . . . . . . 592 JOHN (0.). Action of Organic Acids on Salivary Digestion . . . . 592 S A L K ~ S K I (E.) and Me KUYAGAWA . Hydrochloric Acid in Gastrio Juice . . . . . . . . . . . . . 593 &louring Matters of Yellow Silk and its relation to Vegetable Poisoning by Bydrocyanic Acid applied to the Surface of Yhysiologiml Action of Potassium Ferro- Physiological Action of the Soluble Salts of Strontium .cyanide . . . . . . . . . . . . . 99 LEVY (M.). Theso-called Liver of Helixpmdia . . . . . 235 Sulphate . . . . 347 Relation of Dextrose to the Prote'ids of the Blood . . . In what form is Iron Absorbed ? . . . . . . Effect of Peptone on the Clotting of Blood and Lymph . Excretion of Uric Acid and Nitrogen inCONTEXTS. MUNK (I.). Absorption of Fats in the Absence of Bile . . . . LEHMANN (F.) and J. H. VOGEL. Digestibility of Meadow Hay, Beans, Amaus (M.) and C. PAQ~S. Chemicai Theory of the Coagulation of the Blood . . . . . . . . . . . . . LBPINE (R.) and BAERAL. Destruction of Sugar in Blood . . . . PATON (D. N.). Muscular Work and Prote'icl Metabolism . . . . STEWART (G. N.). Electrolysia of Animal Tissues . . . . .PATON (D. N.) and J. M. BALFOVR. Human Bile . . . . . 8TERN (R.). Oxyhaemoglobin in the Bile . . . . . . . RICHTER (P.). 1ncreast.d OutpuL of Nitrogen in Cerebral Hyperthermia, Fever, and Artificial Overheating . . . . . . . . STOCKMAN (R.). Excretion of Baleams in the Urine . . . . . SALKowsKI (E.). Hrsmatsporphyrin' in Urine . . . . . . HARLEY (V.) and 5. TORDP. Uniisual Pigment in Urine . . . . HEINZ (R.) . Physiological Action of Saline Solutions and Various Drugs . RICHTER (P.). Physiological Action of Antipjretics . . . . . STUTZER (A.). Action of certain Organic Acids on the Digestion of Prote'ids . . . . . . . . . . . . . STUTZER (A.). Effect of Salt on Digestion . . . . . . . STUTZER (A.). Influence of Heat on the Digestibility of Fodder . . STUTZER (E.).Influence of Fat, on the Digestibility of Prote'ids. . . KERN (E.) and H. WATTENBERG. Effect of Increasing the ProtePds in Food Rations of Grown Animals . . . . . . . . VIAULT. Oxygen in the Blood of Animals at Great Altitudes . . . MUNTZ (A.). Increase of the Quantitj of Hemoglobin in the Blood, accord- ing to the Conditions of Existencc . . . . . . . . BUTTE (L.). EH'ect of Medicines, and especially of Valerian Extract, on the Destruction of Dextrose in the Blood . . . . . . . L~PINE (R.) and BABRAL. Isolation of the Glycolytic Ferment of the Blood . . . . . . . . . . . . . MUNK (I.) and A. ROSENSTEIN. Human Chyle and Lymph . . . WALTHER. Synthesis of Fatty Acids in the Animal Organism . . . SOHRODT (M.) and 0. HENZOLD. Butter Fat . . . . . . DUFOURT (E.). M~RXER (K.A. IF.) and J. SJOQUIST. Urea . . . . . . JURGENS (A.). Schreiner's Base (Spermine) . . . . . . ROSENBEBG. Diastatic Ferment in Urine . . . . . . . EBSTEIN ( W.) and A, NICOLAIER. Artificial Preparation of Sphaeroliths of Uric Acid Salts . . . . . . . . . . MARTIN (S.). Pathology of Prote'ids . . . . . . . . COPEMAN (a. M.). Specific Gravity of Blood in Disease . . . . ZWAARDEMAKER. Tdiosyncrwy of Certain Animals with respect to Phenol. STOCKMAN (R.) and D. B. DOTT. Physiological Action of Thebaine and Narcotine and their Derivatires . . . . . . . . SIEGFRIED (If.). Hemoglobin . . . . . . . . . GAD (I.) and J. F. REPMANS. kfyelin. . . . . . . . LUSK (a,). Influence of Carbohydrates on Protend Metabolism . . . MUNK (I.). Muscular Work and Excretion of Urea .. . . . BRIJBAKER (H.). Inorganic Constituents of Bone and Orgaris of Normal and Rachitic Children . . . . . . . . . . WEISKE (H.). Influence of Acid Mineral Salts on the Composition of Bone HBUBEE (h'.), C. MEYER, and M. PER NO^. Iron in the Lirer and Spleen . JOHNSTONE (W.), Composition of Butter Fat . . . . . . MTJNK (J.) and A. ROSENSTEIN. Human Lymph and Chyle . . . ROSIN (H.). Indigo-red (Indirubin) in Urine . . . . . . . PATsrN (G.). Analysis of Pathological Liquids . . . . . . SPITZER (W.). Action of Opium and Morphine on the Intestine . . FALKENBERG (W.). Poisoning by Aniline, Chlorates, and Mercuric Barley, Swedes, and Rice Meal . . . . . . . Influence of Alkalis on the Glycogen of t.he Lirer . Xli PAQE 593 595 596 5% 596 597 598 599 600 t100 601 601 601 602 751 V 52 752 752 753 753 754 754, 755 755 757 757 755 758 759 7 ti0 760 761 761 762 762 845 846 846 847 847 8a 84.8 849 849 850 85 1 852 Chloride.. . . . . . . . . . . . 853xlii CONTENTS. PAGE (HEBER (A.). Physiological Action of Lupetidine and Allied Substances in relation to their Chemical Constitution . . . . . . . D’APSONVAL (A.). Use of Liquefied Carbonic Anhydride for the rapid Filtration and Sterilisation of Organic Liquids . . . . . RACHPORD (B. K.). lntluence of Bile on the Fat-splitting Properties of Pancreatic Juice . . . . . . . . . . , CHITTENDEN (R. H.) and F. P. SOLLEY. Digestion of Gelatin . . . CHITTENDEN (R. H.) and R. GOODWIN. Myosm-peptone . . . . NISSEN (W.). Influence of Alkalis on the Secretion and Composition of Bile SAPTOPI (G.).Chemistry of Sheep’s Milk Cheese . . . . . CHITTENDEN (R. H.) and J. A. HABTWELL. . HORTON-SMITH (P.). Peptonised food^ . . . . . . . WRIGHT (A, E.). Intravascular Coagulation . . . . . . RINQER (S.) and H. SAINSBUPY. . HAYCRAPT (J. B.). New Method for Estimating the Specific Gravity of the Blood . . . . . . . . . . . . . FREUND (E.) and F. OBERMAYEP. The Blood in Leucocythsemia . . ARAKI (l’.). . ZLLLHSSEN (H.). Lactic Acid and Glucose in Organs with Impeded Circu- lation and in Hydrocpnic Acid Poisoning , . . . . , KOSSEL (A.). Chemical Composition of the Notochord . . . . HAMMARSTEN (0.). Mucoid dubstanco in Ascitic Fluid . . . . GOTTLIPB (R.). Excretion of Iron . . . . . . . . WOLKOW (M,) and E. BAUMANN. Alcaptonuria . . . . . . WINTLPNITZ (H.). Proteid in Normal Urine .. . . . . I?;ALEOWSKI (JL.). Haematoporphyrin in Urine . . . . . . MCKENDPICE (J. G.) and W. NODG GRASS. Physiological Action of Nickel Carbon Oxide. . . . . . . . . . . . MAWET (W.). Human Respiration, Air being Re-breathed in a Closed Vessel . . . . . . . . . . . . . MAPCET (W.). The Respiratory Exchange of Gases . . . . . CASH (J. T.) and W. R. DUNSTAN. Action of Paraffin Nitriles on Blood Pressure. . . . . . . . . . . . BIEBNACKI (E.). Influence of Temperature on Digestivo Ferments . . EDKINS (J. d.). . CHITTENDEN (R. H.), C. NORRIS, and E. E. SXITH. Influence of AIcohol on Proteld Metabolism . . . . . . . . . . STUDEYUND. Proteld Requirements of Healthy Men . . . . . BPINCK (J.). Nutrition of Muscle . . . . . . . . BRADFORD (J. E.). Etfect of Partial Extirpation of the Kidnejs on Nutri- tion .. . . . . . . . . . . . NOVI (I.). Influence of Sodium Chloride on the Chemical Composition of the Brain . . . . . . . . . . . . DELBPINX (H.). Deposits of Iron and Glycogen in the Tissues . . . HEPFTEP (A.). Lecithin in the Liver . . . . . . . . ORAFFENBERQER (L.). Composition of the Bones of Aged Rabbits . . SIEDEL (J.). Amount of Fat and Dry Matter in the Milk of some Hill- bredcows . . . . . . . . . . . HENKEL (T.). Citric Acid a Normal Conatiiuent of Milk . . . . SCBEIBE (A.). Origin of Cilaic Acid in Milk . . . . . . CAXERER (W.). Nitrogenous Substances in Human Urine . . . . HOYPE-SEYLER (G.). Urobilin in Various Diseases . . . . . HALLIBUPTON (W. U.). Hrenmtoporphjrinuria . . . . . . BRELIOZ (A.).Rhinoliths . . . . . . . . . . BRUNTON (‘l‘. L.) and J. T. CASH. Chemical Constitution and Physiological Action . . . . . . . . . . . . . GIBBS (W.) and E. T. REICHERT. Action of Related Compounds on Animia . . . . . . . . . . , . RINGEB (S,). Caseinogen . . . . . . . . . SEBELJN (J.). Proteids of Milk . . . . . . . . Proteoses and Peptones . Action of Salts on Heat Coagulation Formation of Lactic Acid and Glucose in the Orgtlnism . Action of Pancreatic and Rennet Extracts on Cdseyn. 854 854 948 9441 950 950 951 951 951 953 053 953 954 1123 1124 1125 1126 1126 1127 1128 1128 1130 1130 1130 1270 1270 1270 1271 1272 1272 1272 1273 1273 1274 1274 1275 1275 1275 1%76 1276 3 277 1278 1279 1279 1279 1280CONTENTS . xliii HUNTER (W.). Tuberculin . . . . . . . . . .Roos (E.). Carbohydrates in the Urine . . . . . . . ARAEI (T.). Formation of Lactic Acid and Glucose in the Organism . . KERN (E.), H . WATTENBERG. and T . PPEIFFEB . Influence of Work on the Material Exchange of Sheep . . . . . . . . . HORBACZEWBEI (J.). Production of Leucocytosis in Mammals . . . GIBBB (W.) and E . J . REICEIERT . Action of definitely related Chemical Compounds on Animals . . . . . . . . . . SOHLESINGER (A.). Diastatic Action of Human Saliva . . . . FERMI (C.). Gelatin as a Retlgent lor Enzymes . . . . . . " Neutral Sulphur .. and Metaholism . . . . . . WRIGHT (A . E.) . Tissue Fibrinogens . . . . . . . . MWNY (I.). 1)ecomposition of Albumin in Fasting . . . . . K ~ N I G (J.). Importance of Aeparagine for Feeding . . . . . ALCERTONI (P.). Action of Sugars in the Body . .. . . . NEBELTHAU (E.). Formation of Glycogen in the Liver . . . . JONES (E . L.) . Speci6c Gravity of the Blood RWDENEO . HARN (M.). Influence of Sulphonal on Proteld Metabolism . . . HIRSCHFELD (F.). Influence of Increased Muscle Activity on the Decom- position of Albumin . . . . . . . . . . Influence of Acid Mineral Salts on the Composition of Bones . . . . . . . . . . . . . WBISEE (H.). . . . . . . ARTHWS (M.). Glycolysis in the Blood FBEWDBEUQ (A.). Influence of Acids and Alkkis An tde Aiktllinity 0; Human Blood, and on the Reaction of the Urine . . . . . KLINGENBEBG (K.). Oxidation of Aromatic Substances in the Animal Orgrtnism . . . . . . . . . . . . NEBELTHAW (El) . Formation of Gtlycuronic Acid during Inanition . . WOOD (H .C.) and J . MARSHALL . . LABBB-(D.) and OWDIN . Therapeutic and Physiological Effect of Ozone . KOBERT (R.). Saponins . . . . . . . . . . SALOMON ((3.). Xanthine Substances in Urine . . . . . . Elimination of Urea in Fever . BINZ (C.). Quinine as a Protoplasmic Poison . . . . . . Chemisti y of Vegetabts Physiology and Agriczcltwe . MIQUEL (P.). The soluble Ferment of Urea . . . . . . LEONE (T.). Nitrification and Denitrificrttion in Soils . . . . . LEONE ('I.). Reducing Power of Micro-Organisms . . . . . DEBRAYX and LEGRATN . Biogenesis of Hydrogen Sulphide . . . . JWMELLE (H.). Ctdorophyllic Assimilation of Trees with Bed Leaves . BOUBQWELOT (E.). Sugars in Mushrooms . . . . . . . MAREE ((3.). Loss of Sugar in Beetroot . . . . . . . BUSGEN (M.). Behaviour of Tannin in Plants .. . . . . PAQNOWL . Cultivation of Wheat in Sterile Siliceous Soils . . . . THoMsoN ( A.). Behaviour of Sandy Soil towards SuperpLosphate . . STOELABA (J.). Composition of Bone-Meal . . . . . . . MEBZ (J.). Amount of Fat in Bone-Meal . . . . . . . NEWMAYER (I.). . SCBWLZE (E.). Chemical Composition of Vegetable Cell Membranes . . TAHARA (Y.). Crystalline Constituents of the Seed of Cataputim minoris . KUHN (M.). Examination of Potato Spirit Liquor . . . . . Action of Yeast on the Animal and Human Organism HEWELEE (0.). Antiseptic Properties of Sodium Fluoride . . . . LOEW (0.). Catalytic Reduction of the Sulphonic Group . . . . BERTRAM (J.) and E . GILDEMEISTER . Kesso Oil . . . . . LORW (0.) . Poisonous Action of Hydrazine . . . . . . WCLEY (H .W.). Composition of Sorghum Seed . . . . . . FERNBACH (A.). Apparatus for the Cultivation of Pure Yeast . . . PAQID 1283 1393 1392 1392 1302 3393 1522 1523 1523 1523 1524 1524 1524, 1525 1525 1526 1526 1527 1528 1628 1528 1529 1529 1530 1531 1531 1531 100 101 102 102 102 103 1u3 104 104 105 105 105 106 %37 237 237 238 238 238 239 24Q 352xliv CONTENTS. PAGE FRANKT~AND (P. F.) and G. C. FRANKLAND. The Sitrifying Process and its Specific Ferment . . . . . . . . . . . 352 HANEIN (E. H.). A Bacteria-killing Globulin . . , . . . 352 CHABBIB (C.). Antiseptic Action of Methylene Fluoride . . . . 353 ATWATEK (W. 0.) and C. D. WOODS. Acquisition of Atmospheric Nitrogen by Plants . . . . . . . . . . . . 353 SOHLOESIKQ (T. jun.) and E. LAURENT. Fixation of Gaseous Nitrogen by Leguininosm .. . . . . . . . . . . 353 FRANK (B.). The Fungus Symbiosis of the Leguminoss . . . . 353 REISS. Nature of Reserve Cellulose and its Mode of Solution during Germination of Seed , . . . . . . . . . 356 MARCACCI (A.). Conversion Products of Starch . . . . . . 337 FORTI (C.). Presence of Cholesterol and a Soluble Carbohydrate in Melon Seeds . . . . . . . . . . . . . 357 PAUL (B. H.) and A. J. COWNLEY. Amount of Thelne in Tea . . . 358 SAARE. Acidity of Potato Starch. . . . . . 358 ARMSBY (H. P.) and W. IT. C'ALDWELL. EFFEONT (J.). Action of Miiieral Acids on the Lactic and Butyric Fer- mentations . . . . . . . . . . . . 488 HIRSCHFELD (E.). Influence of Artificial Gastric Juice on the Acetic and Lactic Fermentations . . . . . . . . . . 488 MAXWELL (W.).Behaviour of the Fatty Substances and the rdle of Lecithins during Normal G'erminatioii . . . . . . . . . 489 HILGER (A.) and F. VAK DEB BECKE. Change in the Nitrogenous Substaucev of Barley during Germination. . . . . . . . . 489 GUIGNARD (L.). Localisation of Active Principles in the Seeds of Crucifer= 490 SCHULZE (E ). Nitrogenous Bases in Seeds . . . . . . . 490 Przzr (A.). Composition of the Leaves of Maclura auvantiacu . . . 490 FOEMENTO (E.). Behaviour uf soine Vegetable Substances towards Copper and some of its Compounds . . . . . , . . . 491 ATWATER (W. 0.) and C. D. WOODS. Acquisition of Atmospheric Nitrogen by Plants . . . . . . . . . . . . 491 L'H~TE (L.). The Nitrogenous Substance of Arable Soil . . . . 492 KNIERIEM (W. v.). Effect of Artificial Munilring on Clover Land and Medows .. . . . . . . . . . . 492 DEH~RAIN (P. P.). Experimental Plots of Mangold arid Sugar Beet at Chignon, in 1890 . . . . . . . . . . . 493 STORCH (V.). The Souring of Cream . . . . . . . . 603 SCHOMPER (A. F. W.) [? SCHIMPER]. Assimilation of Mineral Salts by Green Plants . . . . . . . . . . . . 604 MBE (E.). Influence of Internal Causes on the Presence of Starch in Leaves . . . . . . . . . . . . . 604 ERABBK ((3.). Action of the Diastase Ferment on Starch Grains within the Plant . . . . . . . . . . . . . 605 WAAQE (I!.). Formation of Phlorogliicinol in Plants . . . . . 605 BEETHELOT and G. ANDR~. Presence and Function oE Sulphur in Plants . 606 G~EARD. Fats obtained from the Furgi Lactarius vellerew and L. p?perat?us . . .. . . . . . . . . 606 LIEIERNIK (A.). Constituents of the Seed Pods of Pisurn sativum and Phascolua vulgaris . . . . . . . . . . . 606 PRAZMOWSKI (A.). Root Nodules of the Pea . . . . . . 607 BEUTHELOT and G. ANDH~. Nitrogen Compounds in Vegetable Soils . . 610 BERT HELOT. Volatile Nitrogen Compounds evolved from Vegetable Soils . 611 KOSTYTCHEPP (P. A.). Formation and Properties of Humus . . 611 MAEBCKEB (M.). Root . . . . . . . 612 CROOKSHANK (E. 'M.) i n d E. F. HERROWN. Tubercle Bacillus . . . . . . . . . . . 762 Maize'Dried in the Field and as Silage . . . . . . . . . . . . 359 BOSSHARD (E.). Wine Analyses. . . . . . . 359 Economy of Phosphoric Acid in the Growth of Beet Cultivation Prodiets of theCONTEXTS. XlV PAGE SCHARDINGER (I?.). Bacterial Decomposition of Cane-sugar with Forma- tion of a New Lactic Acid .. . . . . . . . VILLIERS (A.). Conversion of Starch into Dextrin by the Butpic Ferment. SAPOSCHNIEOFF (W.). Formation and Migration of Carbohydrates in Leaves . . . . . . . . . . . . . FBAKK (E.). Assimilation of Nitrogen from the Air by Bobinia p e u d - acacia . . . . . . . . . . . . . VAN Srmm (L. L.). Analysis of the Milk of Ripe and Unripe Cocoanuts . LASKOWSEY (N.). Analysis of Beetroot Seed . . . . . . ~ ~ E H ~ R A I N (P. P.). Composition of Drainage Waters . . . . . LINOSSIER ((3.) and G. ROTJX. Alcoliolic Fermentation and the Conversion of Alcohol into Aldehyde by " Champigtion du Muguet " . . . FRANK (B.) and R. OTTO. Assimilation of Xitrogen by Plants . . . AVBERT (E.). Simultaneous Erolution of Oxygen and Carbonic Anhydride by Cactse.. . . . . . . . . . . . LESAGE (P.). Influence of Salt on the Fermentation of Starch in Vegetable Organs containing Chlorophyll . . . . . . . . WORTMANN (J.). Presence and Function of Diastasein Plants . . . 8cavLzE (E.). Formation of Nitrogenous Organic Bases by the Decompo- sition of Prote'ids in the Vegetable Organism. . . . . . KOHL. Physiological Importance of Calcium Oxnlate in Plants . . . MONTEVERDE. Calcium end Magnesium Oxalatc iu Plants . . . . IJERTHELOT and ANDRB. Peculiar Odour of s o i l . . . . . . STUTZER (A.). Analyses of Fodders . . . . . . . . MAYBR (A.). Climatic Conditions for the Development of Nicotine in Tobacco Plants . . . . . . . . . . . DEHERAIN (P. P.). Drainage Waters from Bare and Cultivated Soils .FERRY (R.). Sugars present in Fungi . . . . . . . , PIZZI (A.). Composition of the Leaves of Maclura ausnntiaca . . . BRISI (G.) and T. GIGLI. Cheniicd Composition and Anatomical Struc- ture of the Fruit of the Tomato (Lycopwsicarn wculenta) . . . PassEaINI (N.). Composition of the Fruit of Toniatos (Solanurn lyco- persicurn) . . . . . . . . . . . . LINTNER (C. J .). Non-nitrogenous Extract-substance from Barley, Malt, and Beer. . . . . . . . . . . . . OSWALD (F.). . WARDEN (C. J. He). Soil containing Iron and Chromium from the Andaman Islands, East Indies . . . . . . . . MAYER (A.). Soil AnalyPes . . . . . . . . . . WLADIMIROFF (A.). Osmotic Experiments on Living Bacteria . . . ABNATJD (A.) and A CHARRIN. Secretions of Microbes . . . . JUMBLLE (H.).Assimilation by Lichens . . . . . . . LmmE (P.). Influence of Salt on the Quantity of Starch contained in the Vegetating Organsof Lepidium salivum. . . . . . . MERCK (E . Dextrose from lpecacuanha Root . . . . . . TEUMMEL t!.) and W. KWASNIK. Macassar Oil. . . . . . KURSTEN (R.). Constituents of Rhizoma Podophylli . . . . . DH MARNEFPE ((3.). Decomposition of the Silicates in Soil by Lime and Gypsum. . . . . . . . . . . . . LAWRENT ( g . ) . Value of Nitrates and Ammonium Salts aa Foods for Fer- ments and other Plan1.s. . . . . . . . . . CABLES (P.). Charact'eristics of Fig Wine . . . . . SCLAVO and Gosro. New Fermentation of Starch . . . OPITZ (E.). Fat and Ethereal Oil of Sabadilla Seeds . . . . . OPITZ {E.). Fats of Amanitapastherina and Boletus luridus . .. OSBORNE (T. B.). ProteSds of Oat Kernels . . . . . . . H%BERT. Development. of Wheat., and Formation of Starch in the Grain . 'I'SC~IRCH (A.). Formation of Phlobaplienes . . . . . . KELLNER (O.), KOZAI (Y.), and Y. MOBI. Changes occurring during Ensilage . . . . . . . . . . . . Constituents of the Fruit and Seeds of Illicium anisaturn 763 363 763 564 764r 764 765 854 855 856 856 856 856 857 857 858 858 858 859 954 954 955 956 957 957 958 958 1131 2132 1132 1133 11 33 1133 1133 1135 1135 1135 1 2 M 1284 1285 1285 1285 1287 1287xlvi CONTENTS. ARNAUD (A.) and A. CHARRIN. Transformation and Elimination of Orgamc Matter by the Pyocyanic Bacillus . . . . . . . . SPAMPANI (G.). . NICKEL (E.). Physiology of the Tannins and Trihydroxybenzenes . . S z r u s s ~ (2.v.) and A. CSERHATI. Experiments with Green Maize . . MWNTZ (A.). Formation of Nitrates in Soils . . . . . . ROBERTS and WINQ. Depreciation of Manure by Exposure to Wet and Fermentation . . . . . . . . . . . ELIOX (H.). Mnnufactmre of Pure Yeast . . . . . . . EFPRONT (J.). . BOUTROVX (I,.). Bread Fermentation . . . . . . . NOBBE (F.), E. SCHMID, L. HILTNEB, and E. HOTTER. Nitrogen Absimila- tion of the Leguminose. . . . . . . . . . BBPERINCK (M. W.). Artificial Infection of Viciafabu with Bacilluv rudi- cirola . . . . . . . . . . . . . BOKORNY (T.). Formation of Starch from Formaldehyde . . . . KEIM (W.). Ripening of Cherries. Fermentation of Cherry and Currant Juice, and Colouring Matters of Red and Black Currants . . . SCHULZE (E.). E. STEIGER, and W. MAXWELL.Chemical Composition of some Leguminous Seeds. . . . . . . . . . PICHARD (P.). . WINOGRADSKY (S.). Formation and Oxidation of Nitrites in Soils . . PAGNOUL. Nitric and Animonirtcal Xitrogen as Manures . . . . TOGEL (J. H.). Loas of Nitrogen during Decomposition of Nitrogenous Organic Matter, and the Means of Limiting or Assisting it . . . XELLNER (O.), Y. KOZAI, Y. MORI, and M. NAGAOKA. Manuring Experi- ments with Rice , . . . . . . . . . . Substitution of Manganeee for Iron in Plant Nutrition Action of Hydrogen Fluoride and of Fluoridea on Yeast Influence of Iron and Calcium Sulphates on Nitrification Ana 1 y tica 1 Chemistry. MULIJER (J. A). Estimation of Hydrogen Chloride in Solutions of Hydroxylamire Hydrochloride . . . . . . . BLUM (L.). Estimation of Sulphur in Inorganic Sulphides .. . . COCHIUS (F.) and T. MOELLRR. Estimation of Nitrogen by the Schultztt- Tiemann (Schloeesing’R) Method . . . . . . . . FOERSTER (0.). Estimation of Nitrogen in Sodium Nitrate . . . SCHEIDTNG (F.), Estimation of Nitric Nitrogen as Nitric Oxide. . . WAQNER (R. L.). Estimation of Nitrogen in Organic Substances by Means of Alkaline Yermanganate . . . . . . . . . BLUM (L.). Detection of Foreign Raw Phosphates in Powdered Brtsic Slag . STOCELASA (J.). Estimation of Water in Superphosphates. . . - FRESENIUS @.). Separation of Barium from Strontium . . . . RUSSMANN (A.). Separation of Barium, Strontium, and Calcium . . MINOR (W.). Estimation of Cadmium in the Products of Zinc Manufacture and in Calamine . . . . . . . . . . . MINOR (W.). Estimation of Cadmium aa Sulphide by Precipitation with Sodium Bulphide Solution .. . . . . . . . DONATE (E.) and G. HATTENSAUE. Volumetric Estimation of Zinc and Copper . . . . . . . . . . . . . BEUF (H.). Estimation of Lead by Phosphomolybdic Acid . . . . MCCAY (L. W.). Separation of Copper from Arsenio by the Electric Current . . . . . . . . . . . . . ELEMP (G.). Estimation of Aluminium in Commercial Aluminium . . YOUNG (W. C.). Solubility of A h - JONES (R.). Estimation of Iron Oxide and kluminrt in Phosphates . . ~ O L T ~ I E N (P.). . VAN BYLERT (A.). Estimation of Antimony by Narsh’e Method . Eetimation of Alumina in Bread, &c. minium Phosphate in Acetic Acid . . . . . . . Titration of Chromat,es, Rarium Salts, and Rulphates . PAGE 1394 1394 1395 1395 1395 1395 1532 1532 1532 1533 1 S39 1539 1539 1541 1543 1345 1545 1547 1547 107 107 107 107 107 109 109 110 110 111 112 112 112 113 114 114 114 114 115 115COKTENTS.xlvii NEUGRBAUER (E . L.). Estimation of Hardness of Natural Waters . . DICEMANN (F.). Examination of Water for Contanhation by Qas-Worke . SEYDA (A . ). Detection and Estimation of Organic and Inorganic Poisons Roos (L.) and E . TPOMAS . Method of Distinguishing between Plastered VITALI (D.). Analysis of Siilphureous Waters . . . . . . in Corpses . . . . . . . . . . . . HAQRR (H.). Detectio~ of Paraffin in Beeswax . . . . . . Wines and Wines mixed with Sulphuric Acid LiszL6 (E.). Estimation of Dissolred Solids in Wine . . . . MUTER (J.). Detection of Mathylated Nitrous Ether . . . . . glucinol .. . . . . . . . . . . KUHN (M.). Estimation of Sugar in Milk . . . . . . . MINOR (W.). Estimation of Ash in Raw Sugar . . . . . . REINEE (0.). Estimation of Starch . . . . . . . . CoLasaNTr (a.) . New Application of Molisch's Test . . . . . COLASANTI la.). Reaction of Thiocvanic Acid . . . . . . . . . . MUTER (J.). Analysis of Carbolic and Sulphurous Disinfecting Powders . HERZIG (J.) and 5 . ZEISEL . Detection of Diresorcinol in Synthetical Phloro- OST (H.). Estimation of Sugars by Means of Copper Potassium Carbonate Solution . . . . . . . . . . . . . NIEDERHAusER (E.). Schneider's Method for the Estimation of Malic Acid inWine . . . . . . . . . . . . . T ~ T R (J.). Comparison between Methods for the Esliniation of Tartaric Acid . . . . . . . . . . . . Estimation of Tartaric Acid in the Crude Products of Tartaric Acid Factories .. . . . . . . . . . WOLFMANN (J) . Estimation of Tartaric Acid . . . . . . CLAAsEN (E.). Estimation of Citric Acid in Parts of Plants VIOLLETTE (0.). Optical AnalSsis of Butters . . . . . . MUTER (J.) and L . DE KONINGH . Analyses of Lard . . . . . WILLIAMS (R.). Estimation of Resin in Soap . . . . . . FOERSTER (F.). Estimation of Camphor . . . . . . . MALTscHEFFsKY (P.). Esrimation of Tanin in Tea . . . . . MIQUEL (P.). Estimation of Urea . . . . . . . . HEATON (C . W.) and S A . VASEY . . WARDEN (C . J . H.). Rapid Method of Estimating Urea in Urine . . SPENCER (U . L.). Estimation of Thei'ne in Tea SEATON and H . D. RICEMOND Estimation of Quinine DA SILVA (F.). Reaction of Coca'ine . . . .. . . . OBOLONSKI (N.). Detection of Colcbicine in Corpses JOLLBS (A) . Detection of Bile Constituents in Urine JoLms (A.). Detection of Albumin in Bacterial Urines . . . . ADENEY (W . E.). Gas Appamtus . . . . . . . . F~RSTER (0.). Lacmold . . . . . . . . . . TELBISZ (J.). CoaBsrTA (P.). Amount of Volatile Fatty Acids in Rancid Butters . . VIOLLETTE (C.) Butter and Margarine . . . . . . . . . . . . . . . . . . . . BUISINE (A.) and P BUISINE Beeswax Simple Method of Estimating Urea . . . . . . . . . . . . . . . . . . . . . . . . . . . . . JOLLES (A.). New Test for Albumin MINOR (W.). Estimation of Free Hydrochloric Acid in Stannous Chloride Solutions . . . . . . . . . . . . . SAULZBR (T.). Detection of Hypochlorous Acid in Chlorine Water . JOHNSTONE (A.). Detection of 'Traces of Iodine in the Presence of mu& Chlorine .. . . . . . . . . . . . DONATH (E.). Separation and EetimnLion of Tellurium . . . . AMAT (L.). Estimation of Hypophosphorous, Phosphorous, and Hypophos- REITMAIR (0.). The 4'Citrate Method" of Phosphoric Acid Esiimation : ( 3 0 0 ~ ~ (F . A.) and P . E . BBOWNINQ . Reduction of Arsenic Acid in KABSNER ((3.1. Estimation of Peroxides of the Alkaline Earths . . phoric Acids . . . . . . . . Analysis . . . . . . . . . . . . PAQE 116 116 117 117 122 123 123 123 124 123 125 127 127 127 128 128 128 128 129 129 129 130 130 130 130 131 131 131 132 132 133 133 134 134 134 135 135 136 136 240 241 241 242 242 242 243 243 244s 245xhiii CONTENTS . PAQB STUTZER (A.). BAUMANN (A*) . VANINO (L.). ROSEXHEIM (A.).EstiGation of Vanadic Acid in Vanadotangstates . . 247 Eetimation of Ferric Oxide and Alumina in Phosphatic Valuation of Pyrolusite by means of Hydrogen Peroxide . T'itration of Permanganate and of Bleaching Powder by Mannres . . . . . . . . . . . . . 245 2.15 Hydrogen Peroxide . . . . . . . . . . 246 HOPFMANN (H . 0.) Drv Assay of Tin Ores . . . . . . 2443 ZALOZIECKI (R.). Estimation of Ferrocpanides . . . . . . 247 SAEQEN (J.). Estimation of Sugar in Blood . . . . . . 248 OBERMEYBR (F.). Modification of Jaffgs Inclimn Test . . . . 248 WARREN (T . T . P . B.). SCALA (A.). Examination of Oils, Fat.@, and Allied Substances . Estimation of Formic Acid in Presence of Acetic and Butyric 248 Acids . . . . . . . . . . . . . 248 GR~GER (M.). iodometric Estimation of Acids and Alkalis .. . . 360 FAIRLEY (T.). of Uranium . . . . . . . . . . . . 360 GOOCH (F . A.) and J . R . ENSIQN . Mixtures of Alkaline Rromides and Iodides . . . . . . 361 GOOCH (F . A.) nnd F . T . BROOKS . WANKT. YN (J . A.). Priestlefs Method of Measuring Oxygen in Air . . 362 PHILLIPS (€I . J.). 362 ARWJTINSEY (P.). The Kjeldahl-Wilfarth Method . . . . . 362 ARNAUD . Cinchonfirnine as a Test for Nitrates . . . . . . 362 JONES (0.). Phosphorus in Pig.iron, Steel; and Tron'Ore . . . . 363 DENIGES ((3.). Distinction between Araenic and Antimony . . . 364 KIssLrNG (R.). Sodium Carbonates : Detection of Traces of Alkalino Hydroxides . . . . . . . . . . . . 3641 LUDEKING ((2.). Analysis of tbe Barium Group . . . . . . 364 STAHL (W.). Metallurgical Assay of Lead Waste .. . . . 365 LUNQE ((3.). Analysis of Sodium Aluminate . . . . . . 365 LUNQE (G.). Volumetric Estimation of Alumina . . . . . 365 MYHLERTZ (F . (3.). Estimation of Manganese in Slags . . . . 366 K~NNICUTT ( L . P.) and Q . W . PATTERSON . Chrome Iron . . . . . . . . . . . . 366 WARREN ( H . N.). Separationof Tin and Antimony . . . . . 366 LEYBOLD (W.). Estimation of Cyanogen Compounds in Coal-gas . . 367 ZALOZIECEI (R.). Estimation of Ferrocyanides in Gas Refuse . . . 367 ELION (H.). Analysis of Wort and Beer . . . . . . . 368 OLIVERI (V.) and M . QPICA . 369 JoLLEs (A.) The Cheinical Detection of GI!-cosu~ia . . . . . 369 BORNTRAQER (H.), Test for Resorcinol nnd Thymol . . . . . 370 COLLISCHONN (F.). Estimation of Acetone . . . . . . . 370 HUPPERT (EL) . Estimation of Acetone in Urine .. . . . . 370 SCHNEIDER (M.). 371 SCHNEIDER (M.). Estimation of Malic Acid in Wine . . . . . 371 PH~LIPS & CO . Analysis of Tartar and Wine Lees . . . . . 372 VITS (F.). Estimation of Caffe'ine in Tea . . . . . . . 372 BUJARD (A.) and A . KLINGER . Detection of the Coloiiring Matter of AlkannaRoot . . . . . . . . . . . 372 DENIGES ((3.). Detection of Chlorides. Bromides, and Iodides . . . 495 CORVI (A.). Volumetric Estimation of Chlorides in Urine . . . . 495 R O S E N ~ L D (M.). 496 RUBNER (M.). Detection of Carbonic Oxide in Blood . . . . . 496 LUNGE (G.). Anolyticul Methods for Alkdi Works . . . . . 496 WATSON (J.). Estimation of available Soda in Commercial Caustic Sods, . 408 MUSSET (F.). Test for Thiosulphate in Sodium Hjdrogen Carbonate .. 498 HTNTZ (E.) and H . WEBER . Analysis of Commercial Sodium Fluoride . 498 HINTZ (E.) and H . WEBEB . Analysia of Commercial Barium Hydroxide . 499 Detection of Minute Quantities of Hydrogen Peroxide and Direct Estimation of Bromine in Detection of lodine, Bromine, and Chlorine in presence of one another . . . . . . . 361 Estimation of Sulphur in Copper . . . . . Estimation of Chromium in Volumetric Estimation of Glycerol in Wine . Estimation of I3 ydrogen Potassium Tartrate, Free Tar- taric Acid. Malic Acid, and Mineral Salk in Wine . . . . . Eat imation of Nitric arid Nitrous Acid in Fotable WatersCONTENTS. xlix FREsENIUs (I%.). Separation of Barium from Ctdcium . . . . CARNOT (A.). Detection and Estimation of Small Quantities of Alumhiium in Iron and Steel .. . . . . . . . . . GRUBER (v.). Estimation of Ferric Oxide and Alumina in Phosphates . HPFFMANN (H. 0.). Dry Assay of Tin Ores . . . . . . MOHLER (E.). Analysis of Brandy and Alcoliol . . . . . . SCHENCE (F.). Estimation of Sugar in the Blood . . . . . HIESCHSOHN (E.). Testing Oil of Cawia . . . . . . . HOLDE. Estimation of Acidity in Lubricating Oils . . . . . GRITTNEB (A.). Estimation of Mineral Oils in Fat, Oils . . . . WARREN (T. T. P. B.). Estimation of Oils, Fats, &c. . . . . . WARREN (T. T. P. B.). Examination of Oils, Fate, and Allied Substances . BBIJLL~~ (R.). Adulteration of Olive Oil . . . . . . . BRTJLLE (R.). Analysis of Olive Oil and Seed Oils, Butter, and Margarine . VIETH (P.). Composition of Butter Fat as Determined by Lhe Reichert- VIETH (P.).Analjsis of Butter Fat by the Reichert-Wollny Method . . SJ~STROY (A.). Marchand‘s Method for Estimating Fat. in Milk . . BABCOCK (S. JI ). New Metbod for the E8timtltion of Fat in Milk . . LEWEOWITBCH (J.), Analysis of Fats . . . . . . . . MAXWELL (W.). Estimation of the Fatty Substances in Vegetable Organ- isms . . . . . . . . . . . . . DIBTERICH (E ). Estimation of Morphine in Opium . . . . . KREMEL. Estimation of Colchicine in Colcllicum Seeds , . . . MILKOWSKI (2. v.). Examination of Brewers’ Pitch . . . . . SMITH (S. H.). Estimation of Urea . . . . . . . . R~~DORFP {F.). Weighing Dried Filters . . . . . . JOLLES (A.). New Method of Estimating Uncombined Hydrochloric Acid in Gtastkic Juice . . . . . . . . . . . GROGBE (M.). Potassium Iodate as Original Standard for Iodometry, Acidimetry, and Alkalimetry .. . . . . . . . DENIQ~S ((3.). Potassium Bromide as Indicator in Chlorimetry . . . VAN~NO (L.). Technical Valuation of fileaching Powder . . . . OFFE~MANN (H.). Estimation of Fluoriiie . . . . . . . DE KONINCII (L. L.). Gasouetric Absorption of Oxygen . . . . LINossIsa ((3.). Estimation of Oxygen Dissolved in Water . . . LB ROY ((3. A.). Volumetric Estimation of Sulphur Dichloride . . . LUNQE ((3.). Purification of Sulphuric Acid for Kjeldahl’s Process . . STDTZER (A.). Estimation of Nitric Nitrogen by Alumiiiium . . . ULSCH (K.Y. Estimation of Nitric Acid by Reduction to Ammonia . . DE KONINCK (L. L.) and A. NIHOUL. Ioclometric Estimation of Nitrates aid Chlorates . . . . . . . . . .. GUILLAVME-GENTIL (B.), Estimation of Phosphoric Acid in Urine . CASSAL (C. E.), Detection and Estimation of Boric Acid in Milk and Cream . . . . . . . . . . . . . JANNAscH (P.). New Method for Decomposing Silicates . . . . STEWART ((3. N.). Estimation of Inorganic Salts in Small Quantities of B l o o d . . . . . . . . . . . . . GEITTNEE (A.). Estimation of Zinc and R’itrogen in Pickled Railway Sleepers . . . . . . , . . . . . . THOM~ (E.). Detection of Traces of Copper in Distilled Water . . . REIs (M. A. v.) and F. WIGGERT. . OSEX (J.). Elementary Analysis by an EIectrothermal Method . . . DELISLE (A.). . BERTHELOT and (3. ANDEB. Estimation of the Inorganic Constituente of Soils . . . . . . . . . . . . . STTJTZEE (A.) and 0. REITMAIR. Estimation of Fuse1 Oil in Spirits .. SCHEIDINQ. Analysis of Dyilamite . . . . . . . . CRISMEB (I,.). Potassium Mercuro-iodide as a Reagent for Aldehydes . SALKOWSEI and T. TANIG~TI. Acetone in Urine. . . . . YOL. LY. d Wollny Method . . . . . . Volumetric Estimation of Cobalt . New Potash Apparatus for Use in Elementary Analyses PAQE 600 501 501 602 503 504 504 505 505 505 506 506 606 507 603 508 503 503 511 511 512 512 512 6 13 613 614 615 615 615 616 616 617 617 61 7 617 618 619 619 619 619 620 620 620 621 621 622 622 623 624 6241 CONTESTS. PAGE WAUNER. Urochloralic Acid in Urine. . . . . . . . 624 BTJISINIC (A.) and P. BUISINE. White Wax . . . . . . . . . . . . 625 EDKINS (J. S.). Modified Fat Extraction Apparatus . . . . . 625 GORODETZKY (VT.). Estimation of Fat in Milk . .. . . . 625 JEAN (I?.). The Oleorefractometer . . . , . . . . 625 VENTTJROLI (F.). Volumetric Estimation of Albumin in Urine . . . 627 PATUREL ((3.). Estimation of Humus in Soil by Raulin's Process . . 62'7 BEHRENS (H.) . Reactions 'for Microcheniical Mineral Analysis . . . 766 CHATARD (T. M.). Apparatus for the Estimation of Wnter in Mineral Analysis. . . . . . . . . . . . . 766 FAWIZKY (A.). Detection and Estimation of Hydrochloric Acid in Gastric Juice . . . . . . . . . . . . . 767 MAGNIER DE LA SOURCE (L.). Mode of Combination and Detection of Sulphuric Acid in Plastered Wines, and detection of the Free Acid in Wines . . . . . . . . . . . . . 768 CHATARD (T. M.). Separation of Titanium, Chromium, Aluminium, Iron, Barium, and Phosphoric Acid in Rock Analysis .. . . . 768 DE CEALMOT (G.) and B. TOLLENS. Estimation of Pentaglucoses (Pentoees) in Vegetables . . . . . . . . . . . . 768 STRIEGLER. Estimation of Invert Sugar in Molawes . . . . . 769 LOGES ((3.) and C. CLAESBEN. Estimation of Free Fatty Acids in Fodder. 770 REITMAIR (0.). Alterability of some Food Fats . . . . . . 770 WAAGE (T.). Detection of Tannin in Plants . . . . . . 770 MORNER (I(. A. H.) and J. SJOQUIST. Estimation of Urea. . . . 771 PEZZOLATO (A.). Estimation of Nicotine in Presence of Ammonia . . 772 LOOF (G.). Ejtimation of Morphine' . . - . . . . . 771 PRUNIEE (L.). Assay of Quinine Sulphate by thc Ammonia Process . . 772 CIOTTO (F.) and P. SPICA. !L'oxicologid Observations . . . . 772 EDWARDS (V.). Ejeldahl's Process . . . . . . . . 862 ILosvAY (L.).minatinq Gas . . . . . . . . . . 862 BBETET (H.). Mineral Waters . . . . . . . . . . . 862 MINOR (W.). Estimation of Metallic Zinc in Zinc-dust . . . . 863 MINOR (W.) . taining Lead . . . . . . . . . . . . 863 WARWICK (A. W.). Assny of Lead Ores by the Cyanide Process . . 863 LBCCO (M. T.). Detection of Mercury in Toxicological Researches . . 864 BAYER (I(. J.). Analysis of Sodium Aluminate . . . . . . 864 BLABEZ (C.). Influence of Extractive Matter on the Real Alcoholic Strength of Spirits. . . . . . . . . . 865 HONIQ (M.). Estimation of Crude Fibre and Starch . . . . . E465 ZAUNSCHIRM (H.). Analysis of Celluloids . . . . . . . 866 LIEBERXANN (L.). Gum Arabic and Gum Senegal . . . . . 866 NICKEL (E.) . Formation, Detection, and Significance of Furfuraldehyde .865 MOHLER (E.). Bensitive Reaction for Tartaric Acid . . . 867 JOHNSTONE (W.). Estimation of Soluble and Insoluble 'Fatty Acids in Butter . . . . . . . . . - 868 FIRTSCH (G.). New Method for Testing the Purity oi But'ter . . . 868 VIOLLETTE (M.): Analysis of Butter . . . . . . . . 869 FILSJNGER (F.). Iodine Numbers forCocoa Butter . . . . . 869 WELLEMANN (C.). The Elaxdin Reaction with Fatty Oils . . . . 870 BAUDIN (E.). Oil of Resin in Oil of Turpentine. . . . . . 870 Ko110BINsKI (E.). Estimationof Tannin in Hops . . . . . 870 ANDREWS (L. W.). Detoction of Coniine in a Case of Poisoning. . . 871 HOLM (E.). Addition of Phenolphthalein to Mbargarin . . . . 872 MACWILLIAM (J. A.). New Test for Prote'idu . . . . . 8 7 2 TATE (W.). Dry Reactione in Qualitative Analys'is .. . . . 959 Bleaching of Beeswax: Composition of Detection of Sulphur not Combined with Hydrogen in Illu- Estimaion of Free and Combined Carbonic Anhydride in Estimation of Zinc Carbonate and Silicate in Calamine con- BENEDIKT (R.). Fnb Analpis . . . . 6 8 7 0CONTENTS. li HART (E.) and 13. CEOASDALE. Stnndardising Acidimetric and Alkalimetric Solutions. . . . . . . . . . . . SONDBK (K.). The Liquoscope: an Instrument for comparing the Re- fractive lndices of Liquida . . . . . . . . . ULSCH (K.). Estimation of Nitric Acid by Reduction to Ammonia . . ZECCHINI (M.). Nitrates in Wine . . . . . . . . METZ (E. E.). Densimetric Estimation of the Phosphorus in lron . . COOPER (W. J.). Assaying Lead Ores by Fusion with Potassium Cyanide. WAEN-ICK (A. W.).Assaying Lead Ores by Fusion with Potaseium Cyanide . . . . . . . . . . . . . LUDW~Q (E.) and E. TILLNEB. Estimation of Mercury in Animal Tissues. MOORE (I?.). Volumetric EJtimation of Manganese . . . . . JANNASCH (P.) and J. F. MAC(3EEQORY. Separation of Manganese and Zinc . . . . . . . . . . . . . BLUM (L.). Estimation of Manganese in Iron and Steel . . . . GRWBER (v.). Glaser’s Method for the Estimation of Ferric Oxide and Alumina in Phosphates . . . . . . . . . KATABEIN (El.). Tanniu in Urine . . . . . . . . YETNIEE (L.). Fmctional Crystallieation of Quinine Sulphate . . . SPENCBH ((3. L.). Estimation of The’ine i u Tea . . . . . . LUNGE ((3.). Measurement, of Cjtas~s . , . . . . . . MPLIUS (F.) and F. FOEBSTER. Estimation of Small Quantities of Alkali : Recognition of the Neutrality of Water .. . . . . DE KON~NCK (L. L.) and A. LECEENIEE. Estimation of Available OxTgen in Peroridea by Meaus of Gaseous Hydrocliloric Acid . . . . DARTRAM (H.). Xsttmation of Nitrates by the Phenolsulphonic Acid Method . . . . . . . . . , . . . TBEADWELL (F. W.). Estimation of Sulphur . . . . . . NEILSON (‘l’.). Estimation of 8ulphur in Coal, &c. . . . . . MAR (F. W.). Estimation of Barium as Sulphate . . . . . WARREN (H. N.). Separation of Cadmium and Copper . . . . MCKBNNA (A. (3.). Precipitation of Manganese as Am inonium Manpious Phospliute . . . . . . . . . . . . SHEPHERD (H. H. B.). Alcohol Method for Estimating Iron and Aluminium Oxidea 111 Yho~pbata . . . . . . . . . . LE ROY ((3. A.). Separation of Iron from Cobalt and Nickel .. . KRAUSS (C.). Separation and Estimation of Xickel and Cobalt . . . LONQ (J. H.) and J i . E. SAUER. Precipitation of Antimony from Solutions of Potassium Antimony Tartrate . . . . . . . . SMITH (E. F.). . JOLY (A.) and E. LEIDIE. Electrolytic Estimation of Rhodium. . . UEVPEL (W.) and L. M. DENNIS. Volumetric Estimation of Volatile Hydrocarbons . . . . . . . . . . . BORNTRAGEE (H.). Garon’s Aldehgde Reaction . . . . . . VraNoN (L.). Estimation of Acetone in Uenaturalised Alcohol . . . MAQWENNE. Use of Pl~enylhydrazine for the Estimation of Sugars . . KORSEL (A.) and M. KR~JQEE. Saponification by Means of Sodium Ethoxide . . . . . . . . . . . . WAPEEN (H, N.). Saponification of Tallow. . . . . . . GADD (W. L.) and 8. LEES. Estimation of Grease . . . . .KORNBR (A.). Analysis of Ole‘in. . . . . . . . . REP (H.). Burette Yloat for Opaque Liquids . . . . . . FEIEDHEIM (C.) and H. LEO. Xstimatiou of Free Hydrochloric Arid in the Presence of Acid Phoephates by Means of Calcium Carbonate . DENIG$S ((3.). Detection of Chlorine and of Chlorides in Presence of Bromides . . . . . . . , . . . . JOLLES (A. F.). Detection and Estimation of Iodine in Urine . . . CAZENEUVE (I?.). Mett~phenylmedimine as a Test for Active Oxygen . CRISPO (D.). Belgian Method of Estimating tho Soluble Phosphoric Acid of duperpliosphates . . . . . . . . . . Electrolysis of Metallic Phosphates in Acid Solution . . a 2 PAGE 959 959 960 96 1 961 962 962 963 968 963 863 963 ‘363 963 963 1135 1136 1136 1136 1137 1137 1137 1138 1138 1138 1139 1131) 1139 11M) 114-1 114,1 1142 1142 1142 1143 1 1 44 1144 1146 1288 1288 12% 1288 1289 1289lii COSTEXTS .MOEEE (F . X.). Assay of Ferric Hypophosphite . . . . . WARWECKE (H.). Bettendorf‘s Arsenic Reartion . . . . . Carbcnic Anhydride in Air . . . . . . . . . TSCHAPLOWITZ (F.). Estimation of Carbonic Anhydride . . . . WALLER (E.). Estimation of Lithium in Mineral Waters L EBFDINZEFF (A.). Modification of Pettenkofer’s Method of Estimating . . . . HEPPE (G.). . POLBTORPF (K.) and K . BULOW . Separationof Mercuric Sulphide from BLUM (L.). Voluiiietric Estimation of Manganese . . . . . REILSTE~N (F.) and R . LUTHER . Separation of Ferric Oxide from AIumina SMITH ( E . F.). Decomposition of Chrome Iron Ore by means of the Elec- tric Cnrrent . . . . . . . . . . . . NOYES (A) . Detection and Estimation of Titanium . . . . . LONG (.J . H.). Solubility of Thallium Iodide and Estimation of Thallium . THIELE (J.). Separation and Estimation of Antimony . . . . SMITH ( E . F.) and F . MUHR . Electrolytic Estimations BENEDIKT (R.) and M . BAMBRBCIEB . Action of Hydrogen Iodide on Sub- stances containing Sulphur . . . . . . . . . HAYCBAFT (J . B.). Estimation of Uric Acid in Urine . . . . STIFT (A.). Estimation of Ash in Raw Sugar . . . . . . OST (H.). Estimation of Sugars with Potassium Cuprocarbonate . . KNOWLES (J.) and J . A . WILSON . . . . SHUTT (F . T.). Asbestos Method of Milk Snalyeis . . . . . MOLIKARI (E.). Apparatus for the Estimation of Fat in Milk . . . HENZOLD (0.). Estimation of Water in Butter . . . . . . L%zB (B) . Detection of Margarin in Butter . . . . . . KOKIG (J.) and F . HART . . . . PHILLIPS (H . J.). . DVOREOVITCH (P.). Examination of Chinese Tea . . . . . DEPOTO (L.). Quantitative Estimation of Proterds . . . . . ELZINGER (H . 0 . G.). Strength of Solutions estimrited by their Refraction . SMITH (E . F.) and F . MUHR . . . . . KEBLEB (L . F.). Estimat.ion of Nitrogen and Nitrates by Kjeldrrhl’s Method . . . . . . . . . . . . MARTINOTTI (F.). . Estimation of Small Quantities of Silver in Lead Flux Sulphidesof the Arsenic and Copper Groups . . . . . BLUM (L.). Manganese Ammonium Ferrocyanide . . . . . . . . . Estimation of Milk Sugar Examination of Butter and Fates Estimation of Turpentine in Paints and Varnishes ElectrolyticSeparstions Estimation of Total Phosphoric Acid in Manure . LECLERE . Eatimation of Silica in presence of Iron . . . . . WIXTERNITZ (H.). Alkalinity of the Blood . . . . . . GONDOIN (J.). Estimation of Sodium Chloride in Wine . . . . ABELES (M.). Estimation of Sugar in Blood . . . . . . TOCHER (J . F.). SMITH (E . F.). Decomposition of Chromite by the Electric Current . . VIGNA (A.). . JEAN (F.). Analysis of a Mixture of Wax, Paraffin, Stearin, and Stearic Acid . . . . . . . . . . . . . VIZERN and C . NICOLAEI . . . . . Estimation of Tannin and of Free Tartaric Acid in Wines Detection of Sesame Oil in Olive Oil . . . . EstimRtion of Fats in Vaselin ELLINGEE (H . 0 . G.). Optical Analysis of Butter Fat ]<c€IN (M.). Estimation OF Fat in Milk . . . . . . . HAUBENBAK (W.). PAUL (B . H.). Estimation of Caffei’ne . . . . . . . . LAMBEHT ( A.). Estimatiori of Morphine . . . . . . . ELLINGEE (H . 0 . (3.). Optical Estimation of Albumin in Urine . . . Roux (J.). Estimation of Case% in Milk . . . . . . . OWEN ( F A.). Estimation of Indigotin . . . . . . . YRESENIUB (W.). ‘L‘he True Litre or Mohr’s fitre, for Volumetric Analysis . . . . . . . . . . . ~ [ A Y S (K.). Neutral Litmus Paper . . . . . . . . nExraBs ((3.). Test for Hvdrogen Peroxide . . . . . . REIS (P.), and F . WIGGER~ . . . . . . . . Estimation of the Total Alkalolda in Q. uininc Bark . Estimation of Sulphur in lron PAGE 1290 1290 1290 1291 1292 129% 1292 1293 1293 1293 1294 1895 1295 1295 1296 1296 1297 1297 1298 1295 1299 1299 1300 1300 1301 1 302 1302 1304 3 395 13% 1397 1397 1397 1398 1398 1398 1399 1399 1400 14430 1401 14.01 1402 lPO2 1403 1403 1403 14-04 1404 1548 1549 1549 1549CONTENTS. liii VITALI (D.). Sulpliuric Acid in Natural and Plastered Wines . , . PARMENTIER (F.). Estimation of Boric Acid . . . . . . BERTIN-SANS (H.) and J. MOITESSIEU. Detection of Carbonic Oxide in Blood FREYEPI’IUS (R.). Separation of Barium from Calcium . . . . VORTMANN ((3.). Electrolytic Estimation of Metals as Amalgams . . WILM (T.). Separation of Arsenic and Antimony . . . . . JOLY (A.) and E. L E I D I ~ Detection and Separation of Metals of the Pluti- num Group in presence of other Metals. . . . . . . LEPIERRE (C.). Water Analyeis , . . . . . . . . HILCIER (A.) and I(. TAMBA. Detection of Cganogen Compounds . . PANAJOTOW ((3.). Detection of Turkish Geranium Essence in Oil of Roses . . . . . . . . . . . . . SCALA (A.). Estimation of the Impurities in Alcohol by Rose’s Method . CARR~ (L.) Estimation of Phenol . . . . . . . . VOQEL (J. H.). Estimation of Sugar and Tannin in Wines . . . WILSON (J. A ) . Estimation of Cane Sugar in Soup , . . . . LUTHER (E.). Examination of Urine for Sugar . . . . . . SHUTT (F. T.). Babcock’s Method for Estimating Fat in Milk . . . DE NEQRI ((3.) and Gt. FABRIS. Reactioiis of Olire Oil . . . . WILLIAMS (R.). Estimation of Fatty Matter in Turkey-red Oil , . . WILEP (H. W.). Lard and its Adulteratiors . . . . . . MORNER (K. A. H.) and J. YS~QTJIST. Estimat,ion of Urea . . . VITALI (I).). Reactions of Cocai’ne and of Ecgonige . . . . . FERREIRA DA SILPA (A. J.). Ammonium Selenite as & Reagent for Alka- lords . . . . . . . . . . . . . HUGOUNENQ (L.). Extractioii of the Colouring Matter of Wines . . YAPASOGLI (G.). . VOELLER (E”.). Assay of Indigo . . . . . . . . . Method of Detecting Artificial Coloration in Wine . PAGE 1551 1551 1552 1552 1553 1554 1554 1554 1555 1555 1555 1557 1557 1558 1559 1559 1559 1560 1560 1561 1561 1662 1563 1563 1564CONTENTS. liii VITALI (D.). Sulpliuric Acid in Natural and Plastered Wines . , . PARMENTIER (F.). Estimation of Boric Acid . . . . . . BERTIN-SANS (H.) and J. MOITESSIEU. Detection of Carbonic Oxide in Blood FREYEPI’IUS (R.). Separation of Barium from Calcium . . . . VORTMANN ((3.). Electrolytic Estimation of Metals as Amalgams . . WILM (T.). Separation of Arsenic and Antimony . . . . . JOLY (A.) and E. L E I D I ~ Detection and Separation of Metals of the Pluti- num Group in presence of other Metals. . . . . . . LEPIERRE (C.). Water Analyeis , . . . . . . . . HILCIER (A.) and I(. TAMBA. Detection of Cganogen Compounds . . PANAJOTOW ((3.). Detection of Turkish Geranium Essence in Oil of Roses . . . . . . . . . . . . . SCALA (A.). Estimation of the Impurities in Alcohol by Rose’s Method . CARR~ (L.) Estimation of Phenol . . . . . . . . VOQEL (J. H.). Estimation of Sugar and Tannin in Wines . . . WILSON (J. A ) . Estimation of Cane Sugar in Soup , . . . . LUTHER (E.). Examination of Urine for Sugar . . . . . . SHUTT (F. T.). Babcock’s Method for Estimating Fat in Milk . . . DE NEQRI ((3.) and Gt. FABRIS. Reactioiis of Olire Oil . . . . WILLIAMS (R.). Estimation of Fatty Matter in Turkey-red Oil , . . WILEP (H. W.). Lard and its Adulteratiors . . . . . . MORNER (K. A. H.) and J. YS~QTJIST. Estimat,ion of Urea . . . VITALI (I).). Reactions of Cocai’ne and of Ecgonige . . . . . FERREIRA DA SILPA (A. J.). Ammonium Selenite as & Reagent for Alka- lords . . . . . . . . . . . . . HUGOUNENQ (L.). Extractioii of the Colouring Matter of Wines . . YAPASOGLI (G.). . VOELLER (E”.). Assay of Indigo . . . . . . . . . Method of Detecting Artificial Coloration in Wine . PAGE 1551 1551 1552 1552 1553 1554 1554 1554 1555 1555 1555 1557 1557 1558 1559 1559 1559 1560 1560 1561 1561 1662 1563 1563 1564

ISSN:0368-1769    

DOI:10.1039/CA89160FP001

出版商:RSC    

年代:1891

数据来源: RSC

摘要:

14 ABSTRACTS OF OHEMICAL PAPERS, In o r g a n i c C h e m i s t r y , Properties of Liquid Chlorine. By R. KNIETSCH ( ~ n n a l e n , 253, 10U-l.L4).--l'he author has made a series of determinatims of the vapour teiisiori of ch1or;ne from -888" to 146", and of its specific gravity a t tempeiatures ranging from -80" to 77'; the result8 ale given i n tables wild as ciii-ves, and the methods and apparatus employed ale fully described with the aid of various diagrams. 1 he critical tempel ature of chlorine was found to be 146'. F. 8. K. Simple rhd Rapid Evolutron of Pure Gases. By H. HORN- WAGER (Ztit. unitl. C h w i . , 20, 412; see Absfr,, 1890, 849).--l'heINORGANIC CHEMISTRY. 15 productibn of chlorine from a mixture of blenching powder and sodium hrdrogen sulphate was patented by 0, Stuber, on April 5th, 1890.M. J. S. Atomic Weight of Fluorine. By H. MOISSAN (COn7pt. rend., 111, 570-572) .-Sodium carbonate, prepared hy the ammonia process fram carefully purified sadium chloride, was converted into fluoride bg the action of hydrofluoric acid from potassium hydrogen fluoride. The sodium fluoride was tlien converted into sulphate. The results of five determinations varied between 1' = 19.04 and F t 19.08 (Na = 23'05, S = 38.014, arid 0 = 16). Calcium fluoride, obtained in ti crystalline form by adding calcium chloride to a boiling dilute solution (0.2 per cent.) of potassium fluoride, was likowiae converted into sulphate ; P = 19'02 to 19.08. Barium fluoride, obtained by adding potassiuni fluoride to a boiling solution a€ barium chloride, wits treated in the same way; F = The actior, of sulphuric acid on barium fluoride is more difficult to regulate than in the first two cases, and the author regards these re- hults as less trustworthy, Taking the mean of the results with sodiunl and calcium fluorides, P I 19.05.19'05-19 09, C. H, B. Solubility of Oxygen and Hydrogen in Water and in Aloohol. By W. TIMOF~EFF (Zeit. physikal. Chem., 6 , 141-152). - The author, in his investigation, ernplcys an apparatus devised by Ostwald. It consists of an absorption-chamber which is simply a p;pette provided a t one end with a stopc.ock and a t the other with three-wuy tap, by means of which communication can be effected chither with the air or, throuqh a leaden capillary, with a gas burette. The pipette is filled completely with the boiled-out solvent, and a quantity of the gas to be dissolved is introduced into the gas burette and there measured.Coniriiuriicatioti is then made between the two vessels ; a weighed or measured amount o€ water is run out through the stopcock, which is then closed, and the absorber immersed in a vessel of water a t the requisite temperature, From time to time the absorber is taken out of the bath and shaken as vigorously as the flexibility of the lead tube will permit, Mercury is filled into the gas burette as required, in order that the pressure may remain ag nearly that of the atmosphere a8 po~sible. W heu no more absorption takes place, pressure and temperature are adjusted, and a fresh measurement made. The absorption coefficient of hydrogen in water as determined in the ahove way may be expressed by the formula U = 0.0215286 - 0~00019216S + 0.000001722-t2.Bunsen found = 0 4 1 9 ~ 0 with no temperature coefficient. For oxygen in water, the author obt&ns /j 3; OQ41408 at 6.4", and /I = 0.03(jQll a t 12.6", numbers which agree well with W inklcr's results. The values for hydrogen in alcohol a1-e fairly concordant with those of CRI~~US, /j a t 0" being 00676 (mean of two experinients). An iriterpolatiun formula for the absorp- t ~ o n coefficient of uxygen in alcohol of 99.7 per cent. strength is Q =E 0.235'7 - 0*00074,83t + O4U0O093288t2, The solubility of nitro-7G ABSTRACTS OF CRICMICAL PAPERS. Fen, oxygen, carbon monoxide, and methane in water increases about 80 per cent.between 0" a,nd 20" ; the increase in alcohol is much lgss. Hydrogen Nitride (Azoimide). By T. CURTIUS (Bey.., 23, J . W. 3023-2033). See p. 56. Catalytic Decomposition of Ammonium Nitrite. By 0, LOEW (Bey-., 23, 3018-3019). -On adding platinum black, prcpared in the manner described in a previous paper (Abstr., 1890. 453), to ;t 4 to 5 per ceut. solution of ammonium nitrite, an immediate evolution of gas takes place. The first portion consists of a mixture of nitrogen and nitrous oxide, but after a time nitrogen is tlie sole product. No noticeable alteration in the temperature of t8he sol ation occurs. J. B. T. Absorption of Carbonic Oxide by Earth. By BERTHELOT ((lontyt. r e d . , 111, 469--471).-The volume of carbonic oxide re- tained by air-dried clay soil is equal to the volume of air which i t (*an retain, and hence the retention of carbonic oxide by the eartti, after an explosion i n a mine, for example, is riot due to any specific ;tct,ion between the soil and the gas.C. H. B. Double Chloride and Dithionate of Barium. By A. F o c ~ and K. Kr,Css (Ber., 23, 3001--3003).-Wben equivalent cluantities of barium dithiouate, 13aS,0G + 2H20, and barium chloride, BaClz + 2 H r 0 , are mixed in aqueous solution. and the latter allowed to evapo- rate, barium dithionnte first separates, tben, after a time, the double salt, BaS,O,.BaCI, + 4H20, and finally barium chloride. The above double salt forms short, colourless prisms, which hare been obtained 7 mm. in length and 5.5 mm. i n thickness. and belong t o the asym- metric system (u : 7) : c = 0.6720 : 1 : 0.6398; a: = 107" 12', p = 98" ll', y = 90" 57' 30").H. G. C. Action of Hydrogen on Potassium Thallium Sulphide. By R. SCHNEIDER ( J . y7-. Chern. [el, 42, 305-327).-When the author first published his work on thio-salts (Ann,. Phys. Chew., 136, 138, 139), he showed that when potassium thallium sulpliide is heated in llydrogen it is decomposed with formation of hydrogen sulphide, potassium sulphide, and thallium sulphide. Kriiss and Solereder (Abstr., 1887, 1111, on the contrary, assert that the thallium is re- duced to the inetallic state, the potassium remaining a s sulphide. The author has reinvestigated the subject, and his experiments show that the decomposition takes place in t w o stages, according to 1,he temperature ; a t a dark-red heat, it is in accordance w i t h the equation which the author first gave, namely :- K,S,TI,S, +- 4H = 2H,S + K28 + T'1,S; at a prolonged, full, red heat, however, a part of the thallium is re- duced t o the metallic state according to the eqiistion B[K,S,Tl,S,] + 10H = 5HLS + 2&S + TIZS + TI, ;INORGANIC CHEMISTRY.17 hut at, no kemrerature at which the author has been able to obtaiil quantitative results is the whole of the thallium so reduced. Kruss ant1 Schmidt also assert (loc. c i f . ) that the salt of a thio-acid can be reduced by hydrogen when the thio-acid itself can be so re- duced. But ihis is not the case with sodium thioantinionate or Schlippe's salt and potassium indium sulphide, which cannoi; be re- duced by hydroeen notwithstanding t h a t both antimony and indium stilphides are easily reduced.Compare also the behaviour of potaG- si u m pl tl tino thiop 1 atinat e, K4Pt S4, and potassium pall ad ot h iopalladsi te, K,PdS, (this Jouriml, 1871, 317). The specific gravity of potassium thallium sulpliide has been reclc- termined ; it now stands a t 4.60. A . G. B. Researches on the Gadolinium of Marignac. By L. DE Bors- BAUDRAN C'or~ipt. rend., 111, 393-395). - Mariqnac's gadolinia (Abstr., 1869, 4:)6) was fractionated with dilute ammonia. T tie absorption spectra showed that there was a concentration of' samarium in the head fritctions and of didymiurn in the tail. On the other liand, the fluorescence Zp is much stronger in the head fractioiix, whilst the samarium fluorescence is ieeble in these fraction<, and i s not visible in the others. The spark spectrurn shows that all the fractions conhain gadoliniutn.Cleve finds that the greater part of gadolinia cannot be split up by ft.actionat,ion. The impurities, which atme difficult to eliminate, dis- tribute themselves unequally in the different fractions, without, how- ewr, materially affecting the equivalent of the oxide. The author obseived a remarkable terriporury solubility of the oxides of the rare earths in ammonium acettate solution containiug excess of ammoriiw. A solution of gadolitiium chloride, eqtiivslent to 0.5 gram of the oxide per litre, when mixed with acetic acid arid after- n.;rrds with ammonia in excess, remained transparent for a long time, but gradually became turbid, and precipitation was practically coni- ~!lete after a day or two. Heat accelerates precipitat'ion, but makes it iticomplete.Analogous phenomena are observed w i t h lanthat~um, 1-ttrium, and diclymium, especially the first, arid in a lower degreo with cerous chloride. c. H. B. Equivalent of Terbia. By L. DE ROISBAUDRAN (Compt. rend., 111, $74--475).-h previous determinations of the equivalent of the earth Zp (terbia with a v w y deep-Ilrown colonr), the quaiitity of oxygen existing in the earth in the form of peroxide, was uiicerhin. The author has repeated the determinations by the same method, that k, weighing the quantity of the sulpliate formed by a given quantity of oxide, b u t the oxide was previously calcined a t a white heat, and the small quantity of peroxide present was determined.The coloni- of the calcined oxide was much paler, although still very yellow ; i t contaitied 0.16 per cent. of oxygeii as peroxide. The mean equivalent of tbe terbia, is 122.32, which gives 159.48 for the atomic weight of the metal. C. H. U. YCL. LS. C18 ABSTRACTS OF CHEMICAL PAPERS. Ammonium Fluoroxymolybdates. By F. MACRO (Gazxettrr,, 20, 109-121~- Hexagonal ammonium j?uoroxym olyhdate, 3MoOzF,,5NH4F + HzO, prepared by dissolving the laminar fluoroxymolpbdate (Ahstr., 1889,106), or the compound Mo03,2NH4F, in hydrofluoric acid, crpstal- lises in minute, hexagonal prisms, which resenible those of the double salts of molybdenum and niobium of the type 3MnOF3,5NH4F + H,O, and are probably isomorphous with the crystals of hexagonal ammonium flnoroxyhyponioljbdate.The crystals are colourless and t,ransparent at first, but become opaque after prolonged exposure to the air ; they are not dehydrated by heating at 100" ; they dissolve in water, forming an acid solution, which loses hydrogen fluoride on heating, and if the temperature exceeds loo", ammonia is also evolved. Monamnioniurn Jluoroxymolybdate. Mo02F2,NH4F, is obtained in monoclinic crystals on allowing a solution of the preceding compound in hydrofluoric acid to evaporate over sulphuric acid ; a : b : c = 0.63019 : 1 : 1.42549, p = 85" 53'. Fa,ces observed: 010, 001, 110, 111, 337, 335, 667. Plane of twinning (307). The crystals, which are generally twinned, are colourless and transparent, but darken and timi green after st short exposure to the air ; they dissolve in water, yielding an acid solution.T'he crystals may be heated t o 120" without losiiig weight, but decom- pose at a higher temperikture. Delafontaine's acid fluoyomolybdate of ammonium appears t o be identical with the aut8hor's triammonium fluoroxpmolybdate, MoOzF2,3NH4F, and is not isomorphoils with the acid fluoroxytnng- state. S. B. A. A. Double Salts of Tungstic and Vanadic Acids. By F. ROTHEN- BACH (Ber., 23, 3050-3060).-0n adding sodium paraiunpstate to hydrated vanadic anhydride, sodium paratungsto-vanadate is formed, together with a cornpound which crystallises in dark-red octahedra, and has the formula 3(Naz0,4W0,),N~,0,3Vz05 + 38H20. The following salts were prepared from sodium paratungsto- vanadate by double decomposition :- The ammonium salt crystallises in orange-red octahedra of the formula 5 [ 5(NH4),0, 12 W 0 3 1 2 [ 7Vz05,3 (NH&O] + 58Hz0.The bariu,m salt is deposited in light, orange-coloured crystals, which are very sparingly soluble, and have t'he formula 3( 5Ba0,12WO3),2(5VZO5,2BaO) + 94Hzo. From the mother liquors cubical crystals are obtained, which contain sodium chloride, barium tungstate, and bariixm vanadate. The strontium salt crystztllises in orange-red cubes, 3(5Sr0,12WO3),2(5VZO5,2Sr0) + 12dHz0, and resembles the barium compound. The potassiicm salt crystallises iu aggregates of large, light orange-red plates, which have not get been analysed. By the action of magnesium sulphate on sodium para- tungstovanadate, a, componnd of the formula 5NaZ0,12W O3,3V,O5,MgO,N a,O + 42HzoINORGANIC CHEMISTRY.19 i s formed. crystallising in pale orange-yellow prisms. A similay com- pound is deposited from the mother liquors in lustrous, light orange- coloured plates. With sodium tungstovanadate, aluminiuiri sulphate gives a compound of the formula crystallising in dark garnet-red cubes. No coppr salt could be ob- tained. The water of crystallisation i n the above compounds was deter- mined by cautious ignition. The variadic acid and fiungstic acid were precipitated together by means of mercuric nitrate and mercuric oxide. The vanadic acid was determined separately by reduction and titration with potassium permanganate, and also by boiling with phosphoric acid, potassium bromide, and hydrochloric acid ; the bromine which is evolved is absorbed in potassium iodide solution, and the liberated iodine estimated in the usual manner.Bismuth Oxyiodide. By C. ASTRE (J. Pharm,. [ 5 ] , 22,193-200). -Various published methods for the preparation of this oxyiodide yielded products more or less contaminated with sub-nitrahe, with oxide, or with both these compounds. To obtain the pure product, 10 grams of bismuth potassium iodide is decomposed by the addition of 4 litres of water, and the product is washed until iodine is no l o n p r removed. The resulting compound contained Bi, 59.38, and 1, 36-30 per cent. The double iodide employed is best, obtained by triturat- ing normal bismuth nitrate (1 mol.) with potassium iodide (4 mols.), and 50 C.C. of water (sic), extracting with ethyl acetate, and sub- mitting the mixture to spontaneous evaporation.3(Al,0,,9Na,0,48W0~3) ,4( 9V205,A1,0,) + 504H20, J. B. T. J. T. Platinum Thiocarbide. By P. SCHUTZEKBERGER (Compt. ?-end., 1117391-393).-A current of nitrogen or hydrogen charged with the vapour of carbon bisulphide is passed over spongy platinum heated at 400-450”, and when the absorption of t,he bisulphide ceases, the somewhat finely divided black product is allowed to cool, and is powdered and submitted to the same treatment again. The product is a dense, black powder of the composition Pt,CS2. Under a micro- scope, it seems homogeneous, and it cannot be separated into different components by levigation. I t is not attacked by boiling concentrated nitric or hydrochloric acid, and is almost entirely unaffected by warm aqua regia.It is, therefore, not a mixture of platinum sulphide wit,h carbon, and it probably has the constitution S:Pt:C:Pt:S. When heated below redness iir dry oxygen, i t burns with incandescence, atrid yields carbonic anhydride. sulphuric anhydride, sulphurous anhydride, and a, residue of pnre platinum. The formation of this compound may be used f o r the separation, and even the estimation, of carbon bisulphide in any mixture of gases which is free from oxygen. The gaseous mixture is passed over the heated spongy platinum, and the product is afterwards heated in oxygen, the gases formed being absorbed in some oxidising liquid, and the sulphuric acid estimated in the usual way. C. H. l3. c 214 ABSTRACTS OF OHEMICAL PAPERS,In o r g a n i c C h e m i s t r y ,Properties of Liquid Chlorine.By R. KNIETSCH ( ~ n n a l e n ,253, 10U-l.L4).--l'he author has made a series of determinatims ofthe vapour teiisiori of ch1or;ne from -888" to 146", and of its specificgravity a t tempeiatures ranging from -80" to 77'; the result8 alegiven i n tables wild as ciii-ves, and the methods and apparatus employedale fully described with the aid of various diagrams.1 he critical tempel ature of chlorine was found to be 146'.F. 8. K.Simple rhd Rapid Evolutron of Pure Gases. By H. HORN-WAGER (Ztit. unitl. C h w i . , 20, 412; see Absfr,, 1890, 849).--l'hINORGANIC CHEMISTRY. 15productibn of chlorine from a mixture of blenching powder and sodiumhrdrogen sulphate was patented by 0, Stuber, on April 5th, 1890.M.J. S.Atomic Weight of Fluorine. By H. MOISSAN (COn7pt. rend., 111,570-572) .-Sodium carbonate, prepared hy the ammonia processfram carefully purified sadium chloride, was converted into fluoridebg the action of hydrofluoric acid from potassium hydrogen fluoride.The sodium fluoride was tlien converted into sulphate. The resultsof five determinations varied between 1' = 19.04 and F t 19.08(Na = 23'05, S = 38.014, arid 0 = 16).Calcium fluoride, obtained in ti crystalline form by adding calciumchloride to a boiling dilute solution (0.2 per cent.) of potassiumfluoride, was likowiae converted into sulphate ; P = 19'02 to 19.08.Barium fluoride, obtained by adding potassiuni fluoride to a boilingsolution a€ barium chloride, wits treated in the same way; F =The actior, of sulphuric acid on barium fluoride is more difficult toregulate than in the first two cases, and the author regards these re-hults as less trustworthy, Taking the mean of the results with sodiunland calcium fluorides, P I 19.05.19'05-19 09,C.H, B.Solubility of Oxygen and Hydrogen in Water and inAloohol. By W. TIMOF~EFF (Zeit. physikal. Chem., 6 , 141-152). -The author, in his investigation, ernplcys an apparatus devised byOstwald. It consists of an absorption-chamber which is simply ap;pette provided a t one end with a stopc.ock and a t the other withthree-wuy tap, by means of which communication can be effectedchither with the air or, throuqh a leaden capillary, with a gas burette.The pipette is filled completely with the boiled-out solvent, and aquantity of the gas to be dissolved is introduced into the gas buretteand there measured.Coniriiuriicatioti is then made between the twovessels ; a weighed or measured amount o€ water is run out throughthe stopcock, which is then closed, and the absorber immersedin a vessel of water a t the requisite temperature, From time to timethe absorber is taken out of the bath and shaken as vigorously asthe flexibility of the lead tube will permit, Mercury is filled into thegas burette as required, in order that the pressure may remain agnearly that of the atmosphere a8 po~sible. W heu no more absorptiontakes place, pressure and temperature are adjusted, and a freshmeasurement made.The absorption coefficient of hydrogen in water as determined inthe ahove way may be expressed by the formula U = 0.0215286 -0~00019216S + 0.000001722-t2. Bunsen found = 0 4 1 9 ~ 0 with notemperature coefficient.For oxygen in water, the author obt&ns/j 3; OQ41408 at 6.4", and /I = 0.03(jQll a t 12.6", numbers whichagree well with W inklcr's results. The values for hydrogen in alcohola1-e fairly concordant with those of CRI~~US, /j a t 0" being 00676(mean of two experinients). An iriterpolatiun formula for the absorp-t ~ o n coefficient of uxygen in alcohol of 99.7 per cent. strength isQ =E 0.235'7 - 0*00074,83t + O4U0O093288t2, The solubility of nitro7G ABSTRACTS OF CRICMICAL PAPERS.Fen, oxygen, carbon monoxide, and methane in water increases about80 per cent.between 0" a,nd 20" ; the increase in alcohol is much lgss.Hydrogen Nitride (Azoimide). By T. CURTIUS (Bey.., 23,J . W.3023-2033). See p. 56.Catalytic Decomposition of Ammonium Nitrite. By 0,LOEW (Bey-., 23, 3018-3019). -On adding platinum black, prcparedin the manner described in a previous paper (Abstr., 1890. 453), to ;t4 to 5 per ceut. solution of ammonium nitrite, an immediate evolutionof gas takes place. The first portion consists of a mixture of nitrogenand nitrous oxide, but after a time nitrogen is tlie sole product. Nonoticeable alteration in the temperature of t8he sol ation occurs.J. B. T.Absorption of Carbonic Oxide by Earth. By BERTHELOT((lontyt. r e d . , 111, 469--471).-The volume of carbonic oxide re-tained by air-dried clay soil is equal to the volume of air which i t(*an retain, and hence the retention of carbonic oxide by the eartti,after an explosion i n a mine, for example, is riot due to any specific;tct,ion between the soil and the gas.C. H. B.Double Chloride and Dithionate of Barium. By A. F o c ~and K. Kr,Css (Ber., 23, 3001--3003).-Wben equivalent cluantitiesof barium dithiouate, 13aS,0G + 2H20, and barium chloride, BaClz +2 H r 0 , are mixed in aqueous solution. and the latter allowed to evapo-rate, barium dithionnte first separates, tben, after a time, the doublesalt, BaS,O,.BaCI, + 4H20, and finally barium chloride. The abovedouble salt forms short, colourless prisms, which hare been obtained7 mm. in length and 5.5 mm.i n thickness. and belong t o the asym-metric system (u : 7) : c = 0.6720 : 1 : 0.6398; a: = 107" 12', p =98" ll', y = 90" 57' 30"). H. G. C.Action of Hydrogen on Potassium Thallium Sulphide. ByR. SCHNEIDER ( J . y7-. Chern. [el, 42, 305-327).-When the authorfirst published his work on thio-salts (Ann,. Phys. Chew., 136, 138,139), he showed that when potassium thallium sulpliide is heated inllydrogen it is decomposed with formation of hydrogen sulphide,potassium sulphide, and thallium sulphide. Kriiss and Solereder(Abstr., 1887, 1111, on the contrary, assert that the thallium is re-duced to the inetallic state, the potassium remaining a s sulphide.The author has reinvestigated the subject, and his experiments showthat the decomposition takes place in t w o stages, according to 1,hetemperature ; a t a dark-red heat, it is in accordance w i t h the equationwhich the author first gave, namely :-K,S,TI,S, +- 4H = 2H,S + K28 + T'1,S;at a prolonged, full, red heat, however, a part of the thallium is re-duced t o the metallic state according to the eqiistionB[K,S,Tl,S,] + 10H = 5HLS + 2&S + TIZS + TI, INORGANIC CHEMISTRY.17hut at, no kemrerature at which the author has been able to obtaiilquantitative results is the whole of the thallium so reduced.Kruss ant1 Schmidt also assert (loc. c i f . ) that the salt of a thio-acidcan be reduced by hydrogen when the thio-acid itself can be so re-duced. But ihis is not the case with sodium thioantinionate orSchlippe's salt and potassium indium sulphide, which cannoi; be re-duced by hydroeen notwithstanding t h a t both antimony and indiumstilphides are easily reduced.Compare also the behaviour of potaG-si u m pl tl tino thiop 1 atinat e, K4Pt S4, and potassium pall ad ot h iopalladsi te,K,PdS, (this Jouriml, 1871, 317).The specific gravity of potassium thallium sulpliide has been reclc-termined ; it now stands a t 4.60. A . G. B.Researches on the Gadolinium of Marignac. By L. DE Bors-BAUDRAN C'or~ipt. rend., 111, 393-395). - Mariqnac's gadolinia(Abstr., 1869, 4:)6) was fractionated with dilute ammonia. T tieabsorption spectra showed that there was a concentration of' samariumin the head fritctions and of didymiurn in the tail. On the otherliand, the fluorescence Zp is much stronger in the head fractioiix,whilst the samarium fluorescence is ieeble in these fraction<, and i snot visible in the others.The spark spectrurn shows that all thefractions conhain gadoliniutn.Cleve finds that the greater part of gadolinia cannot be split up byft.actionat,ion. The impurities, which atme difficult to eliminate, dis-tribute themselves unequally in the different fractions, without, how-ewr, materially affecting the equivalent of the oxide.The author obseived a remarkable terriporury solubility of theoxides of the rare earths in ammonium acettate solution containiugexcess of ammoriiw. A solution of gadolitiium chloride, eqtiivslent to0.5 gram of the oxide per litre, when mixed with acetic acid arid after-n.;rrds with ammonia in excess, remained transparent for a long time,but gradually became turbid, and precipitation was practically coni-~!lete after a day or two.Heat accelerates precipitat'ion, but makes ititicomplete. Analogous phenomena are observed w i t h lanthat~um,1-ttrium, and diclymium, especially the first, arid in a lower degreowith cerous chloride. c. H. B.Equivalent of Terbia. By L. DE ROISBAUDRAN (Compt. rend., 111,$74--475).-h previous determinations of the equivalent of theearth Zp (terbia with a v w y deep-Ilrown colonr), the quaiitity ofoxygen existing in the earth in the form of peroxide, was uiicerhin.The author has repeated the determinations by the same method, thatk, weighing the quantity of the sulpliate formed by a given quantityof oxide, b u t the oxide was previously calcined a t a white heat, andthe small quantity of peroxide present was determined.The coloni-of the calcined oxide was much paler, although still very yellow ; i tcontaitied 0.16 per cent. of oxygeii as peroxide. The mean equivalentof tbe terbia, is 122.32, which gives 159.48 for the atomic weightof the metal. C. H. U.YCL. LS. 18 ABSTRACTS OF CHEMICAL PAPERS.Ammonium Fluoroxymolybdates. By F. MACRO (Gazxettrr,, 20,109-121~- Hexagonal ammonium j?uoroxym olyhdate, 3MoOzF,,5NH4F + HzO, prepared by dissolving the laminar fluoroxymolpbdate (Ahstr.,1889,106), or the compound Mo03,2NH4F, in hydrofluoric acid, crpstal-lises in minute, hexagonal prisms, which resenible those of the doublesalts of molybdenum and niobium of the type 3MnOF3,5NH4F + H,O,and are probably isomorphous with the crystals of hexagonal ammoniumflnoroxyhyponioljbdate. The crystals are colourless and t,ransparentat first, but become opaque after prolonged exposure to the air ; they arenot dehydrated by heating at 100" ; they dissolve in water, formingan acid solution, which loses hydrogen fluoride on heating, and if thetemperature exceeds loo", ammonia is also evolved.Monamnioniurn Jluoroxymolybdate.Mo02F2,NH4F, is obtained inmonoclinic crystals on allowing a solution of the preceding compoundin hydrofluoric acid to evaporate over sulphuric acid ;a : b : c = 0.63019 : 1 : 1.42549, p = 85" 53'.Fa,ces observed: 010, 001, 110, 111, 337, 335, 667. Plane oftwinning (307).The crystals, which are generally twinned, arecolourless and transparent, but darken and timi green after st shortexposure to the air ; they dissolve in water, yielding an acid solution.T'he crystals may be heated t o 120" without losiiig weight, but decom-pose at a higher temperikture.Delafontaine's acid fluoyomolybdate of ammonium appears t o beidentical with the aut8hor's triammonium fluoroxpmolybdate,MoOzF2,3NH4F, and is not isomorphoils with the acid fluoroxytnng-state. S. B. A. A.Double Salts of Tungstic and Vanadic Acids. By F. ROTHEN-BACH (Ber., 23, 3050-3060).-0n adding sodium paraiunpstate tohydrated vanadic anhydride, sodium paratungsto-vanadate is formed,together with a cornpound which crystallises in dark-red octahedra,and has the formula 3(Naz0,4W0,),N~,0,3Vz05 + 38H20.The following salts were prepared from sodium paratungsto-vanadate by double decomposition :-The ammonium salt crystallises in orange-red octahedra of theformula 5 [ 5(NH4),0, 12 W 0 3 1 2 [ 7Vz05,3 (NH&O] + 58Hz0.Thebariu,m salt is deposited in light, orange-coloured crystals, which arevery sparingly soluble, and have t'he formula3( 5Ba0,12WO3),2(5VZO5,2BaO) + 94Hzo.From the mother liquors cubical crystals are obtained, which containsodium chloride, barium tungstate, and bariixm vanadate. Thestrontium salt crystztllises in orange-red cubes,3(5Sr0,12WO3),2(5VZO5,2Sr0) + 12dHz0,and resembles the barium compound. The potassiicm salt crystallisesiu aggregates of large, light orange-red plates, which have not getbeen analysed.By the action of magnesium sulphate on sodium para-tungstovanadate, a, componnd of the formula5NaZ0,12W O3,3V,O5,MgO,N a,O + 42HzINORGANIC CHEMISTRY. 19i s formed. crystallising in pale orange-yellow prisms. A similay com-pound is deposited from the mother liquors in lustrous, light orange-coloured plates. With sodium tungstovanadate, aluminiuiri sulphategives a compound of the formulacrystallising in dark garnet-red cubes. No coppr salt could be ob-tained.The water of crystallisation i n the above compounds was deter-mined by cautious ignition. The variadic acid and fiungstic acidwere precipitated together by means of mercuric nitrate and mercuricoxide. The vanadic acid was determined separately by reductionand titration with potassium permanganate, and also by boiling withphosphoric acid, potassium bromide, and hydrochloric acid ; thebromine which is evolved is absorbed in potassium iodide solution,and the liberated iodine estimated in the usual manner.Bismuth Oxyiodide.By C. ASTRE (J. Pharm,. [ 5 ] , 22,193-200).-Various published methods for the preparation of this oxyiodideyielded products more or less contaminated with sub-nitrahe, withoxide, or with both these compounds. To obtain the pure product,10 grams of bismuth potassium iodide is decomposed by the additionof 4 litres of water, and the product is washed until iodine is no l o n p rremoved. The resulting compound contained Bi, 59.38, and 1, 36-30per cent. The double iodide employed is best, obtained by triturat-ing normal bismuth nitrate (1 mol.) with potassium iodide (4 mols.),and 50 C.C. of water (sic), extracting with ethyl acetate, and sub-mitting the mixture to spontaneous evaporation.3(Al,0,,9Na,0,48W0~3) ,4( 9V205,A1,0,) + 504H20,J. B. T.J. T.Platinum Thiocarbide. By P. SCHUTZEKBERGER (Compt. ?-end.,1117391-393).-A current of nitrogen or hydrogen charged with thevapour of carbon bisulphide is passed over spongy platinum heatedat 400-450”, and when the absorption of t,he bisulphide ceases, thesomewhat finely divided black product is allowed to cool, and ispowdered and submitted to the same treatment again. The productis a dense, black powder of the composition Pt,CS2. Under a micro-scope, it seems homogeneous, and it cannot be separated into differentcomponents by levigation. I t is not attacked by boiling concentratednitric or hydrochloric acid, and is almost entirely unaffected by warmaqua regia. It is, therefore, not a mixture of platinum sulphide wit,hcarbon, and it probably has the constitution S:Pt:C:Pt:S. Whenheated below redness iir dry oxygen, i t burns with incandescence, atridyields carbonic anhydride. sulphuric anhydride, sulphurous anhydride,and a, residue of pnre platinum.The formation of this compound may be used f o r the separation,and even the estimation, of carbon bisulphide in any mixture of gaseswhich is free from oxygen. The gaseous mixture is passed over theheated spongy platinum, and the product is afterwards heated inoxygen, the gases formed being absorbed in some oxidising liquid,and the sulphuric acid estimated in the usual way. C. H. l3.c

ISSN:0368-1769    

DOI:10.1039/CA8916000014

出版商:RSC    

年代:1891

数据来源: RSC

摘要:

20 ABSTRACTS OF CHEMICAL PAPERS. Min e r a1 o gi c a Z C h e mi s t ry. Bismuth Minerals from Gladhammar. By G. LINDSTR~X (Jahrb. j*. Mia., 1890, ii, Ref. 53; from Ge6l. FiirPn. Forhand., 11, 771).-On examining a series of ores, tbe atithor found a lead-grey to tin-white mineral with a brilliant lnstre. On analysis, it gave the following results :- Bi. Pb. Ca. Fe. Zn. S. Insol. Total. 33.84 48-05 0.69 0-16 0-05 15-92 0-45 99-16 The author is unacquainted with a mineral of this coniposition (compere, lrowever, lillianite, 3Ph(Ag)S + Bi,S,). As an assay of another specimen gave 42.15 per cent. of lead, it is Hamlinite, a New Rhombohedra1 Mineral. By W. E. HIDDEN ant1 S . L. PEKF~ELD (Amer. J. Sci., 39, 511--.’13).-Shortly after t h e discovcry of ‘taerderite (Abstr., 1884, 827, 11 02) at Stoneham, Maine, this mineral was detected occurring as miniite, rhombohedra1 crvstals, :issoc*iated with herderite, margarodite, and the rare glucinum silicate, hertrandite.During the past five years, the authors have kept up a diligent search €or the crystals, but without success. The crystals are hexagorial-rhombohedritl, and vary from 1 to 2 mm. in diameter.. Their hardness is 45, and their sp. gr. 3.229. Qualitative analysis indicates that the mineral is a new species-a phosphate, probably of glucinum and aluminium, containing fluorine. The authors propose for it the name of humliiiite, in honour of Dr. A. C, Hamlin, who is largely interested in the development of the mineral resources of the district in which the new mineral occurs. The formula deduced from these results is 3PbS + Bi,S,.possible that bjelki te also occurs a t Gladhammar. €3. €3. B. B. H. B. Preparatioa of Artificial Molybdenite. By A. v. SCHULTEN (Jahrb, ,f. X t z . , 1890, ii, Ref. 223 ; from Geol. Foren,. b’orAa~~dZ., 11, 401).-The author melted 4 gleams of potassium carbonfite with 6 grams of sulphur in a porcelain crucible, and on cooling added 1 gram of molybdic anhydride. ‘J’he mass was then heated in a well- closed c.rucible to a melting heat, and, on cooling, a fresh portion of the anhydride was added. The process was repeated until 5 t o 6 grams of molgbdic anhydride had been used. On boiling the melted Ilianti with water, a residue of pure crystallised molybdenite, Mod,, was obtained in the form o€ greyish-violet, opaque, hexagonal crystals with a sp.gr. of 5.06 a t 15”. The crystah are very soft, and make grey marks on paper. Flinkite and Heliophy llite from Harstigen Mine, Sweden. By A. HAMBERG (Jahrh. j‘. Miu., 1890, ii., Ref. 834-228, from Geol. Fiiren. ForhundZ., 11, 21 2).-Flinkite, a hydrated manganese arsenate, occurs in khe Harstigen mine, Pajsberg, Wermland, iu greenish-brown crystals with sarkinite on karyopilite. Its sp, gr. is B. H. B.MINERALOGICAL CHEMISTRY. 2 1 3.87. rhombic system, the forms observed being UP, Pm, P, mP00. analysis, it gave results corresponding with the formula, It has a hardness of more than 4, and-crystallise_s in the OIL 4H20,.EMn0,Mn203,As206, a composition very similar to that of sjnadelphite. An optical exauiinntion of the mineral heliophyllite, described by G.Flink as biaxial, showed i t to be always composed of biaxial and uniaxial portions. The author distinguishes two types of this mineral as met with at the Harstigen mine : (1) the coarsely lami- nated variety ; and (2) crystals associated with baryytes and inesite. The optical properties exhibited are similar t o those shown by the mineral ekdemite from Lingban, described by Nordenskiold as optically uniaxial. Further, the minerals appear to be chemically identical, analysis having given the following resnlts :- PbO. FeO + MnO. CaO. A S , ~ , . Sb203. CI. 10.60 - 8.00 11.. . . . . 81.03 0-07 0.08 19.85 0.56 8.05 111.. . . . . 80.99 0.16 0.11 10.49 1.38 7.96 I.. . . . . 83.45 - - 1. Ekdemite (Nordenskiold). 11. Heliophyllite, type I.I11 the same, type 11. Nordenskiiild calculates the fbrrniila, Pb5As208 + 2PbC12, Flink gives PbcAs2O7 + 2PbC1,. The author, however, is of opinion that the more exact formula Pb,As,O,, + 4PbC12 is not improbable. B. H. B. Minerals from Styria. By E. HATLE and H. TAUSS (Jak-b. f. .illit!., 1890, ii., Ref. 1 7 ; from Vwhandl. geol. Reichsanst., 1887, 226-229) .--1 . Pharmacolite from Viillig. 'l'his mineral occurs in ~ h i t e , trauslucent groups of' crystals and crusts with B fibrous texture. As.205. CaO. H,O. 48-60 27-04 24.49 Analjsis yielded the following results :- The mineral is associated with zinc-blende, plena, arsenical pyrites, magnetic pyrites. iron pyrites, quartz, and calcite. 2. Iron-gjmnite from Kraubath. This mineral occurs, with yellow gjmnite, in serpentine.It ha's a hardness of 3, and a sp. gr. of 1.986. Analysis yielded the folIowing results :- SiO,. MgO. FeO. H2O. 41-55 30.24 6.60 20.10 Allowance being made for 1-27 per cent. of ferric oxide dissemi- nated in tlie form of iron mica, the formula is H,,Mgl2E'eSl1O,, + 9HZO. B. H. B. Fluorine and the Synthesis of Minerals. By S. MEUEIER (Compt. 1-end., 111, 509-51 1) .-The iise of aluminium fluoride makes it pomihle to obtain in a compratively short time, and at the tempe-22 ABSTRACTS OF CEIEMICAL PAPERS. rature of an ordinai-y coke fire, several minerals, which under ordinary conditions are difficult to synthesise. 32 parts of calcined silica, 8 parts of fused potassium hydroxide, and 44 parts of aluminium fluoride, yield a regulus which is not completely vitreous but gives a fracture with a silky lustre.Under the microscope, it is seen to contain needles of sillimanite and hexa- gonal lamella of tridymite i n large quantity, together with inclusions of various kinds and globuliform masses which are almost opaque. 43 parts of silica, 20 of calcium oxide, and 60 of aluminium fluoride yield a product which, although chiefly a glass, has a highly lustrous fracture, and contains needles of sillimanite and lamellae of trid ymite. 26 parts of silica, 12 of calcium oxide, 2 of potassium hydroxide, and 25 of aluminium fluoride yield. a decidedly crystalline product containing large quan t.ities of thin plates of labradorite, many of which are macled according to the albite law, whilst the larger have spheroidal inclusions.22 parts of silica, 17 of alumina, 0.2 of ferric oxide, 8 of sodium hydroxide, '2 of potassium hydroxide, and 1 of lime, in a crucible brasqued with cryolite, jie!d a deep grey granulo-crystalline product. The mass is vitreous, but is fuli of inclusions, and contains many crystals of sillimanite, and a large quantity of prismatic crystals of nepheline. 27 parts of silica, 12 of alumina, and 10 of potlassium hydroxide in B crucible brasqued with cryolite, yield a partially vitreous product f u l l of crystalline granules. Under the microscope, largc! numbers of smd1 globules are seen, identical with the leucite of natural amphigenes. C. H. B. Sigterite, a New Felspar. By C. RAMMELSREKG (,Juhrb.f. Min., 1890, ii, Mem. 71--74).-1n an investigation into the properties of eu- dialyte from Sigtero, the author found that this mineral was associated with two others, white albite and another felspar in the form of grey, granular particles.The new felspar has the cleavage of ort'hoclase, and, chemically, is a potassium sodium felspar free from lime, and much more basic than albite and orthoclase. I n thin sections, in- clusions of augite and a small quantity of magnesia-mica were observed. After making corrections for the small quantities of augite present, the mineral gives on analysis the following results :- SiOz. A1,0,. Na,O. KzO. Total. 50.01 30.86 13.90 523 100.00 The formula of the felspar is therefore (NaK),AISi,Olo. words, i t is a combination of albite and an alkali anorkhite. same time, it has the composition of an anhydrous natrolite.I n other At the B. H. B. Minerals from Vesuvius. By E. SCACCHI (Zeit. K?-yst. Min., 18, 99-102; from R. Accud. d i Napoli, 3888, 12).-1. l'hakellite, i~ new mineral. Among the Somrna minerals in the ninseum of the University of Naples there is a substance, hitherto undescribed, whichMINERALOGICAL OHEMISTRY. 23 the author has named from its characteristic combination of trans- parent, colourless needles to white, silky bundles (@&Xhr). This rare mineral occurs in a rock consisting of augite with more or less mica, and occasionally in grey, granular calcite. Optically the mineral is uniaxial, with faint negative birefraction, and therefore belongs to the hexagonal system. It has the hardness of orthoclase, and a sp. gr.of 2.49. Analysis gave the following results :- SiO,. A1,0,. K20. Na,O. Total. 37.73 33.33 29.30 0.37 100.73 Formula : K2A12Si208. 2. Thernioncitvite, from the lava of 1859. The analogy with nepheline is remarkable. This mineral is new for Vesuvius. The Naples museum recently received numerous white, opaque, drusy incrustations from the Fosso grande. On analysis, this mineral, Na,CO, + HzO, yielded 35-44 per cent. of carbonic anhjdride. 3. Soda from the interior of the same lava in crystalline, colour- less, transparent grains. On analysis, the following results were obtaked :- CO,. Na,O. K20. H20. Total. 15.91 22-15 0.41 61.68 100.15 These results correspond with the formula Na,C03 + lOH,O. The mineral cannot have been produced by sublimation, but by the action of carbonic anhjdride which has decomposed the lava and taken the soda from it.4. Altered cowpfonite from the Somma conglomerates. In one yariety of conglomet ate at Vesuvius, zeolites occnr ill association with calcite. Among these, small crystals resembling comptonite are occasionally met with, the change in the chemical composition of the zeolites and the variation from that of comptonite consisting chiefly in a loss of water, an absorption of calcium carbonate, and a change in the ratio of the silica, to the alumina, (compare Abstr., 1887, 17). B. H. B. Amphibolite from Habendorqrin Silesia. By E. DATHE ( J a h ~ h . $. Min., 18W, ii, Ref., 243-244 ; from Jalwb. preuss. geol. Landesnnst., 1889, 309-328) .-The amphibolite (Analysis I) occurring in the hiotite gneiss of Habendorf, consists of hornblende of a greenish-black colour and bdliant lustre.There is a second variety (Analysis 11) composed of light greenish-grey hornblende, with a little pyrrhotite and mica. Under the microscope, olivine, diopside, chromite, and rutile could also be detected. SiO,. Ti02. Fe20,. Cr,O,. Al,O,. FeO. MgO. CaO. I . . 46.47 0.21 4.18 trace 8.68 3.73 22.79 9-05 11 . . 47-82 0.65 0.94 0.65 7.88 3-50 29-56 3.66 42,O. Na20. H,O. CO,. Total. Sp. gr. I .. 0.35 1.14 3.39 - 99.99 2.959 11.. trace 0.43 4.20 0.41 99.48 2.857 B. H. B.24 ABSTRAOTS OF CHEMICAL PAPERS. Chemical Nature of Tourmaline. By C. RAMW ELSRERG (Ju7wb. f. JIi,t., 1890, ii, Mem., 149--162).-1n this paper the author re- calculates some 70 analyses of tourmaline, with a view to controvert the formula: recently arrived a t by Riggs (Abstr., 1888, 660), Jan- nasch and Calb (Abstr., 1889, 4 Z ) , Scharizer (Abstr., 1689, 764)) and Wiilfing (Abstr., 18r39, 765).He is slill of opinion that his interpre- tation of thc tourmaline analyses of 20 years ago was correct, eccording to which they must be regarded as isomorphous mixtures of thres silicates, R'$3iO5. R"3Si05, and R"Si05, in which R' represents H, Na, K, Li ; R" represents Fe, M L ~ , Mg, Ca ; and Rvi represents A12, Fez, B,, Cr2. By G. W. KALB (Jnhd. f. Min., 1890, ii. Ref. 199-203 ; from Innug. Diss. Gottinge,/,, 1890).-Ten varieties of tourmaline analysed by the author may be divided into t.hree groups :-( 1) Lithium tonrmaline, (2) iron magnesium tour- maline, (3) iron tourmaline.From the analyses, the author deduces the general formula R,BO,(SiOa),. [The analyses given appear to be almost identical with those given in a paper by P. Jannasch and G. Cslb (Abstr., 1889, 472).] By M. KOCH (Jah~b. f. Mh., 1830, ii, Ref. 244-245 ; from Zeit. deutsch. geol. Ges., 41, 163-165).- Peridotite occurring in the gabbro mass of the Kaltenthal, in the Harz, contains olivine in angular grains, as much as 23 mm. in size, with biotite, spinel, and titaniferous iron ore. Small quantities of augite and plagioclase are present as accessory constituents. The rock is more basic than any of the basic members of the Harzburg gabbro hitherto examined, as ir, shown by the following analytical results, in which the high percentage of titanium is probably due to tlie biotite :- SiOz. Ti02.Al20,. Fe,O,. FeO. MgO. CaO. K20. 34.98 5.18 10.80 1.42 21.33 19.30 0.43 5.42 NazO. H2O. 503. Total. Sp. gr. 0.17 1:28 trace 100.31 3.27 B. H. H, Composition of Tourmaline. B. H. €3. Peridotite from the Harz. B, H. B. Minerals of the Garnet Group. By W. C. BROGGER and H. HACKSTROM (Zeit. Kvyst. iWin., 18, 209-276).-0f the 12 silicates crystallieing in the regular system, eulytine, zunyite, helvine, danalite, garnet, sodalite, nosean, lapis-lazuli, leucite (maskelynite), pollux, analcirue, aiid faujnsite, the first eight are orthosilicates, and the last four metasilicates. Three of the metasilicates, maskelynite, pollux, and analcirne! belong to one morphological group, whilst faujasite is an isolated species of octahedral type. The orthosilicates are regarded by the author as forming one large group, the garnet group, which may be subdivided into two divisions :-(1) Orthosilicates of tetrahedral character, and (2) orthosilicates of rhom bic dodeca- hedral character.This second division includes holohedral members (the garnet series proper), as well as liemihcdral ones (the alkali Q arn e t s) .MINERALOGICAL OHEMISTRT. 25 The formula? of the members of the first division are as foi1ow.s:- Eulytine ...... Bi4(SiO&. Zunyite . . . . . . Danalite. . . . . . Helvine . . . I . . [A16F2C1(0H),]Al,(SiO~)3. (FeZnMn),[ (ZnFe)zS]Be3(Si04),. (MnE'eCa),(Mn,S)Be,(Si04j3. In this voluminous paper, the author brings forward a mass of facts to prore t,he close connection of the regular orthosilicates.The analyses of all the mineials of this garnet group lead to f o r m u l ~ in which there is 1 mol. of an orthosilicate with 3 mols. of silicic acid. All the members of this group, too, belong to the regular system. A very large number of analyses are discussed. Of these, the followiug have not previously been published : - SiO,. A1,O. I. 36.74 31.96 11. 37-24 31.60 111. 31.65 27.03 IV. 31.99 2732 v. 32.30 27.38 VI. 32-20 27-37 PII. 32.52 %7%1 VIII. 39-48 27-62 IX. 53.13 1.76 X. 55.15 - XI. 55.55 - CaO. 0.2 1 - 9-94 8.21 8.18 6.47 6.60 24.il 26.38 25.95 MgO. Na,O. K20. SO,. 8. C1. HzO. - 85.95 trace 0.11 - 7.11 9.17 25-60 - - - 7.31 - 27.26 - 14.06 - - - - 16.53 - 14.22 - - - 0.11 18.03 0.35 12.62 0.44 0.31 - 0.11 17.98 0.35 13.17 0.46 0.33 - - - - 19.4.5 0.28 10.46 2.71 0.47 - - 19.84 0-29 10.47 2.71 0.47 0.07 16.93 2.62 - - - - 1.31 18.47 - - - - - - 18.52 - __ - - - - I.Sodalitc. 11. Results calculated from the formula Na4( A1 Cl) Al,( SiO,),. 111. Nosean, formula Na4( A1[S04Na]) AlZ(SiO4),. TV. Hauyn, formula Nil,Ca[Al( SO4Na)]Al,( SiO,),. V. Hauyn, analysis. V1, Results calculated from 92 mols. hauyn, 5.2 mols. sodnlite, and 2.7 mols, ultramarine with the formula Na4[A1( S,Na)]A12( SiO,),. VII. Lapis- lazuli. VIII. The same, results calculated from a composition of '76 9 mols. hauyn, 15.7-mols. ultramarine, and '7.4 mols. sodalite. IX. Diopside occurring enclosed in lapis lazuli. X. Results after sub- traction of 8 per cent. lazurite. XI. Results corresponding with formula CaMg( SiO,),. J3. H B. Minerals and Roouks in the Diamond Fields of South Africa.By A. KNOP (Jlrhrt.f. Min., ii, Ref. 97--99).-Tlie matrix of the diamonds, the so-called blue earth, is found on examination to behave like a serpentine which, after decomposition by acid, leaves inicroliths of pyroxenic character. The rock may be described as a serpentine-tuff enclosing, at Jagersfontein, the following minerals : garnet, chrome-diopside, enstatite, chromite, zircon, apatite, idocrase. ~utile, mica, and diamond. These minerals are described in detail by the author, who gives analyses of the chrome-diopside and chrome- irou ore. The author regards the Jagersfontein deposit as having been formed26 ABSTRAUTS OF CHE1\1ICAL PAPERS. from a peridotite, which has been mechanically broken up and trans- ported to a favourably situated locality, where it has become ser- pentinised.The relation of the diamond to the peridotite is thought to be analogous to the occurrence of the diamond in meteorites. B. H. B. Natural Cement from Cairo. By E. SICKENBERGER (Jnhrb. ,f. E n . , 1890, ii, Ref. 275-276; from Zeii. deutscta. geol. Ges., 41, 312--318).-0n the railway between Abbasijeh and Citadelle, near Cairo, there occur stalactitic masses hitherto thought to have been geyser deposits. On examination, they are found to consist of cemented quartz sands, approximating in composition t o artificial mortar. Sand. SiO,. CaO. A1,0, i- Fe20,. GO,. H,O. MgO. SO,. NaC1. 4$90 6-24 22.80 1-47 14.00 3-83? 3-58 0.58 0.24 B. H. B. Obsidian Cliff, Yellowstone National Park. By J. P.IDDINGS (Seventh Awnual Rep. U.X. Geol. Survey, 249-29.i).-The author describes in detail, in a monograph of 4!4 pages, illustrated by 51 plates, the geological occurrence, lithological structure, petrographical and microscopical cliamcters of 0 bsidian Cliff, at the northern end of Beaver Lake, in the Yellowstone National Park. Though obsidian of nearly the same chemical composition occurs in all parts of the world, the obsidian flow at Beaver Lake is especially remarkable for its unsurpassed extent and thickness. lt is the only known occurreuce of rhyolitic obsidian in which a distinctly columnar structure has been developed. It is entirely free from porphyritic crystals, and abounds in spherulitic structures and lithophysm. These are undoubtedly of primary cry stallisation out of a molten glass, which was graduallj- cooling.Since its solidification, too, no alteration, chemical o r mechanical, has taken place. Analyais yielded the following results :- B. H. l3. Eruptive Rocks of the Cab0 de Gata. By A. OSANN (Jahrh. .f. illin., 1890, ii, Ref., 268-270 ; from Zeit. deutsch. geol. GPS., 41, 297-311) .-The author describes in detail the occurrence of eruptive rocks at the Cab0 de Gata, Almeria, Spain. The predominating rocks are andesites, dacites, and liparites. Basalts are eritirelg absent, as also are nephelirie and leucite rocks. Only one rock contains olivine. This occurs in the vicinity of Vera and is described by Calderon as limburgite. It is the youngest of the eruptive rocks of the district, and on analysis gave results approximating most closely to those obtained with olivine-bearing lamprophyres, such as the rninette of the Ballon d’lilsace.l n the rock, biotite only is visible t o the naked eye, whilst olivine, augite, and a little felspar can be detected under the microscope. The analytical results were as follows :- Si02. AI20,. Fe2O3. FeO. MnO. MgO. CaO. K,O. Ne,O. 55.17 13.49 3.10 3-55 0.39 8.55 3.15 1.09 4-43 H,O. 60,. Total. 4.27 3-27 100.46MINERALOOICJAL CHEMISTRY, 27 The rock is named Verite by the author. It should certainly not Meteoric Iron from Magura, Arva, Hungary. By E. WEINSCHENK (Jahrh. f. M ~ ! L . , 1890, ii, Ref. 57-59 ; from Ann. k. k. Hof- nausewms, 4, 93-101 ; compare Berthelot and Friedel, Abstr., 1890, 1384).--In an investigation of the meteoric iron from Magura, Arra county, Hungary, the author succeeded in isolating the following constituents :-- 1.Tin-white regular crystals, hitherto regarded as schreibersite. These appear to have a cleavage perpendicular to the longitudinal axis ; they are stronglp magnetic, very brittle, and soluble in hydro- chloric acid and copper ammonium chloyide, with separation of carbon. The hardness is 54 t o 6, and the sp. gr. 6.977. Analysis (No. I) gave, after subtraction of schreibersite, results corresponding with the formula C(FeNiCo),. For this new mineral, the author proposes the name of cohsnite. d. Thin, silver-white, strongly magnetic lamellq which are but slowly soluble in hydrochloric acid, and which may represent Reichenbach’s t m i t e . The composition (Analysis 11) is in accord with the formula Fe,(NiCo)2.3. Fragments of various shapes, which form the principal maw of the iron. They are highly magnetic, sparingly soluble in hydro- chloric acid, and give on analysis (Xo. IlIj results corresponJing with the formula Fe,(NiCo). The high percentage of cobalt is noteworthy- be classed as a limburgite. B. H. B. Fe. Xi. Co, C. Cu. Sn. Schreibersite. Total. I. 89.83 3.08 0.79 6.43 trace trace 0.63 100*78 11. 71.04 26.64 1.67 0.30 - - - 99.65 111. 87.96 9.19 2.60 0.36 - - - 100.11 4. Crystals of rhornbic mid monoclinic augite. 5. Grains of partly isotropic, partly feebly bi-refractive, diamond proved to be harder than ruby and to burn to carbonic anhydride in a current of oxygen. Colvurless or strongly pleochroic blue grains appear to consist of curundum, whilst small, colourless aggregates may be tridymite.The author compares the varieties of carbon met with in meteoric iron with thoRe in pig iron. The “ hardening-carbon ” corresponds with the carbon given off in the form of hydrocarbons when the meteoric iron is dissolved in hydrochloric acid ; the ordinary carbide carbon corresponds with cohenite ; the grnphitic tempering-carbon Ivith the carbon in the residue when meteoric iron is dissolved ; and, lastly, graphite is met with in both varieties of iron. This perfect analogy leads to the assumption that the conditions under which meteoric iron was formed are coniparable to those under which pig iron is produced, and the presence of the diamond indicates that the carbon dissolved or chemically combined in iron can under certain conditions separate oat in the allotropic form of the diamond.B. H. B.20 ABSTRACTS OF CHEMICAL PAPERS.Min e r a1 o gi c a Z C h e mi s t ry.Bismuth Minerals from Gladhammar. By G. LINDSTR~X(Jahrb. j*. Mia., 1890, ii, Ref. 53; from Ge6l. FiirPn. Forhand., 11,771).-On examining a series of ores, tbe atithor found a lead-grey totin-white mineral with a brilliant lnstre. On analysis, it gave thefollowing results :-Bi. Pb. Ca. Fe. Zn. S. Insol. Total.33.84 48-05 0.69 0-16 0-05 15-92 0-45 99-16Theauthor is unacquainted with a mineral of this coniposition (compere,lrowever, lillianite, 3Ph(Ag)S + Bi,S,).As an assay of another specimen gave 42.15 per cent. of lead, it isHamlinite, a New Rhombohedra1 Mineral.By W. E. HIDDENant1 S . L. PEKF~ELD (Amer. J. Sci., 39, 511--.’13).-Shortly after t h ediscovcry of ‘taerderite (Abstr., 1884, 827, 11 02) at Stoneham, Maine,this mineral was detected occurring as miniite, rhombohedra1 crvstals,:issoc*iated with herderite, margarodite, and the rare glucinum silicate,hertrandite. During the past five years, the authors have kept up adiligent search €or the crystals, but without success. The crystalsare hexagorial-rhombohedritl, and vary from 1 to 2 mm. in diameter..Their hardness is 45, and their sp. gr. 3.229. Qualitative analysisindicates that the mineral is a new species-a phosphate, probably ofglucinum and aluminium, containing fluorine. The authors proposefor it the name of humliiiite, in honour of Dr.A. C, Hamlin, who islargely interested in the development of the mineral resources of thedistrict in which the new mineral occurs.The formula deduced from these results is 3PbS + Bi,S,.possible that bjelki te also occurs a t Gladhammar. €3. €3. B.B. H. B.Preparatioa of Artificial Molybdenite. By A. v. SCHULTEN(Jahrb, ,f. X t z . , 1890, ii, Ref. 223 ; from Geol. Foren,. b’orAa~~dZ., 11,401).-The author melted 4 gleams of potassium carbonfite with6 grams of sulphur in a porcelain crucible, and on cooling added1 gram of molybdic anhydride. ‘J’he mass was then heated in a well-closed c.rucible to a melting heat, and, on cooling, a fresh portion ofthe anhydride was added. The process was repeated until 5 t o 6 gramsof molgbdic anhydride had been used.On boiling the melted Iliantiwith water, a residue of pure crystallised molybdenite, Mod,, wasobtained in the form o€ greyish-violet, opaque, hexagonal crystalswith a sp. gr. of 5.06 a t 15”. The crystah are very soft, and makegrey marks on paper.Flinkite and Heliophy llite from Harstigen Mine, Sweden.By A. HAMBERG (Jahrh. j‘. Miu., 1890, ii., Ref. 834-228, fromGeol. Fiiren. ForhundZ., 11, 21 2).-Flinkite, a hydrated manganesearsenate, occurs in khe Harstigen mine, Pajsberg, Wermland, iugreenish-brown crystals with sarkinite on karyopilite. Its sp, gr. isB. H. BMINERALOGICAL CHEMISTRY. 2 13.87.rhombic system, the forms observed being UP, Pm, P, mP00.analysis, it gave results corresponding with the formula,It has a hardness of more than 4, and-crystallise_s in theOIL4H20,.EMn0,Mn203,As206,a composition very similar to that of sjnadelphite.An optical exauiinntion of the mineral heliophyllite, described byG.Flink as biaxial, showed i t to be always composed of biaxial anduniaxial portions. The author distinguishes two types of thismineral as met with at the Harstigen mine : (1) the coarsely lami-nated variety ; and (2) crystals associated with baryytes and inesite.The optical properties exhibited are similar t o those shown by themineral ekdemite from Lingban, described by Nordenskiold asoptically uniaxial. Further, the minerals appear to be chemicallyidentical, analysis having given the following resnlts :-PbO. FeO + MnO. CaO.A S , ~ , . Sb203. CI.10.60 - 8.0011.. . . . . 81.03 0-07 0.08 19.85 0.56 8.05111.. . . . . 80.99 0.16 0.11 10.49 1.38 7.96I.. . . . . 83.45 - -1. Ekdemite (Nordenskiold). 11. Heliophyllite, type I. I11 thesame, type 11. Nordenskiiild calculates the fbrrniila, Pb5As208 +2PbC12, Flink gives PbcAs2O7 + 2PbC1,. The author, however, is ofopinion that the more exact formula Pb,As,O,, + 4PbC12 is notimprobable. B. H. B.Minerals from Styria. By E. HATLE and H. TAUSS (Jak-b. f..illit!., 1890, ii., Ref. 1 7 ; from Vwhandl. geol. Reichsanst., 1887,226-229) .--1 . Pharmacolite from Viillig. 'l'his mineral occurs in~ h i t e , trauslucent groups of' crystals and crusts with B fibroustexture.As.205. CaO. H,O.48-60 27-04 24.49Analjsis yielded the following results :-The mineral is associated with zinc-blende, plena, arsenicalpyrites, magnetic pyrites.iron pyrites, quartz, and calcite.2. Iron-gjmnite from Kraubath. This mineral occurs, with yellowgjmnite, in serpentine. It ha's a hardness of 3, and a sp. gr. of 1.986.Analysis yielded the folIowing results :-SiO,. MgO. FeO. H2O.41-55 30.24 6.60 20.10Allowance being made for 1-27 per cent. of ferric oxide dissemi-nated in tlie form of iron mica, the formula is H,,Mgl2E'eSl1O,, +9HZO. B. H. B.Fluorine and the Synthesis of Minerals. By S. MEUEIER(Compt. 1-end., 111, 509-51 1) .-The iise of aluminium fluoride makesit pomihle to obtain in a compratively short time, and at the tempe22 ABSTRACTS OF CEIEMICAL PAPERS.rature of an ordinai-y coke fire, several minerals, which underordinary conditions are difficult to synthesise.32 parts of calcined silica, 8 parts of fused potassium hydroxide,and 44 parts of aluminium fluoride, yield a regulus which is notcompletely vitreous but gives a fracture with a silky lustre.Underthe microscope, it is seen to contain needles of sillimanite and hexa-gonal lamella of tridymite i n large quantity, together with inclusionsof various kinds and globuliform masses which are almost opaque.43 parts of silica, 20 of calcium oxide, and 60 of aluminiumfluoride yield a product which, although chiefly a glass, has a highlylustrous fracture, and contains needles of sillimanite and lamellae oftrid ymite.26 parts of silica, 12 of calcium oxide, 2 of potassium hydroxide,and 25 of aluminium fluoride yield.a decidedly crystalline productcontaining large quan t.ities of thin plates of labradorite, many ofwhich are macled according to the albite law, whilst the larger havespheroidal inclusions.22 parts of silica, 17 of alumina, 0.2 of ferric oxide, 8 of sodiumhydroxide, '2 of potassium hydroxide, and 1 of lime, in a cruciblebrasqued with cryolite, jie!d a deep grey granulo-crystalline product.The mass is vitreous, but is fuli of inclusions, and contains manycrystals of sillimanite, and a large quantity of prismatic crystals ofnepheline.27 parts of silica, 12 of alumina, and 10 of potlassium hydroxidein B crucible brasqued with cryolite, yield a partially vitreousproduct f u l l of crystalline granules.Under the microscope, largc!numbers of smd1 globules are seen, identical with the leucite ofnatural amphigenes. C. H. B.Sigterite, a New Felspar. By C. RAMMELSREKG (,Juhrb.f. Min.,1890, ii, Mem. 71--74).-1n an investigation into the properties of eu-dialyte from Sigtero, the author found that this mineral was associatedwith two others, white albite and another felspar in the form of grey,granular particles. The new felspar has the cleavage of ort'hoclase,and, chemically, is a potassium sodium felspar free from lime, andmuch more basic than albite and orthoclase. I n thin sections, in-clusions of augite and a small quantity of magnesia-mica wereobserved. After making corrections for the small quantities of augitepresent, the mineral gives on analysis the following results :-SiOz.A1,0,. Na,O. KzO. Total.50.01 30.86 13.90 523 100.00The formula of the felspar is therefore (NaK),AISi,Olo.words, i t is a combination of albite and an alkali anorkhite.same time, it has the composition of an anhydrous natrolite.I n otherAt theB. H. B.Minerals from Vesuvius. By E. SCACCHI (Zeit. K?-yst. Min., 18,99-102; from R. Accud. d i Napoli, 3888, 12).-1. l'hakellite, i~new mineral. Among the Somrna minerals in the ninseum of theUniversity of Naples there is a substance, hitherto undescribed, whicMINERALOGICAL OHEMISTRY. 23the author has named from its characteristic combination of trans-parent, colourless needles to white, silky bundles (@&Xhr). Thisrare mineral occurs in a rock consisting of augite with more or lessmica, and occasionally in grey, granular calcite. Optically themineral is uniaxial, with faint negative birefraction, and thereforebelongs to the hexagonal system.It has the hardness of orthoclase,and a sp. gr. of 2.49. Analysis gave the following results :-SiO,. A1,0,. K20. Na,O. Total.37.73 33.33 29.30 0.37 100.73Formula : K2A12Si208.2. Thernioncitvite, from the lava of 1859.The analogy with nepheline is remarkable.This mineral is new forVesuvius. The Naples museum recently received numerous white,opaque, drusy incrustations from the Fosso grande. On analysis, thismineral, Na,CO, + HzO, yielded 35-44 per cent. of carbonic anhjdride.3. Soda from the interior of the same lava in crystalline, colour-less, transparent grains.On analysis, the following results wereobtaked :-CO,. Na,O. K20. H20. Total.15.91 22-15 0.41 61.68 100.15These results correspond with the formula Na,C03 + lOH,O. Themineral cannot have been produced by sublimation, but by the actionof carbonic anhjdride which has decomposed the lava and taken thesoda from it.4. Altered cowpfonite from the Somma conglomerates. In oneyariety of conglomet ate at Vesuvius, zeolites occnr ill associationwith calcite. Among these, small crystals resembling comptonite areoccasionally met with, the change in the chemical composition of thezeolites and the variation from that of comptonite consisting chieflyin a loss of water, an absorption of calcium carbonate, and a changein the ratio of the silica, to the alumina, (compare Abstr., 1887, 17).B.H. B.Amphibolite from Habendorqrin Silesia. By E. DATHE ( J a h ~ h .$. Min., 18W, ii, Ref., 243-244 ; from Jalwb. preuss. geol. Landesnnst.,1889, 309-328) .-The amphibolite (Analysis I) occurring in thehiotite gneiss of Habendorf, consists of hornblende of a greenish-blackcolour and bdliant lustre. There is a second variety (Analysis 11)composed of light greenish-grey hornblende, with a little pyrrhotiteand mica. Under the microscope, olivine, diopside, chromite, andrutile could also be detected.SiO,. Ti02. Fe20,. Cr,O,. Al,O,. FeO. MgO. CaO.I . . 46.47 0.21 4.18 trace 8.68 3.73 22.79 9-0511 . . 47-82 0.65 0.94 0.65 7.88 3-50 29-56 3.6642,O. Na20. H,O.CO,. Total. Sp. gr.I .. 0.35 1.14 3.39 - 99.99 2.95911.. trace 0.43 4.20 0.41 99.48 2.857B. H. B24 ABSTRAOTS OF CHEMICAL PAPERS.Chemical Nature of Tourmaline. By C. RAMW ELSRERG (Ju7wb.f. JIi,t., 1890, ii, Mem., 149--162).-1n this paper the author re-calculates some 70 analyses of tourmaline, with a view to controvertthe formula: recently arrived a t by Riggs (Abstr., 1888, 660), Jan-nasch and Calb (Abstr., 1889, 4 Z ) , Scharizer (Abstr., 1689, 764)) andWiilfing (Abstr., 18r39, 765). He is slill of opinion that his interpre-tation of thc tourmaline analyses of 20 years ago was correct, eccordingto which they must be regarded as isomorphous mixtures of thressilicates, R'$3iO5. R"3Si05, and R"Si05, in which R' representsH, Na, K, Li ; R" represents Fe, M L ~ , Mg, Ca ; and Rvi representsA12, Fez, B,, Cr2.By G.W. KALB (Jnhd. f. Min.,1890, ii. Ref. 199-203 ; from Innug. Diss. Gottinge,/,, 1890).-Tenvarieties of tourmaline analysed by the author may be divided intot.hree groups :-( 1) Lithium tonrmaline, (2) iron magnesium tour-maline, (3) iron tourmaline. From the analyses, the author deducesthe general formula R,BO,(SiOa),. [The analyses given appear to bealmost identical with those given in a paper by P. Jannasch andG. Cslb (Abstr., 1889, 472).]By M. KOCH (Jah~b. f. Mh., 1830,ii, Ref. 244-245 ; from Zeit. deutsch. geol. Ges., 41, 163-165).-Peridotite occurring in the gabbro mass of the Kaltenthal, in theHarz, contains olivine in angular grains, as much as 23 mm. in size,with biotite, spinel, and titaniferous iron ore.Small quantities ofaugite and plagioclase are present as accessory constituents. Therock is more basic than any of the basic members of the Harzburggabbro hitherto examined, as ir, shown by the following analyticalresults, in which the high percentage of titanium is probably due totlie biotite :-SiOz. Ti02. Al20,. Fe,O,. FeO. MgO. CaO. K20.34.98 5.18 10.80 1.42 21.33 19.30 0.43 5.42NazO. H2O. 503. Total. Sp. gr.0.17 1:28 trace 100.31 3.27B. H. H,Composition of Tourmaline.B. H. €3.Peridotite from the Harz.B, H. B.Minerals of the Garnet Group. By W. C. BROGGER and H.HACKSTROM (Zeit. Kvyst. iWin., 18, 209-276).-0f the 12 silicatescrystallieing in the regular system, eulytine, zunyite, helvine,danalite, garnet, sodalite, nosean, lapis-lazuli, leucite (maskelynite),pollux, analcirue, aiid faujnsite, the first eight are orthosilicates, andthe last four metasilicates.Three of the metasilicates, maskelynite,pollux, and analcirne! belong to one morphological group, whilstfaujasite is an isolated species of octahedral type. The orthosilicatesare regarded by the author as forming one large group, the garnetgroup, which may be subdivided into two divisions :-(1) Orthosilicatesof tetrahedral character, and (2) orthosilicates of rhom bic dodeca-hedral character. This second division includes holohedral members(the garnet series proper), as well as liemihcdral ones (the alkaliQ arn e t s) MINERALOGICAL OHEMISTRT. 25The formula? of the members of the first division are as foi1ow.s:-Eulytine ......Bi4(SiO&.Zunyite . . . . . .Danalite. . . . . .Helvine . . . I . .[A16F2C1(0H),]Al,(SiO~)3.(FeZnMn),[ (ZnFe)zS]Be3(Si04),.(MnE'eCa),(Mn,S)Be,(Si04j3.In this voluminous paper, the author brings forward a mass offacts to prore t,he close connection of the regular orthosilicates. Theanalyses of all the mineials of this garnet group lead to f o r m u l ~ inwhich there is 1 mol. of an orthosilicate with 3 mols. of silicic acid.All the members of this group, too, belong to the regular system. Avery large number of analyses are discussed. Of these, the followiughave not previously been published : -SiO,. A1,O.I. 36.74 31.9611. 37-24 31.60111. 31.65 27.03IV. 31.99 2732 v.32.30 27.38VI. 32-20 27-37PII. 32.52 %7%1VIII. 39-48 27-62IX. 53.13 1.76X. 55.15 -XI. 55.55 -CaO.0.2 1-9-948.218.186.476.6024.il26.3825.95MgO. Na,O. K20. SO,. 8. C1. HzO.- 85.95 trace 0.11 - 7.11 9.1725-60 - - - 7.31 -27.26 - 14.06 - - -- 16.53 - 14.22 - - -0.11 18.03 0.35 12.62 0.44 0.31 -0.11 17.98 0.35 13.17 0.46 0.33 ---- 19.4.5 0.28 10.46 2.71 0.47 -- 19.84 0-29 10.47 2.71 0.47 0.0716.93 2.62 - - - - 1.3118.47 - - - - - -18.52 - __ - - - -I. Sodalitc. 11. Results calculated from the formulaNa4( A1 Cl) Al,( SiO,),.111. Nosean, formula Na4( A1[S04Na]) AlZ(SiO4),. TV. Hauyn, formulaNil,Ca[Al( SO4Na)]Al,( SiO,),. V. Hauyn, analysis. V1, Resultscalculated from 92 mols. hauyn, 5.2 mols. sodnlite, and 2.7 mols,ultramarine with the formula Na4[A1( S,Na)]A12( SiO,),.VII. Lapis-lazuli. VIII. The same, results calculated from a composition of'76 9 mols. hauyn, 15.7-mols. ultramarine, and '7.4 mols. sodalite. IX.Diopside occurring enclosed in lapis lazuli. X. Results after sub-traction of 8 per cent. lazurite. XI. Results corresponding withformula CaMg( SiO,),. J3. H B.Minerals and Roouks in the Diamond Fields of SouthAfrica. By A. KNOP (Jlrhrt.f. Min., ii, Ref. 97--99).-Tlie matrixof the diamonds, the so-called blue earth, is found on examination tobehave like a serpentine which, after decomposition by acid, leavesinicroliths of pyroxenic character. The rock may be described as aserpentine-tuff enclosing, at Jagersfontein, the following minerals :garnet, chrome-diopside, enstatite, chromite, zircon, apatite, idocrase.~utile, mica, and diamond.These minerals are described in detail bythe author, who gives analyses of the chrome-diopside and chrome-irou ore.The author regards the Jagersfontein deposit as having been forme26 ABSTRAUTS OF CHE1\1ICAL PAPERS.from a peridotite, which has been mechanically broken up and trans-ported to a favourably situated locality, where it has become ser-pentinised. The relation of the diamond to the peridotite is thoughtto be analogous to the occurrence of the diamond in meteorites.B. H. B.Natural Cement from Cairo. By E. SICKENBERGER (Jnhrb. ,f.E n . , 1890, ii, Ref. 275-276; from Zeii. deutscta. geol. Ges., 41,312--318).-0n the railway between Abbasijeh and Citadelle, nearCairo, there occur stalactitic masses hitherto thought to have beengeyser deposits.On examination, they are found to consist ofcemented quartz sands, approximating in composition t o artificialmortar.Sand. SiO,. CaO. A1,0, i- Fe20,. GO,. H,O. MgO. SO,. NaC1.4$90 6-24 22.80 1-47 14.00 3-83? 3-58 0.58 0.24B. H. B.Obsidian Cliff, Yellowstone National Park. By J. P. IDDINGS(Seventh Awnual Rep. U.X. Geol. Survey, 249-29.i).-The authordescribes in detail, in a monograph of 4!4 pages, illustrated by 51plates, the geological occurrence, lithological structure, petrographicaland microscopical cliamcters of 0 bsidian Cliff, at the northern endof Beaver Lake, in the Yellowstone National Park.Though obsidianof nearly the same chemical composition occurs in all parts of theworld, the obsidian flow at Beaver Lake is especially remarkable forits unsurpassed extent and thickness. lt is the only known occurreuceof rhyolitic obsidian in which a distinctly columnar structure has beendeveloped. It is entirely free from porphyritic crystals, and aboundsin spherulitic structures and lithophysm. These are undoubtedly ofprimary cry stallisation out of a molten glass, which was graduallj-cooling. Since its solidification, too, no alteration, chemical o rmechanical, has taken place.Analyais yielded the following results :-B. H. l3.Eruptive Rocks of the Cab0 de Gata. By A. OSANN (Jahrh..f. illin., 1890, ii, Ref., 268-270 ; from Zeit.deutsch. geol. GPS., 41,297-311) .-The author describes in detail the occurrence of eruptiverocks at the Cab0 de Gata, Almeria, Spain. The predominatingrocks are andesites, dacites, and liparites. Basalts are eritirelgabsent, as also are nephelirie and leucite rocks. Only one rockcontains olivine. This occurs in the vicinity of Vera and is describedby Calderon as limburgite. It is the youngest of the eruptive rocksof the district, and on analysis gave results approximating mostclosely to those obtained with olivine-bearing lamprophyres, such asthe rninette of the Ballon d’lilsace. l n the rock, biotite only is visiblet o the naked eye, whilst olivine, augite, and a little felspar can bedetected under the microscope. The analytical results were asfollows :-Si02.AI20,. Fe2O3. FeO. MnO. MgO. CaO. K,O. Ne,O.55.17 13.49 3.10 3-55 0.39 8.55 3.15 1.09 4-43H,O. 60,. Total.4.27 3-27 100.4MINERALOOICJAL CHEMISTRY, 27The rock is named Verite by the author. It should certainly notMeteoric Iron from Magura, Arva, Hungary. By E.WEINSCHENK (Jahrh. f. M ~ ! L . , 1890, ii, Ref. 57-59 ; from Ann. k. k. Hof-nausewms, 4, 93-101 ; compare Berthelot and Friedel, Abstr., 1890,1384).--In an investigation of the meteoric iron from Magura, Arracounty, Hungary, the author succeeded in isolating the followingconstituents :--1. Tin-white regular crystals, hitherto regarded as schreibersite.These appear to have a cleavage perpendicular to the longitudinalaxis ; they are stronglp magnetic, very brittle, and soluble in hydro-chloric acid and copper ammonium chloyide, with separation ofcarbon. The hardness is 54 t o 6, and the sp. gr. 6.977. Analysis(No. I) gave, after subtraction of schreibersite, results correspondingwith the formula C(FeNiCo),. For this new mineral, the authorproposes the name of cohsnite.d. Thin, silver-white, strongly magnetic lamellq which are butslowly soluble in hydrochloric acid, and which may representReichenbach’s t m i t e . The composition (Analysis 11) is in accordwith the formula Fe,(NiCo)2.3. Fragments of various shapes, which form the principal maw ofthe iron. They are highly magnetic, sparingly soluble in hydro-chloric acid, and give on analysis (Xo. IlIj results corresponJingwith the formula Fe,(NiCo). The high percentage of cobalt isnoteworthy-be classed as a limburgite. B. H. B.Fe. Xi. Co, C. Cu. Sn. Schreibersite. Total.I. 89.83 3.08 0.79 6.43 trace trace 0.63 100*7811. 71.04 26.64 1.67 0.30 - - - 99.65111. 87.96 9.19 2.60 0.36 - - - 100.114. Crystals of rhornbic mid monoclinic augite.5. Grains of partly isotropic, partly feebly bi-refractive, diamondproved to be harder than ruby and to burn to carbonic anhydride ina current of oxygen.Colvurless or strongly pleochroic blue grains appear to consist ofcurundum, whilst small, colourless aggregates may be tridymite.The author compares the varieties of carbon met with in meteoriciron with thoRe in pig iron. The “ hardening-carbon ” correspondswith the carbon given off in the form of hydrocarbons when themeteoric iron is dissolved in hydrochloric acid ; the ordinary carbidecarbon corresponds with cohenite ; the grnphitic tempering-carbonIvith the carbon in the residue when meteoric iron is dissolved ; and,lastly, graphite is met with in both varieties of iron. This perfectanalogy leads to the assumption that the conditions under whichmeteoric iron was formed are coniparable to those under which pigiron is produced, and the presence of the diamond indicates that thecarbon dissolved or chemically combined in iron can under certainconditions separate oat in the allotropic form of the diamond.B. H. B

ISSN:0368-1769    

DOI:10.1039/CA8916000020

出版商:RSC    

年代:1891

数据来源: RSC

摘要:

28 ABSTRACTS OF CHEMICAL PAPERS.Organic Chemistry.Condensation of Acetylene by the Silent Discharge. ByBERTHELOT (Compt. ?*end., 111, 471--472.)-If the product. of the con-densation of acetylene under the influence of the silent discharge isleft exposed to the air, it absorbs about one quarter of its weight ofoxygen, and can easily be detached from the glass in the form of ayellow, resinous pellisle. It continues to alter spont,aneons!y in thevessel in which it is placed, with formation of a carbonaceous sub-limate which is probably the result of a secondary change. Whensubjected to dry distillation, i t undergoes sudden and explosive de-compositrion, which seems to be exothermic, wihh production of aconsiderable quantity of water, together with some acetic acid, andacetouic liquids which have an odour of caramel, and are similar to,if not ident,ical with, %he products from sugar or tartaric acid. Neitherbenzene nor furfuraldehFde is obtained, and distillation with soda-lirncyields acetone and other simple products.It is clear therefore thattlie condensation of acetylene under the influence of the silent dis-charge is very different from its condensation under the infinerice ofheat, C. H. I3.Combination of Mercuric Cyanide with Lithium Salts. ByR. VARET (Coinyt. rend., 111, 526-527>.-A concentrated solution oflithium iodide is added drop by drop to a saturated solution ofrriercuric cyanide heatred a t 50-60". A further quantit,y of mercuriccyanide is then dissolved in the liquid and more lithium iodide isadded.The liquid is concentrated to a, syrup, filtered, and allowed tocool, when it deposits the compound HgCy2,2LiCy,Hg12 + 7H20 i nlarge nacreous lamellae, which are hygroscopic, very soluble in water,and lose 3 mols. H,O a t IOO", but cannot be completely dehydratedwithout, decomposing. When the salt is carefully heated, it gives offwater and becomes yellow, a sublimate of mercuric iodide forming atthe same time. At a higher temperature, the salt melts and decom-poses into mercuric iodide, mercury, cyanogen, aiid mercurms iodide.Dilute acids decompose the salt with liberation of hydrocyanic acidand precipitation of mercuric iodide, whilst mercuric cyanide a-nd alitliium salt of the particular acid remain in mlution.Coppersnlphate, when heated with a sclution of the salt, qrecipitates cuprouscyanide and mercuric iodide, a result, which indicates tha,t all thecyanogen is not combined with the mercury. These reactions showthat the constitution of the compound is expressed by the formuhgiven.I f lithium bromide is added gradually and in small quantity to afiaturated solution of meimwic cyanide heated at go", the liquid, oncooling, deposits crystals of the compound HgCy,,LiBr + 3+ H,O.They are hygroscopic and very soluble in water, lose 14 mols. H,O at loo", but cannot be dehydrated without decomposing. When heatedgently, i t yields no sublimat,e of mercuric bromide, hut a t a hightempersture i t undergoes complex decomposition. When heated witOItUANlC CBE MISTRY.29copper mlpliatc solution, no cjanogen is evolved, and no precipitateis formed ; it follows that all the cyariogen is combined with themercury.A mercury lithinm cyanochloride is obtained by evaporating asolution of mercuric cyai)ide containing an excess of litliium cliloi-ide.It is so hygroscopic that its composition could not be ascertained.C. H. B.Ethylene Dithiocyanate. By. C. PARENTI (Gnxzetfa, 20,178--183).-By tIeating perthiocyanic acid with alcoholic pchash,E'leischer (this Journal, 18i1, 391) obtained a compound isomericwith potassium thio- and ibothio-cyanate, but differing from thest,compounds in several respects (Annalen, 179, 204). The acid formcdh v decomposing this salt with sulphuric acid was considered to be adithiocyanic acid.To prepare the ethylene derivative, perthiocyw [ti(:acid and ethylene bromide in molecular proportion are dissolved inthe least possible quantity of alcohol, mixed with ail alcoholic solut ono€ potassium hydroxide, and boiled for 5 to 6 hours. The filteredliquid, on cooling, deposits a semi-crystalline mass, part of which isinsoluble in boiling water, and remains in hard ill-defined crystalswhich melt a t 137-140". The soluble portion, on recrystallisationfrom boiling water, is obtained in slightly yellowish prisms which meltat 349-150°, and are readily soluble in hot water and alcohol, b u t ,insoluble in ether and benzene. It dissolves in cold conc*entratedsnlphuric acid, and is reprecipitated unaltered on the addition ofwater.After fusion, it resolidifies at 13O", but t h i s temperature isI-educed to 118" after successive fusions. The aqueous solutionirs nut coloured by ferric chloride even after acidification with hydro-chloric acid ; on heating the alkaline solutions, the respective thio-cjanates are formed. The constitution of this salt is prohablyK*C,H,*N. The compound melting a t 137--140" has the composi-tion CaN,S3(C2H4), ; it is slightly soluble in cold concentratedsulphuric acid, and, on warming, a gr*een liquid with a bluefluorescence is prGduced from which sulphur separates after a time.S. B. A. A,FS\\cs/Diacetylcarbinyl Acetate. By A. COMBES (Compt. rend., 111,4~1--423).-Chlo1~aceryIat etone (Abstr., 1890, 1394), when boiledwith potassium acetate in presence of alcohol, yields a pale-jellow liquid which boils at 74.5" under a pressuie of 21 mm.,itlso a large quantity of ethyl acetate.The new product hasthe composition C,H,O,; it bas an acid odour, but yields nitnietnllic derivatives, and reduces Fehiing's solution and aminoniecald v e r nitrate in the cold. It yields a very unstable hydiazoiieCll,H14N202, which resinitit s rapidly when exposed to air and light,and crystallises from ether in large coloui less rhomboidal tableswhich rapidly become red n h t n exposed to light. If this hydrazoneis treated with excess of phenylhydrazine in alcoholic solutiou, i tyields an oaazone CI5H,a4, very soluble in ether, from which it i30 ABSTRACTS OF OHIEMICAL PAPERS.precipitated by light petroleum in crystals melting a t 143-1144'. Itis the osazone of acetol, and can also be obtained by the direct actionof phenylhydrazine on a hot solution of the compound C,H,O, inacetic acid.The cornpound C,H,03 is in fact the acetate of acetol, formed inaccordance with the equations CHAc,Cl + AcOK = CHAc,*OAc +KC1 ; CHAC,.OAC + EtOH = CH,AC.OAC + AcOEt.I n order to avoid the secondary action of the alcohol, monoclilor-acetylacetone was boiled for four or five hours with potassiumacetate in presence of glacial acetic acid, and the product was pouredinto water and mixed wit,h concentrated cupric acetate solution.Agreen precipitate separates, and is purified by solution in chloroformand precipitation with ether ; it forms deep-green crystals of the com-position (C,H,O,),Cu, and is the cupric salt of diacetylcarbinol,CHAc,*OAc, which contains a basic hydrogen atom in the groupZCH-OAC.The copper salt is dissolved in dilute sulphnric acid,and the solution is extracted with ether. Aiter the ether has beenexpelled, the diacetylcarbinyl acetate is obtained as a colourlessliquid boiling at 111" under a pressure of 21 mm. It reducesFehling's solution and ammoniacal silver nitrate iii the cold, has astrongly acid reaction, and decomposes carbonates with formation ofcrystallisable metallic derivatives. When treated with phenyl-hydrazine, it yields a viscous liquid which boils without decompositionin a vacuum a t 235--'240", and which, when treated with hot sulph-uric acid or with oxidising agents, yields a beautiful, blue colour-ing malher, insoluble in watw, but.soluble in chloroform or sulphuricacid, and having all the characteristics of a pyrazole-blue.Attemph to obtain diacetylcarbinol by saponification of the acetatehave not yet been successful. C. H. B.Indian Geranium Oil: Oxidation of Geraniol. By F. W.SEMMLF;R (Bey., 23, 2965-2968 ; see also Abstr., 1890, 951),---Fmthe oxidation of geraniol, potassium dichromate (10 grams) is dis-solved in sulphuric acid (12.5 grams) and water (100 grams), and thcgei-aniol added (15 grams all a t once), the mixture being a t first wellcooled, and af Lerwards allowed GO become warm, and vigorouslyshaken for half an hour. The whole is then made slightly alkalineand distilled in a current of steam.The distillate contains an oil,which has a pleasant odour resenibliiig oranges and lemons, and is amixture of the oxidation product with ethereal oils formed by t,heaction of the sulphuric acid on geraniol. To separate the latter, theoil is mixed with s saturated solution of sodium hydrogen sulphite,and allowed to remain for 24 hours. The crystalline magma is the11collected, pressed between filter-paper, washed with ether, mixed withsodinm carbonate, and distilled i n a current of steam. A clear, C0lOUJ'-less oil, haviug the composition C,,HI6O and the above-mentionedcharacteristic odour, is thus obtained, aiid appears from its genera]reactioiis to be an aldehyde. It is at present being more closelyexamined.Alkttl-ine potassium permanganate acts on geraniol in a differentORQANIO CHEMISTRY.31manner, yielding a polyvalent alcohol, which has the closest rcsembl-ance to the sugars. H. G. C.Dihydric Alcohols derived from Isobutaldehyde. By E.STOBODA and W. FOWEK (Monatsk., 11, 383--398).-1t has been pre-viously shown (compare Abstr., 1884, 37, 832) that when alcoholicpotash acts on a mixture of isobutaldehyde and acetaldehyde, methyl-isopropyleth ylene glycol, OH-CHMe*CHP@.OH, boiling at 206-20i0,is formed. When valeraldehyde and benzaldehyde are substitutedfor acetaldehyde, isobut~lisop~o~ylefhylene glycol,CHMe2*CH,*C H (OH) *CHPrfl*O€T,which melts a t 79-80" and hoils a t 23 1-232", and pheniyZisopmpjII-ethylene gZ!/coZ, OH*CHPh-CHP@*OH, melting at 8 1 - 4 2 " and boilingat 286-287", are formed respectively.In the formation of isohutyl-isopropylethylene glycol, potassium isobutyrate is the only other pro-duct; i t must therefore be supposed that a molecule of isohut-aldehyde unites with a molecule of valeraldehyde through their alde-hydic carbon atoms, which, a t the moment of condensation, take upeach an atom of hydrogen, fiirnished by the oxidation of anothermolecule of isobutaldehyde by a molecule of potassium hydroxide.The three glycols yield diacetyl derjvat'ives, when heated for18 hours, in sealed tubes, a t 200", with an excess of acetic anhydride.The compounds thus obtained from methylisopropyl glycol, isopropyl-isobutpletliylene glycol and phenplisopropylethylene glycol, haverespectively the formulae CloHI9O4, C13H2204, and C1sH2004, and theboiling points 220", 240-242", and 295-297".Cn treatment with sulphuric acid, the three glycols behave as pina-cones, and lose the elements ul a molecule of water ; isopropylisobutylglycol is converted by cold concentzated sulphuric acid into ana-pinncoline, C,H,,O, which boils at 150" and has the odour of camphor,and by hot dilute acid into a ,%pinacpline, (C9H180)2, which boils at274" and is without odour.The other glycols give similar products.G. T. M.Sugars derived from Rhamnose. By E. FISCHER anti 0. PILOTY(Ber., 2 3, 3 102-21 10) .--Hh amnose (isodulcite) is metk ylpentose,has the formula CH,*[CH*OH],-c'HO, and, like the other heptoses,yields sugars richer in carbon.I t is proposed to term these deriva-tives rhaninohexose, rhwm noheptose, and rhamnooctose.RhamnitoZ, CH3*[CH.0H],.CH2*OH, is prepared by the reduction ofrharrinose with sodium amalgam, aiid crystallises from alcohol oracetone in t,riclinic prisms, which melt a t 121", and are insoluble i nether. It is sweet t o the taste, is only partially decomposed on dis-tillation, and does not reduce alkaline copper solution. It is readilyoxidised by nitric acid, and is reduced by hpdriodic acid. The yield is60 per cent. of the rhamnose.Rhnwinohexonic acid, CE,*[ CH.OH],COOH, is already known by thename isod~~lcitolcarbox~lic acid, or rhamnosecnrboxylic acid (comp.Ahstr., 1888, 806)..Ehawmohexose, CH,.[ CH*OH-),*CHO, is prepared by the reductionof rhamnohexolactone with sodium amalgam at a low temperature 32 ABSTRACTS OF CBRMIUAL PAPERS.the yield is 60-65 per cent.of the lactose. The compound crysta7-lises from methyl alcohol in thick plates which melt a t 180-181"with decomposition, and exhibit all the characteristic properties ofsugar. I t does not ferment with yeast. The phenylhydmzone isreadily soluble in water, The OSnzune is obtained in stellate groupsof yellow needles which melt a t 200" with evoliition of gas, arid arereadily soluble in aJlcohol, but nearly insoluble in water.BhamnolrexitoZ, CH,*[CH-OH],.CH,.OH, is prepared in a similarmanner to rhamnitol, and crystallises from alcoltol in small, colourlessprisms which melt a t 173", with previous softening at 170°, and haveno action on alkaline copper solution.Rhnmnoheytonic acid, CH,.[CH-OH],.COOH, is formed by theaction of hydrogen cyanide on rhamnohexose ; on evaporatiC~n, i treadily passes into the l:ictone, which cr~stallises from a,lcohol i nstellate groups of colourless needles melting a t 160", with previour;softening a t 158" ; t'he yield is 63 per cent.of the sugar.Rlmmnohepforiic hydyazide, C8H,,O7*N2H2Ph, is formed by the actionof phenylliydrazine acetate on the acid 01' lactone ; it crystallisesfrom water in slender, white needles which melt above 215" withevolution of y i s , and are very sparingly soluble in alcohol.Iiharnnohepfosc', CH,.[CH.0H]6*CH0, is prepared by the reductionof the lactone, and could not be obtained i n crystals; it is readilysoluble in water or alcohol, but insoluble in ether.The pheny7hydr-rrzone crystallises from water in colourless, sleiider needles ; on treat-ment with hydrochloric acid, the su'?ar is regenerated. The ornzonr!is deposited in slender, yellow needles, which are very sparinglysoluble in water o r alcohol, and melt a t about 200" with decomposition.Bhamnoctonic acid, CH,*[ CH*OH],.COOH, is prepared fromrhamnoheptose; on evaporation, the luctoire is formed, and is beatpurified hy means of the phen) lhydrazone ; it crystallises from waterin colonrless, concentric needles which melt at 171-172" withoutdecomposition, aiid are readily soluble in water or alcohol, but spar-ingly so in acetone.The pheizylhydmzide, CH,* [ CH*OH],.CO*N,H,Ph, cry stallises fromwater in slender, white needles melting a t 220".Rhtr~~zsioctose informed in small quantity by the reduction of the lactone ; i t readilyreacts with alkaline copper solution, and yields an osaxoae, which isinsoluble in water, and melts at 216".The following table gives the speGific rotatory powers of the rham-nose compounds, as far as they are known :-Rhamonolactone ............Rhamnose ................. + 8" to 9"Rhamnitol. ................. + 10.7Rhamnohexonolactone ....... + 83.8Rhamiiohexose .............. - 6 1-1Rhamnohexitol (approximate). + 11.6Rhamnoheptonolactone ...... + 55.6Rlmmnoheptose (approximate) + 8.4H hamnoc t onolac t one ........Specific rotation.-- 5 1 -20J. B. TORGANIC CHEMISTRY.33Arabinose from Wheat Bran and Rye Bran. By E. STEIGERand E. SCHULZE (Ber., 23, 3 1 10-3113). --It has been previouslypointed out by Tollens and his pupils that in all probability the for-mation of furfuraldehyde from wheat bran and from rye bran by theaction of sulphuric acid depends 011 the previous decomposition ofpetitaglucoses (aratinose and xylose) ; neither of these compoundshas, however, hitherto been isolated from the product of the reaction.Wheat bmn, freed from starch and alburiiinoiis mat,ter, is boiled forseveral hours with 3 per cent. dilute siilphuric acid; the acid isneutralised with barium carbonate, the solution filtered, concentrated,and extracted with alcohol ; on evaporation, arabinose crystallises out ;i t waq identified by its specific rotatory power, arid its ozazone.The arabinose is probably formed by the hydrolysis of a compoundwhich the aiithors term metarahan.This is a constituent of the cellmembrane, and cannot be prepared qnite pure. I t gives a cherry-red colour on warming with hydrochloric acid and phloroglucinol,and is insoluble iri water, arid in cold dilute alkalis or acids. Onwarming, it readily dissolves, and becomes converted into sugar.Other samples of wheat bran gave similar results, as did also1.J-e bran. No galactose or mannose could be detected in any of thesolutions. J. B. T.Starch. By C. SCHEIBLER and H. MITTELMEIER (Be?.., 23,3060--3O75) .--The autliors give 3 historical review of the investip-tion of starch and of tlic compounds derived from it by hydrolysis,followed by a sketch of the recetit work arid present theories on thes u bjeot.The experimental Imrt of the present communication is l i m i t ~ l toan investigation of dextrin.Commercial dextrin can be purified by precipitation with alcohol,care being taken that tlie quantity of alcohol piwent never exceeds85 per cent.of the total solutiott ; after precipitating three times, theproduct ceases to give an insoluble osazotie, and after repeating theoperation several times the dextrin timy be considered to be free fromsugar. Good results arc also obtained by dialysis and subsequelktprecipitation with alcohol, but a product free from sugar could not beproduced by fermentation.Pure dextrin becomes yellow or brown on heating with potash, andit readily reduces alkaline copper sdlution, thns showing that, as it isitself not a definite compound, its constituents must beltlng wholl~,o r in great part, to the class of sugars which contain an aldehydic orketonic group.This view is supported by th9 fact that, on digesting solid dextrinwith excess of phenylhydrwzine a t ordinary temperatures, it dis-solves, and on heating with alcohol a white precipitate is obtained ;t h i s is washed free from phenylhydrazine, and purified bydissolving in water and precipilatiiig with alcohol.This corn-pound contains 1.02 per cent. of nitrogen, corresponding with theformula C96H62080*S2HPh, and closely resemhles dextrin i n itschemical properties and i n solubility ; it is decomposed by hydro-chloric acid in a manner similar to the pheiiylhydrazones of sugarsVUL.LS. C34 ABSTRACTS OF GHk;M1CAlA PAPERS.wit,h high molecular weiyhts. By heating on t,he wat,er-bath f o rtwo hours with phenylhydrazine acetate, and treating the productwith alcohol, a, pale-yellow osazo?ze i s formed, which is less soliible inwater than the phen-ylhydrazone, and may be precipitated bv alcohol.The percentace of nitrogen varies somewhat. thus showing t h a t i n a l lprobability the body is a mixture of osazoiie with unaltered phenyl-hydrazone.An aqueous Kolution contdining 8 per cent. of dextrin is repeate3lytreated with smnll quanrities of sodium amalgam, dilute acetic acidbeing added from time to time ; after several days, alcohol i s addedto the slightly acid solution, and the insoluble product pnrified byrepeatpdly dissolvirig in water and precipitating with alcohol.Theauthors propose t o call this colonrless compound de.i-tvitol; i t does notredilce alkaline copper solution, is inst-)luble in phcnylhgdrazine evciion warming, and the solution (300s not brcomc yellow on boiling withp Itash. Ry the action of concentrated acids or of diastase on dex-ti-itol, a liquid is formed which readily reduses alkaline copper sulu-tion.An 8 per cent. aqueous solution of dextrin is liented with R fewdrops of bromine and allowed t o stand uiltil the colour disappeai-s, asecond quaiit,ity of hromine is then added, and, as soon as this hasrettcted, the dextrin is precipitated with alcohol in order to frve i tfrom hydrobmmic acid ; the product is disholved in v a t e r n,nd timteilwith hromine as before, the process being repented until t h e c7exti.inceases t o reduce alkaline copper solution.After repeated purifica-tion, a white powder is obtained which is soluble i n phenylliydi-mine ;an aqueous solution reddens litmus paper, and decomposes calciiimcarboi,ate on warming. No precipitate is obtained with lime-waterand lead wetate ; hy the action of diastase, or by heating with amineral acid, a product is obtained which readily reduces alkalinecopper solution.The above results all point to the presence of a n aldehydic group indextrin, and this view is supported by the fact that the products ofhydrolysis are also aldehydes.By the hydroljsis of starch, the authors have only obtainedglucose, but? from commercial “ starch sugar ” they have isolated anunfermeritable compound which rcwxnhlcs dextrin, and, from theanalysis of its osazone, has the formula C1LH22011, being thus isomeiicwith maltose.J. B. T.Stereochemical Isomerides of Nitrogen Compounds. By A.HANTZSCH and A. WERNER (Uer., 23, 2764-2769 ; see also Abstr.,1890, 34t\, 9iO).-Ttie authors in this paper sum u p their views withregard l o the isomeric relatioiiships of the oximes as follows :-(1.)The oximes X:C:N*(I)H behave as titutumeric compounds, and yieldtwo different a1 kjl der.ivat,i ves having the struct ura1 form.; 1~X:C:N*OR and X:C-N*R, wbich may be distinguished as “ o x ~ - g e nethers ” and “ nitrogen ehhers.” (2.) Cert’ain asymmetrical oximesexist i r twc otereoc~hemically isomeric: forms, which, accoding t o thethcbry propwed by the authors, are represented by the formula3‘0ORGAN10 CHEMISTRY.3 5X y Y( 3 . ) Each of these isomerides can yield twoN-OH’ x‘G*y andIT0.Nstructurally isomeric etliyl derivatives, and therefore an asymmetricaloxime of the formula $>C:N*OH should yield four alkyl dwiva-tives, namely :-I n 110 one case have all four alkyl derivatives been prepared, onlythree being known in most cases, two of these being “oxygenethers ” and one a “ nitrogen ether.” I n the case of furfuraldoxime,however, the two isoineric 9‘ nitrogen ethers ” have been prepared,thus giving an indirect proof of this part of the theory.Auwers and Meyer have suggested that the isomerism of theoximes is due, not to the nitrogen atom, but t o the asymmetricalconstitution of the hydroxjlamine itself, as represented in theformulae $>C:N*O/H and T>C:X*O (Abstr., 1890, 1264).Theauthors point, out that this hypothesis does not explain the existenceof two isomeric nitrogen ethers, and also that the formulm proposedby Auwers and Meyer do not represent distinct isomerides, but onlyphases of an intermolecular atomic motion, which pass one into theother by the simple rotation of the hydrogen atom of the hydroxylgroup around the axis N-0. Further, ~ f , owing to the combinedatti*action of the nitrogen atom as well as that of’ tlie oxygen atom,the h5drogen atom tskes up a position intermediate between the two,it rnust) be also supposed that thy oxygen atom is attracted out of theplijne by the hydrogen atoms of the wmido-group; this, however,siniply means, in other words, that the h j droxglttmine moleculeassumes the tetrahedral configuration /I\ , which is simply aspecial case of the authors’ general hypothesis.Sccording toBehrend’s hypothesis (Abstr., 1X90,575), the isomeric benzaldnximesshould show very slight differences in their piiysical properties, but,as a matter of fact, the two coriipoiirids are completely distinct.Moreover, the latter hypothesis gives no explanation of the readyformation of benzonitrile from isobenzaldoxime.In concliision, the authors state that their hypothesis, like thoseof Van’t HOE arid Wislicenas, is riot dependent on any specialassumption as to the direction of valencies, &c., but is simply deducedfrom general s j mmetrical relations.Attempts to prepare Stereochemical Isomerides of NitrogenCompounds.By A. BANTZSCH (Bey., 23, 2769--2773).-’l’heinvestigation described in this paper was undertaken to detjermine, ifpossible, the conditions nnder which stereochemical isomerides of‘HNHOEHH. G. C.a 36 ABSTRACTS Ofr OHEMICAL PAPERS.iiitrogeii compounds are formed. ( 1 . ) The study of t'he question ofthe existence ct' an asynirnetricnl nitrogen atom i n derivatives ofammonia and of hydrazine has not yet led to any positive results (seealso Kraft, following abstract). (2.) All attempts to ohtain stereo-chemical isomerides of compounds, other than the oximes, with Rdouble linkage between the nitrogen and carbon atom, have beenwit,Iront success.It was found that urethanes do not condense withcarbonyl coimpoclnds according to the equation=CO + H,NC@OR = =C=N*COOR + HzO,and that isomeric derivatives cannot, be obtained fmni benzylidinc-;tniline (this vol., p. 50). Further, i t was found that nitriles(lo not form additive compounds in the mauncr represented by theequation :-N-Y - - N YX.? + z X.6.Z *( 3 . ) The compounds which yield isomeric oximes incliide almost allaromatic aldehydes and asymmetrical ketones, their meta- and para-substitution products, arid also diketones of the benzile type andphenylglyoxylic acid.The fatty aldehydes and ketones, and all com-pounds containing even a single alcohol radicle, CtLHZ,L+l. in comhina-tion with the carbonyl group, yield only a single oxinie. This is alsothe case with all compounds containing a carbonyl group in a closedchain, and in all aromatic a1dehTdes and ketones in which substitutionhas taken place i n the ortho-position relatively to the carbonyl group.When substitution has taken place in both ortho-positions, the com-pound does not yield any oxime. This agrees with the results of Kehr-mann, but the author differs from Kebrniann in so far as he regardsthe configuration of the molecule, rather than the space which i toccupies, i s determining the possibility of the existence'of isomerides.H. G.C.Displacement of Halogens by the Amido-group. By E.SEELIG (Be?.., 23, 2971- 2972). - In the usual process for thedisplacement of a halogen by the amido-group by treatment withwith aqueous or alcoholic ammonia, the reaction, as a rule, does notstop with the simplc! displacement, but proceeds further, with forma-tion of secondary and tertiary bases. If, in place of the solution ofammonia in water or in alcohol, phenol diluted with 15 per cent. ofvrater and saturated with gaseous ammonia is employed, the reactionproceeds much more smoothly. Thns benzyl chloride treated withthis reagent, gives 24 per cent.. of the theoretical yield of benzglamine,whereas with aqueous or alcoholic ammonia, only traces of t,he arnineare obtained. Ethylene bromide, heated in a similar manner, gives ayield of 38 per cent.of ethylenediamine hydrate. H. G. C.Isobutylamine. By H. MAL~IOT (Couzpt. Tend., 111, 528-529).-The author has investigated the conditions which give the largesty~elcl of isobutjlamine by the reaction of isobutyl chloride wit1ORGANIC CHEMTS FRY. 3 7ammonia. The chloride was heated witn different proportions ofammonia in sealed tubes a t 100" for various periods of time. Details oft h s experiments are given. The best results are obtained when 1 mol.of isobutyl chloride is heated with 10 or 15 mols. of ammonia; in thefirst, case the quantity OE diisobutylemine formed is twice as great asin the second, but it is easily removed by washing with water. Themixture must be heated for 3 to 34 days.C. H. R.Action of Secondary Amines on Imido-ethers. By A. Pmsclr(Rer., 23, 892 7-2933) .-Tetrethylsziccinamidine hyJrochloriJe.NH:C(NE~)*CH2*C(NH)*NEt,.2HC1, is prepared by the action ofdiethylamine on et,hylsuccinirnidinc hydrochloride ; after remainingfor about eight days, it separates in lustrous, prismatic crystals. Onrecrystallisation, ammonia is eliminated, and tetrethllZsuccitl,imid~~~,~C H: C ( N E tz)CH,*C(NEt,)hydro c h 1 o r i d e , I >N,HCl, is formed, crystallising in large,thin plates. The &at&ckioride is deposited in yello wish-red, Iu~troiis,pointed Drisms which melt at 202".>N,HCl, 7 H:C ( NPra,)CH,*C (NPra,)TetrapropyIsuccirLil?i idiiie hydrochloride,which closely resembles the tetrethyl derivative, is 'prepakd by thcaction of dipropylamine on phen-ylsuccinimide hydrochloride ; theintermediate succinamidine could not be isolated ; the condensationtakes place much more readily than with diethylamine.The nitrate,C,,H,,N,,SHNO,, melts a t 53". The ylntinochloride is very spariuglysoluble in water, from which it crystallises in large, pale yellowplates melting at 174".The constitution of the above compounds cannot be regarded asbeing definitely proved, but the fwmulse assigned to them appear tobe the most probablep-Bromopropaldehyde and p-Bromopropionic Acid. ByL. LEDERP:~; ( J . pi-. Chew. [2J, 42, 384). /j-Bmrnopropnldehyde isobtained by passing dry hydrogen bromide into well-cooled acyalde-hyde to saturation, and evaporating the excess of acraldehyde at; itlow temperature.It is a thick, yellowish oil, and does not crystallise; it soon decomposes at, the ordinary temperature, and, whenheated to 45" in abwnce of air, i t evolves hydrogen brsniide andch a 1's.p-Bromopropionic acid, obtained by oxidising the aldehydo with woll-cooled nitric acid (sp. gr. 1-48> and extracting with ether, crystsllisekin large, colourless tables which melt, a t 62*5", and dissolve in theusual solvents (Beokurts and Otto, Abstr., 1885, 506). The ethyl saltJ. H. 1'.boils atl 89" (40-50 mm.). A. G. r3.Action of Hydrocyanic Acid on Unsaturated Aldehydes. ByG. JOHANNY (Xonatsh., 11,399-412 ; compare Gauiier, Bull. SOC. Chim.,25, 481; Lobry de Bruyn, Abstr., 1885, 242; 1886, 924).-Whenmethylethglacraldehyde is heated with am equal volume of anhydroushyclrocyanic acid in sealed tubes for 50 hours at 45", the hydrocyanide38 ABSTRAOTS OF OHEMIOAL PIPERS.CsHloO,HCN, is formed, but the compound is so uristable that itcannot be isolated in a pure state, although its acetyl dei-irativeCHEt.CMe*CH( CN).OAc, obtaiiied by heating it with excess ofacetic anhydride in a iaeflux apparatus, may be distilled without de-composition at l l ~ - l 1 4 ° under a reduced pressure of 35 mni.a- Hydro3 y -p-prop2/lidiliebutyrait~i~e7CHEt:CMe*CH (OH).CONH,,is formed when the above-described acetj-1 compound is treated withfive times its weight of fuming hydrochloric acid and the mixture isallowed to remain a t or.din;try temperatures i n a closed flask forthree days.From an alcoholic solution, it crystallises i n colourless,rhombic plates which melt a t 100--101”, arid on heating with milk oflime, ammgnia is evolved, and the calcium salt of a-hpdroxypropyl-idenebutyric acid, (CTH1103)2Ca, + BHzO, obtained ; this crystallisesfrom water in needles. G. ‘1’. $4.Molecular Weight of Glycocine and its Anhydride, ByT. CURTIUS and H. SCH~JLZ (Iler., 23, 3U41--304Y).--I)etermina-tions of the molecular weights o€ amidoacetic acid and of variousderivatives by R8aoult’s metliod, with water as the solvent, give re-sults in accordance with the simple formula NH,*CH,.COOH.Similar experiments with the auhydride point t o the FurmulaThe results previously obtained from vaponr density determina-tions by Hofmann’s method are thus fully confirmed.J. B. T.Glycocine. By J. MAUTHNER and W. SUIUA (Monatsh., 11,373-382 ; compare Abstr., 1889, 139) .--The authors have preparedglycocine by a more satisfactory method than those previously de-scribed, in the following way :-‘I0 a well-cooled solution of chlor-acetic acid (100 grams) in water (10G c.c.) or alcohol, 20-22 percent. aqueous ammonia (1 litre) was gradually added. After i*emain-ing for a week a t ordinary temperatures, the solution was heated,first alone, and then with lead oxide, to expel ammonia; after filter-ing, the lead was precipitated by the addition of freshly preparedammonium sulptiide, the lead salyhido filtered off, the solution evapo-rated to dryness, aid the crystalline mass thus obtained dissolved ina little water and boiled with copper carbonate.On cooling thefiltered solution, copper glycocine crystal lised out in masses ofneedles which, when recrystallised from a, little water, gave, besidesthe needles, a number of bluish-violet, glistening scales. ‘l‘liese scaleshave a similar composition, (C,H,NO,),Cu + H20, to tho needles, but,give up their water of crystallisation at a much lower temperature.‘I’he modification crystdlising in scales may be obtained by heatingthe needles with a quantity of water insufficient to completely dis-solve them, rapidly filtering, and allowing the solution to crysta1:ise.The yield of copper glycocine obtained by this method was about 28per cent. of theoryORGANIC CHEJIISTRY.39Calciiinz 07"fhOtoZyZylycocine, (C9HloN02)2Ca + 3H,O.-This salt isprepared bv a rnetliod siinilar to that used in the preparation ofcalcium orthophenylglycocine (compare Abstr., 1889, 1068). Whencrystallised from water, it forms flat,, glistening needles which are in-soluble in absolute alcohol. On clry distillation with calcium formate,:(r product was obtained which appears to be orthotolindole (compareRascheri, Abstr., 1887, 956).Culciiim a-nap hthylghjcocine, ( C12HIoN02),Cn + 3H20, is obtainedby dissolvifig a-nap~thylglycocine in dilute ammoilia, and precipi-tating the warm solution with cttlcium chloride. When crystallisedfrom dilute alcohol, the sitlt forms clusters of flat needles. On heat-ing with calcium formate, a mlxtailce W R S obtained .which resemblesSctilieper's a-naphthindole jibid., 963) in crystallising in needles, buthas a lower melting point, 163".Yhenylylyc~oci~z~pal.nrcc?.bo,o!/l~~ ucid, C9H9N01, is ol3tained by boilingfor several hours a mixture of paramidobenzoic acid (25 grams),chloracetio acid (20.6 grams), and sodium carbonate (32.8 grams),dissolved in water (1 litre).On acdifjing the cooled solution, a yellowpuwder (yield 50.2 graius) is precipitated, and this, on recrystallisa-tion from water, forms a crystdline rnass which melts with decom-position at dlY--221". The barium salt, C,H7NOiBa + 4H20, andthe calcium salt, C9HiN04Cn + 3H,O. are white, crystallinc pow-ders ; the copper salt, C9H7N01Cu + ;3H,O, is a dark-green aniorph-ous powder.G. T. M.Constitution of Diazo-fatty Acids. By T. CURTICS (Ber., 23,3036- 3US 7) .-€€ydmz.ine 01- It ydrazopropion ate,rH>CMe*COOH,N2T-r4, NHis obtained from hydraziiie hydrate arid pyruvic acid as ,z colourless,uystalline powder melting a t 116".Meihyl a-hyd~.rrzo~l.oiwioizate, > CMeeCO OMe, is prepased in aNHsimilar manner from met,hyl pyruvate and hydrazine hydrate ; i tmelts a t 82", and on treatment! with niercuric oxide yields a methjla-diazopropronate, N,CMeCOOMe. which boils a t 1,:3--55" uiider apressure of 32 mm. Tho same cctmpound has previously been pre-pared i n small qnantities from methyl a-anlidopropionate arid sodiumnitrite. !Phis result proves coriclusi~~ely that in the diazo-fatty acidsthe tm7o nitrogen atoms are linked t o the same carbon atom.YHJ.B. T.Action of Bromine on Angelic Acid and Maleic Acid. ByR. F~TIIG (Anruden, 259, 1---40).-When Wislioeilus wafi engagedin developing his theoiy of the rotation of atomic configurations,there were on record various obsexations m:ide by the author andhis pupils which were riot in accoi dsuce with the n e w theory ; manyof the author's experiments were, therefore, repented by Wisllcenuswith results which agreed better with his t heoreticul views, bu40 ABSTRACTS OBI CHEMICAL PAPERS.which were totally at variance with those previously olitained bythe author.The author has repeated some of the experiments in question withthe utmost care, and has shown that his previous statements m eabsolutely correct in every detail.One of the most important points of difference which receivedattention was the inrestiption of the action of bromine on angelicacid. I t had been stated by Fittig and Pagensfrcher (Abstr., 1878,4.55) that angelic acid combines with bromine, yielding tiglic aciddibromide as principal product, ; a small quantity of another sub-stance, which could not be obtained in a pure condition, beingpmduced a t the same time.Wislicenus and Puckert (Abstr., 1889, 587) found, on the otherhand, that tiglic acid dibromide is not produced hy the ncsion ofInrDmine on angelic acid: they obtained a substance with totallydifferent, properties, the investigation of which proved t o their mintisits complete dissimilarity from tiglic acid dibromide.Now, as the author had obtained 27 grams of pure tiglic aciddibromide from 15 grams of angelic acid, and had proved the identity-of the product with the substame obtained directly from tiglic acid,not only by a general, but also by w crystallographic, examination,and as, furthermore, his observations had been contirmed by Schmidt(Aiznalen, 208, 252), Wislicenus' results were received with gre it,astonishment, and the reinvestigation of the subject, was commenced.In the first place, a sample of the so-called angelic acid dibromide,prepared by Wislicenus and Puckert, was examined by the author,and found to be want,ing in all the properties of a pure chemicalcompound ; it seenjed to consist principally of tiglic acid dibromide,mixed, howevein, with various substances, amongst others calciumcompounds and resinous matters.The author then began various experiments 011 the action ofbromine on angelic acid.The acid employed melted a t 44", anti as i thad been kept for 1'2 years, it would seem tlhat angelic acid does not,become converted into tiglic acid on keeping, as is supposed bySchmidt. The acid was very carefully dried, and then distilled ; itboiled a t 185", and underwent no change into tiglic acid, either whenboiled or when distilled with stearn. Wislicenus and Piickert'sstatement that w r e angelic: acid is coni-erted into tiglic acid onboiling with water cannot therefore be confirnied. The pure angelicacid was treated with bromine in carbon bisulphide solution a t 0" i ndiffused daylight, moisture being carefully excluded ; several experi-ments were made under various conditions, in some cases t)he solutionof the acid being added t o the bromine solution, in others trhe processbeing reversed.In all t h o experiments, which are described in great detail, a larqequantity of tiglic acid dibromide was obtainec1,and the identity of theproduct with t h e dibromide prepared directly from tiglic acid wasproved, by direct con~parison as well as by a crystallographic examin-a tion.These results show that the statements puhlished by the authormore than 12 J a r s tigo are absolutely correct in eve1.J- detail ; it mayORGANIC CHEJIISTRY.41therefore, be coiisidered as proved, that when angelic acid is treatedwith bi-omine in carbon bisulphide solution at 0" in diffused daylight,it is almost completely converted into tiglic acid dibromtde in thecourBe of a few hours.A number of careful experiments were also made in order to in-vestigate the behaviour of angelic acid with bromin5 in absence ofsunlight ; it was found that, whatever the conditions, the principalproduct is always tiglic acid dibromide, hut thnt another substauw,which is not produced €rom tiglic acid under the same conditions, isalso formed in small quantities.Although, then, the formation oftiplic acid dibromide takes place quickly in presence of diffused s u n -light a t O", and the yield is almost quantitative, in the dark thereaction takes place only very slowly, even at the ordinary tempern-ture, and a larger quantity of a more readily scluble compound isproduced.The preseiice of this readily soluble compound has greatinfluence on the behaviour of the tiglic acid dibromide ; i t makes it,much more readily soluble in all ordinary solvents, retards its crystal-lisation, and causes it to deliquesce with water. The nature of thisbye-product, could noh be determined, but i t is probably an isomerideof tiglic acid dibromide ; the snbstance prepared by Wislicenus aiidPiickert evidently contains both these compounds.After referi-ing to several minor errors in the statements andresults published by Wislicenus, the author criticises Wislicenus'experiments on the action of bromine on malei'c acid, and points outt h t the coiiclusions drawn therefrom by Wislicenus are directlyopposed to the present theories.i n conclusion, the author protests against the way in whichWislicenus is nwustomcd to trust, to his memory alone in referring tothe literature of chemistry ; in rnauy cases, the author iind others aremade to st,ate and affirm in their papers, the refereuces to which areall given, just what Wislicenus hiniself believes a t the time, whereasthe actual Statements are sometimes the exact contrary and some-times do not appear at all in the articles referred to, but exist solelyin Wislicenus' imagination.F. S . K.Syntheses of Nitriles and of ,&Ketonic Ethers. By L.BOUVEAULT (Cowpi. rend., 111, 531-533) .--It has previously beenshown (Abstr., 1889, 841) that the products of the action of sodium onpropionitrile jn presence of ether contain the compoundNH:CE t.CMeNa.CN,and it follows that the mixed compound oht'ained by the action ofsochrn on the two nitriles R*CH,.CN and R'.CI)U' ( J .pyakt. Chem.['L], 39, 188, 230,245) will have the constitution NH:CR'.C:RNa.CN.If this derivative is treated with an alkyl iodide, as in the case oEpropionitrile, it will form the compound R'*C(NH)*CR"R.CN, whicliwill be converted by hydrochloiaic acid into a 6-ketonic nitrilcli'*CO*CR"R.CN. These nitriles can readily be converted into alkylsalts by dissolving them in the corresponding alcohol and saturatingthe solution with dry hydrogen chloride.Xethylic weth y7pr01)io111/7acc.tate, COEt-CHMe.COOMc~, boils at 185"42 ABSTRACTS OF CHEMICIAL PAPERS.arid is identical with Israel's met,hyl propionylpropionate* (dnnrrleir,23 I, 197) ; methyl di~mrtliylpro~ion,ylacettcte, COEt.Chfe,*COOMe, isa colourless liquid which has a camphoraceous odour and boils a t188-188.5" (corr.) under a pressure of 760 mtn.These changes me quite general, and all the /3-lcetonic alkyl saltscan he obtained from their nitriles.Met h y 1 me thy Ip ropiony 1 acetate shows powers of condensationsimila: to those of ethyl acetoncetixte ; it coritbines with aniline toform arnetEiylethyloxyqniiioliiie melt irig a t iL95", aiid insoluble iiiether ; water, methyl alcohol, and carbanilide are formed a t the sametime.The @-ketonic nitriles, when heated in sealed tubes with hydro-chloric acid, yield ketones.a reaction discovered by E. v. Meyer.The nitrile COR.CR'&".CN will yield the ketone CO R*CHR'R", andin bhis way7 all the ketones can be obtaiced in which the two atomsof carbon ;nit,ed to the cxrboriyl are not botl-1 tertiary.C. H. B.Syntheses with Ethyl Sodiocarbamate. By F. KRAFI' (BY.,23, 278%?78i) .-When ethyl car.bama,te is treated with fiuely-divided sodium i l l ethei-eal solution, it is converted into a white,ailiorphous sodium compound, NHNa-COOEt, which is very hygro-scopic, has an alka,line i.eactioii, and is reconverted by dilute acidsinto ethyl cat-bamste. The displacement of sodium by methyl doesnot take place very readily, it being necessary to beat the mixture ofethyl sudiocarhamate and methyl iodide diluted with ether, a t I l O " ,in a sealed tube.The product, after heparating the sodium iodide andevapoi ating the etlier, is fractioriated, and yields regenerated ethylcarbarxiate and ethyl methylcarbawlate, NHMe*COOEt, boiling at 1 70".Ethyl chlorocarbonate acts on the sodium compound snspeuded inether a t the ordinary temperature. After the reaction is over,suflicient water is added to dissolve the sodiam chloride formed, thesolution is extracted with ether, and the extract, after evaporation oCtlie ether, is fractionated. At 110", a solid substance commences toseparate, but a t 210--215" an oil passes over, leaving a solid residuewhich consists of cyanuric acid. On refractionating the oil, morecyanuric acid is obtained, but ttie greater portion passes over at 215',and solidities after a time to a crystdline mass closely resemblinq<:thy1 carbamate, and having the same riielting point of 50", but i tboils 35" higher, and does not volatilise on remaining in the exsiccator.Its mxilysis agrees with the formula ChH,,NO1, and it is therefore, asexpect e 2, ethi'! imidoilicadoa y late, N H (C 0 0 E L ) 2.H.G. C.Methyl Cyanosuccinate and Cyanotricarballylate. By L.B A ~ ~ T H E (Compt. rend., 111, 343--345).-Methyl sodiocjanacetate isprepared by the ixctiori of sodiiim methohide on methyl cyanacetate iitpresetice of excess of metliyl alcohol, the product being heated in awntev-bath for several hours with methyl rnoriochloracetate. Theliquid is then mixed with water, and the reddish oil which separatesis dissolved in ether, dried, aud distilled.'l'he fraction which boils a t 196-204' under R pressure of45 mm.is methijl cywosuccittatr, COOJ4e.CH;CH(CnT)*COOMe, aORUANIC CHEMISTRY. 43oily, colourless liquid, insoluble in water, but soluble in methyl andethyl alcohols and in alkalis. The fraction boiling at 215" under thesame pressure solidifies after some hours, and is purified by re-crystal I isation from methyl alcohol. It is methyZ cyaizotricics"bulZyZut~,C .V*C (CH,*COO Me),-COOMe, and forms white, prisma tic crystals1vhicl.i melt a t 46*5-47*5", and are soluble in ethyl and methyl alcoholsand in ether, but insoluble in water and alkalis. It is formed in thesitme manner as ethyl cyanotricarballglate (Abstr., 1888, p.937), andcan, in fact, be obtained by the direct action of methyl mono-chloracetate on methyl sodiocyanosuccinate. C. H. B.Ethyl Allylcyanosuccinate. By L. BARTHE (Coinpf. ?.end., 111,348--343).--20 grams of ethyl cyanosuccinate is mixed with asolution of 2.3 grams of sodium in 60 grams of alcohol, 16 gra>ms ofally1 iodide is added, and tjhe liquid is heated in a water-bath forabout 30 hours i r i an ampparatus with a reflux condenser. The product,alter separation of the alcohol by distillation, is extracted successivelywith water arid ether. The latter dissolves the ethyl allylcyano-succinate, which is obtaiiied as a colouyless, oily liquid boiling at'Lo?--~I(J" (coi-r.) under a pressure of 35 mm.The so-called Sulphite Liquor" and the Rotation ofGlyconic, Galactonic, and Rhamnonic Acids.By F. WELD,C. H. B.J. B. LINOSAP, W. SCHNELI,E, and B. 'YOLLENS (Be?.., 23, 2993-2993).-The so-called " sulphitr-liquor " obtained in the cellulosc works isa very slightly milky liquid, which, besides calcium sulphate andpotassium sulphide, contains much organic matter. On distillingthe liquid with sulphuric or hydrochloric acid i t yields furfur-aldehyde and fiirfuramide, showing che presence ( f pentoses (xylose).The quantity of the latter is small. If the liquid obtained afterhydyolysis with sulphuric acid he separated from gummy matters byprecipitation with alcohol, it yields, on treatment with phenylhydraz-i n e, considerable quantities of niannoseph eny lhy drazone.By theaction of nitric acid, the evaporated liquor yields rriacic acid, showingthe presence of galactan or galactose, and the presence of vanillin hasalso been shown hg the phluroglucinol reaction.The specific rotatory power of certain acids of the sugar group,and of their calciiim salts, has also been examined, with the followinqresults (see also Fischer, Absti.., 18'30: 1398) :-Gluconic acid.-Withcal(.ium gloccnate, [a],, = +7". Tf' this salt is dissolved in waterand a n equivalent, quantity of hjdrochloric acid, it shows, after10 minutes, a, specific rotatory power of +2--3", calculated as freegluconic acid, C6H,,O7 ; after 5 days, the rotation remains constant,[aJn = +9*8-10*4°. If the mixture of calcium glucoriate andhydrochloric acid is heated a t first for half an hour.at lC)O",[aID = +19", and this rotiltion is reduced to one half in two to threeweeks. Gnlactonic acid.-Caicium galact onate, and an equivalent ofhydrochloric acid, gave, a t first, [alD = -10*56", and after 2--3 weeks,[aID = -4G.82". After henting for half an hour on the water-hath,LaJn = --57.84", which, after r2maining for 14 days, sank to -53.36"Crystallised galactonic lactcne gave, a t first, [aIu = -58.29, wbic44 ABSTRhCTS OF CHEMICAL PAPERP.scarcely altered on being kept for a time. Rhnmnonic acid.-With greatclificulty, strontinm rhamnonate, (CsH,,06)2Sr + 7 or 7+H20, rmd anammonium salt were obtained in a crystalline condition. The former,when dissolved in hydrochloric acid, gave. at first, [aID = -7*67",and after 5-6 days, the constant number, [ a ] D = -2!3*21", and afterheating, -34*:30", which sank in 5-6 days to -;30.12".Rharrinoniclactone gave, immediat,ely after solution, the result [ a ] , = -34.26,calculated like the foregoing, for rhaninoriic acid, C6H,,06. In threedays the rot'atioii had scarcely altered. H. G. C.Constitution of Benzene and Naphthalene. By ,4. CLAUS(.7. pr. Chem [2], 42, 458--469).-A reply t9 the critkisms whichHamberger has recently pasked on Claus' formulz (compare thisvol., p. 1299). A. G. B.Substitution in Aromatic Hydrocarbons. By 0. S RP EK(Nonutsh., 11, 429-432).-With the object of obtaining parabromo-benzyl chloride, bromine (126 grams) was slowly added, in the dark,to a mixture of benzyl choride (100 grams) and iodine ( 5 grams).The solid product, after many recrystallisations from alcohol, meltedat 59", and coiisisted of a mixture of parabromobenzyl hrornide, whichmelts a t 61", with a small quantity of a compound containing chlorinein both the nucleus and tlhe side chain.A similar result was obtainedwhen chlorine acted on parabromotoluene in direct snnlight. Thecrystalliiie product obtained melted a t !i2", and consisted chiefly ofparabromobcnzyl bromido. The formation of this compound is easilyacci bunted for if one supposes that clilorobenzyl chloride is sitnultane-ously formed ; examination of oily bye-products points to such beingthe caw. G . T. M.Derivatives of Orthodibromobenzene. By P. SCHIFF (Monntsh.,11, 329-349) .-A more satisfactory method of obtaining orthodi-bromohenzene than those described by Riese (this Journal, 1873, 63j,and Korner (ibid., 18i6, i, 214), is as follows:-Bromobenzene isadded gradually to 6-7 times its weight of well-cooled nitric acid ofsp.gr. 1-53, and the resulting nitro-compounds crystallised fromalcohol, when the chief product, paranitrobromobenzene, me!ting at126-127", first separates (yield 80 per cenr. of tlieory). On heatingthis compound with the corresponding quantity of bromine and ferricchloride for 50 hours a t 85-90' (cornpare Scheufelen, Aostr., 1886,340 j, para-orthonitrodibromobenzene, niel ting a t 58-59' (yield90 per cent. of theory), is obtaiced, and this, on elimination of tbenitro-group, is converted into orthodib~~omobeazene, which, when pure,boils at 224", solidifies a t - 5 O , and melts at -1 O (compare Meger andWursfer, %his Journal, 1874, 757, i 5 9 j .Pure metadibromobenzene,after being frozen in a mixture of solid carbonic anhydride and ether,melts a t 1-9".When dibromonitrobenzene is treated with ten times its weight ofconcentmted nitric acid, of sp. gr. 1-53, and t h e mixtnre is warmedin a water-bath f o r 12 hours, two dibrcmodinitrobenzenes (a- and /3-ORGANlC CHEAlISTEtT. 43are formed, and may be readily separated by fractional crjstallisationfrom acetic acid.a-Dib,.o?nodinitrobenz~ne is less soluble in acet,ic acid and i n nl(:oholthan t8he p-compound. It crystnllises from alcohol in rieedles meltinga t 114-115". On iaeduction with uiii and Iiydrochloric acid, i t is crm-1-erted into dibromodiamidobenzene, which crjstallises from dilutealcohol in needle8 melting, with decomposition, at 157".On treat-ment with alcoholic ammonia a t 110-120", i t gives a, dibromonitro-anilirie, crystallising from alcohol in orange-yellow needles me1 ting a t204--205", and this, by elimination of the amidogen group, is con-verted iiito the original nitrodibromobenzene, and seems to beidentical with the dibromonitraniline melting a t 202", obtained fromdibromaniline, [Br, : NH, = 1 : 2 : 41, by acetylation, nitration, andsubsequent elimination of the acetyl group ; a-dibromodinitrobenzenehas, consequently, the constitution (Brz : (NO?), = 1 : 2 : 4 : 51.p-Dibi-omodiniti*obenzene is very soluble in alvohol and in acetic acid,a n d crptdlises from the former in needles: and from the latter and fromcarbon bisulphide in small, rhombic plates [a : b : c.= 1 : 0.854 I. : 0.57001.O n treatment with alcoholic ammonia, it gives a dinitrobrumaniline,which crystallises froni alcoliol i n yellow needles melting a t 153" ;this is identical with the compound obtained by Leymann (Abstr.,1882, 1057) by the brominntion of metadinitmniliae [l : 3 : 41. Thecompound has, consequently, the constitution [Br, : (NO,), =On diazotising the dibromaniline above-mentioned, dibromophenol,[Ur, : OH = 1 : 2 : 41, which may be readily suhlinied, and crystal-lises from water in needles melting a t 79-80', is obta'ined.1 : 2 : 3 : 5 ] .G. T.M.Change of Propyl into Isopropyl in the Curnine Series. BJ-0. WIDMAK (Rer., 23, 3080 - 3O88).--;P~~~tr - ethyZpropyZbei/zer/e,C6H413tPra, prepared by liea ting a mixture of parabromopropyl-benzene and ethyl bromide with sodiiini, bolls a t 202-205" (corr.),and has a specific gravity of 0.867 at' 19'. It yields terephthalic acidas sole produce of oxidation with alkaline permaugnnate soln tion,\I hilst with dilute nitric acid, propylbenzoic acid, together with alittle ethylbenzoic acid, is formed.By the action of sulphuric acid on ethylpropylbenzene, a mixtureof two sulphonic acids is obtained: these are converted into sulphon-amides, and sepnrated by repeated cry stallisation from alcol~ol.1' cwa- et h ylpp1'opyl b e w e m - a-su 1ph muwid e,C,H,EtPPSO,NH, [Et : Pr : S = 1 : 4 : 61,crystallises from dilute alcohol, or from a mixture of benzene and livhtpc'troleum, in long, flat needles meltiiig a t 112-113" ; on oxidihtionwith chromic acid solution, it yields sulphonamidethyl benzoic acid,[Et : COOH : S = 1 : 4 : 6).P a r a - s t h ~ l ~ ~ r o ~ ~ ! ~ l b e n z e t i e - ~ - l - s z l l t , i ~ e , [Bt : Pr : S = 1 : 4 : 51, isdeposit2d in cubical crystnls which melt a t 108", and on oxidation,wive sulphonamideprop~lbenzoic acid.The oxidation of an ethyl46 ABSTRACTS OF CHEMICAL PAPERS.proup in the para-position does not, therefore, bring about the changeof piwpyl into isopropyl ; i n this respect the ethyl group resembles therro~)yl, isopropyi, and acetyl groups ; consequently, the rearrangrmentto isopropyl appears to take place exclusively in the paramethyld eriuat ives.J. B. T.Behaviour of Phenols and Hydroxy-acids towards the AlkaliHydrosulphides. By F. FUCHS (Monatsh., 11, 363--372).--Theaiithor has previously shown (Abstr , 1889, 496) t>hat the hydroxylicI drogen of hydroxr-acids and phenols, derived from aromatic 'ly tgdrocarbons, is not displaced by metal, on treatment with an alkalihydrosulphide. The h \ droxy-acids of the fatty series, such as malic,citrir., and tartaric acids, behave in a precisely similar way; tetra- andlwnta-metbylphloroglucinols decornpose hydrosuiphides as if theywere monobasic acids, an action which the presence of carbony1 groiipsmav possibly deteiinine ; on the other hand.tetra- and penta-ethyl-pbloroglucinols have no such action, although the substitutioii ofbrorniiie in 1 he /?-position brings abont, deconiposition of the hydro-sulphide. This difference in the behaviour of methyl and ethylderivatives appears to depend on the relative weights of themolecules.Ortho- and meta-nitrophenols have no action on sodium hydro-sulphide, whilst paranitrophenol decomposes it. The sutstitntion ofa nitro-group in the ortho- or meta-position in a phenol seems,therefore, not to affect the replaceabilitv of the hydroxylic hydrogen,whilst, its substitution in the para-position does. This view is con-firmed by the beh.aviour of nitroeugenol, in which the nitro-group isort ho- to the hydroxyl.Tiibromoresorcinol behaves as a nionobasic acid, only one ofthe hydroxylic hydrogen atoms beiiig displaced by soditim frorn theIiydro~ulphide. Wben one hydroxjl group is displaced by ethoxyl.nosuch substitution occurs. The action of some other nitro- andhalogen-substit uted phenols on Fodiuin hydrosulphide has been deter-niined, and the msults depend both on the number and the position ofthe substituted groups, although no general conclusions can yet bedrawn. G. T. M.Constitution of Thymol and Cymene Derivatives. By G.MAZZARA (Chzzetta, 20, 140-149) .-3.3awitrolthymyl benzoate,CBHMePr(N02)2.0Bz [I : 4 I 2 : 6 : 31,prepared by heating the coirreaponding dinitrothymol with benzoicchloride for about two hours a t 160" to 180", crystallises from alcoliol illyellow, rhornbohedid plates, melts a t 1 2 7-128", and dissolves readilyin light petroleum and benzene.MeNH, /'\ NArnidob emarniclot hymol, I l o / %I%, prepared bF reducing\/ HPORGANIC OH EMISTRY.47tile preceding compound with tin and hydrochlwic acid, crystallisesfrom alcohol in yellow plates and from light petroleiim in prisms,melts at 106-108", and is tinged faintly violet by light. It is notaltered b7 boiling with hpdrochlorjc acid or with dilute (20 per cent.)snlphul-ic acid. The platinochloride crystallises from alcohol in yellowneedles which decompose at! 215".MeNEIBz /'Renzo~laml:dobe~eamidoth~n~ol, I I N\)CPh, prepared by"\/ OPrheat,ing a solution of the preceding cornpound i n benzene with benzoicchloride, crystallises from alcohol in bulky, wlrite needles and meltsa t 174--17;".It may be boiled with hydrochloric or dilute sulph-uric w i d without change.The formation of the above benzenjlamido-derivatives is i naccordmre with the hypothesis that in dinitrothynol one of thenitro-groups is in the ortho position with respect to t h e hodroxyl.The anthor i s n l h o investigating the actlion of acrtic anliydride ont h e corresponding a m i d d e r i v a t i v e with the view of obtaining aflirther confirmat,ion of this constitution by the formation of a nethen y 1 d e rivnt i ve.pre-pared by heatinq dinitrotjhFmol with acetic chloride, crystallises from:ilcohol in prismatic tufts, melts at 85", and dissolves i n light petro-leum. ether, and chloroform. The author considei*s t h a t the di-nitrocymene melting at 54", previously described (Abstr., 1890, 753).haq the constitution [Me : NO, : Pr : NO, = 1 : 2 : 4 : 61 and that theliquid and solid dinitrobromocymenes prepared by Fileti arid Crosa(Abstr., 1889, 493) hare respectively the constitutionsU;nitrothymyl aretafe.C,HMePr(NO,),.OAc [l : 4 : 2 : 6 : 31,[Me: Br: Pr :NO,: KO2 = 1 : 2 : 4:5: 6 and = 1 : 2 : 4: 5 : 31.S . H. A. A.Constitution of Thymoquinone and Carvacrol Derivatives.By G. MAZZAKB (Gnzzetta, 20, 183--19O).--l,initrocn/.rtaci"ol,C,HMePr( NO,),.OH [ 1 : 4 : 3 : 5 : 21 ,prepared by Carstanjen (Abstr., 1877, 614), erystallises from lightpetroleum in tufts of yellowish needles which turn red even indiffused light, and melt a t 11 7".The.LeiixcyZ derivative, C6HMcPr(NOJ2-OBz [l : 4 : 3 : 5 : 21, preparedlike t8he corresponding thymol derivative, crystalliscs from alcohol inlarge, Fellow, p r i s m ~ t i c plates which melt at 98-100", and turn brownwhen exposed too the light'.DiarnidocaruacwL C6HMePr(?TH2).2-OH, is prepared by heatingdinitrocarracrol (15 grams) for aboot an hoar, with tin (47 grams)aitd fuming hydrochloric acid (145 grams). The hydmchlo&e formswhite plates which are coloured violet by exposure to light; the baseis a red powder which softens at about 190".It, dissolves in dilute ~lcohol.Nitroarnidocurvacrol benzoate,C6H&tePr(NO2) (NH,)*OBz [1:4 : 3 : 3 : 2348 ABSTRACTS OF CHEMICAL PAPERS.is prepared by heating dinitrocarvacrol benzoate (10 grams) forabout an hour with tin (22 grams) and fuming hydrochloric acid(70 grams).It crystallises in rose-coloured scales which have ametallic lustre. I h forms R white sublimate a t 200". softens at, 230",and melts a t 280-283". The platinocldoride, (C17H,~N204),,H2PtCl,,crystallises in yellow needles which lose part of their acid at 30-40".The physical propert>ies of this cornpound and the absence of atiynitrobenzenyl derivative, together with the formation of a benzuyl-derivative (not yet described) with benzoic chloride, indicate that theIiitro-grnup in this compound is in the urtho-posit#ion with yegard tothc liydrox~l.MePrdinitrocnrvacrol benzoate with t i n and hydrochloric acid for 5 hours.It crystallises from alcohol in violet prisms which soften a t 125" andmelt a t 130-132O.The formation of a benzeriyl derivative fromdinitrocnrvacrol benzoate arid of a hydroxythymoquinone by theoxidation of the aruido-derivative shows that in dinitrocarvocrol one ofthe nitro-groups is in the ortho-pnsition and the other in the pava-position with respect, to the hydroxyl.Phenylazo- and phenyldisnzo-carvacrol (Abstr., 1885, 1 132), whichrespectively yield thymoyuinone and hydroxythymoquinone on oxida-tion, will accordingly have the constitntinns [Me : OH : Pr : N2Ph =I : 2 : 4 : 51 and [Me : OH : NzPh : Pr : NJ'h = 1 : 2 : 3 : 4 : 51.S. B. A. A.Action of Chloral on Resorcinol and of Aldehyde on Pyrogal-101. By H. CAUSSE (IjuZZ. SOC. Cliim., [ 3 ] , 3, 861-867).-Resorcinol(1 00 grams) and sodium hydrogen sulpliate (20 grams) are dissolvedi i i water ( 1 1iti.e) and c-hlural hydrate (50 grams) is added to themixture, which after some time deposits colourless, oily crystals ; ifwarmed a t loo", yellow crystals are deposited resnlting from thedehydration of the former.. The colourless cr;ystlals are insoluble illwater and in benzene, but dissolve in alcohol or ether, whilst theirsolutions in alkaline hydroxides exhibit. a remarkable fluorescence.At, 25d0, they become yellow, and decompose without fusion.With;wctic anhydride, this substance yields a crystalline diacetyl derivative,whic'h melts a t 2 5 2 O with decomposition. Analysis gives the formula,CI4Hl2Os, and the satne compound resulting from the heating at 103"of equal parts of resorcinol and of glyoxylic acid points to its havingthe constitution COOH-CH (O*CsH,.0B)2.P~rogalfol (50 grams), sulphuric acid (5 grams), aIdehyde (25 C.C.o f a 10 per cent.solution) and watw, (500 grams) are heated at 100"f o r several hours and successive quantities of 10 per. cent. sulphiiricacid are added, when crystals separate out, and by the addition ofmore aldehyde and acid further crops are obtainable. Froni themass of crystals. the colvurlcss a r e alone separatd and recrystallisedf'mm alc,)hol, separating as smibll, colourless needles having the corn-position CeHsOs, containing 2 niols. HJI, which are successively losORGANIC CHEMISTRY. 4 9at 39' and 80". The substance is insoluhle in water, benzene, andchloroform, slightly soluble in alcohol and ether, but is dissolvedemily by alkaline hydroxides.At 260", i t decomposes, and yieldspvrogallol a t a slightly elevated temperature. It has the constitutionCHMe:02'CGHJ.0H ; with acelic anhydride, i t forms a monacetylderivative whicli crjstallises in white prisms which melt a t 280".Formation of Ethereal Salts and Amides in presence ofWater and Alkali. By 0. HINSHEKG (Bey.. 23, 2962-2965).-1thas been shovn by Bnnmann and his pupils (Abstr.. 18S7, 2%;lbX8, 1296 ; 1889, 370) that benzoiu chloride may be used for detect-ing the hydroxyl-, aniido-, and imido-groups in certain cornpouridsby acting on them wit,h that reagent in aqueous solution in presenceof alkali. This reaction was, however, first employed for the pre-paration of benzoyl compounds by Schotten (Abstr., 1885, 176).The author has further examined the action of other acid chloridesaiid of acetic anhydride under similar conditions, and finds that cum-plete acetylatiori of the primary and secondary amido-bases and the:irotnatic diamido-bases readily takes place on shaking them withacFtic anhydride and iced water.Pheaylace tic chloride acts onnionhydric alcohols and pheno's, and primary and sccwrldary amido-hases belonging to both the fatty and arama,tic groups in the samemanner as benzoic chloride. Iliamines m d polyvalent alcohols,such as glucose, can also be readily converted into phenylaceticderivatives.Phenylsulphonic chloride is wi h i i t action on tertiary amines, butacts on botlh secondary and primary amines very readily.Thefk)riiler yield solid or viscous products. insoluble in acids and alkalis,whilst the latter form sulphonarnides which are readily soluble inalkalis. This reaction may therefore be employed to asvcrtainwhether an amido-compound belorigs to the primary, secondary, ortertiary series, and also forms a ready method for the separation of amixture of members of the three classes.I f the tertiary Lase is vo1;itile with sheam, the mixture of basesafter treatment with phenylsulphonic chloride and alkali and appt ox-imiite neutralisation, may be distilled in R current of steam. Thesulphonamide of the secondary compound then remains as an in-soluble precipitate in the residue, and may be filtered off, and the1)rimary cornpound obtained from the filtrate by precipitation withhydrochloric ticid.If the t e r t i a r j base is not volatile with steam,the mixture is extracted with ether and the tertiary base separatedfrom the sulphonamide of the secondary base by shaking the etherealsolution with dilute hpdrochloric acid. The sulphonamide of theprimary base is obtained bg precipitating with hydrochloric acid theirqueous solution reiirairiing after the extraction with ether. To recon-r e r t the sulphonamides into the bases, they are heated with hydro-chloric acid in a sealed tube a t 160".The reaction with phenj lsulphonic cliloride is not given by nmidocompounds whicli already contain an acid o r other strongly negativeradicle, such as the acid amides and halogen and nitro-derivatives ofthe arnido-bases.On the other hand, complicated substance; such asT. G. N.VOL. r,x. 50 ABSTRACTS OF CHEMICAL PAPER!!.fibrin and peptone yield white products, soluble in alkalis, whichliztve, however, not a t present been obtained in the crystalline form.:EX. G. C.Polemical. By 0. RKBGFFBT (Gazzettn, 20, 122-1 23) .-A con-troversial note in 1-efwence t o the papers piiblished by A. BischoE(Be?., 22, 1774) R.tid A . 13ischoff arid A. Hausdorfer (&id., 1795) ont h e action of aniline on chloracetic acid. S. B. A. A.The Condensation Products of Aromatic Aldehydes withAromatic Amines. Ry A. HAXTZSCH (Be?-., 23, 2773-2776).-Thehe condensation products, c-f which t h e best known i s benzylidine-aniline, CHPh:NPh, resenihle the oximes, innsniuch as thc>y contain acarbon and a nitrogen atom united togrt,lier by double linkage, and itseemed, therefore, important to determine, if possible, wliether thesealso exist in isomeric forms.An atternpt was first made to convertben7ylidine-aniline into an isomeric compound by treating it withbromine, under which conditions the plane symmetrical tolane di-bromide is converted into the axial symmetrical isomeride. The reactionwas c-arricd oiit, i n carbon bisulphide solutiou, and a yellow. amorphoiiscompouud obtained, which was shown by analysis to he hwzylidi?ze-anilin: dib?-oj/jide, C,,H,,NBr,. J t melts with decomposition at nbont142", is insoluble in wilter and ethor, but dissolves in cold alcohol.It is very readily decompnsed, but, instead of re-forming benzylidine-aniline, it splits u p into lserizaldehyde and parabrrmnniline.This takcsplace most readily on heating with ppidine. Wit,h reducing agents,i t loser; hydrogen bromide and n c t bromine, and is converted bysodium hydrogen siilphite into t,he additive product, 2C,H,*CHO +2C6HJBr-NH, + SO,. corresponding with the aniline compound de-scribed by Sohiff (Abstr., 1811. 304).Beiizylidine-aniline also yields a di-iodide. CI3Hl1EI.?, ohtained bymixing the fo~qiner n i t h iodine in benzene solution. It forms well-developed, dark brown needles, which melt a t 110" with decaoni position,do not yield iodaniline 011 heating with pyridine, and on reduction1-e-form benzylidine-auiline.No isonieride of the latter can, therefore,be obtained i n this marinerAttempts were also macic t o obtain isomeric condensation productsfrom substituted benzaldehydes and substituted aniliues, but withoutsuccess. H. G. C.Orthohydroxybenzylamine. By F. TIEMANN (Eel.., 23,3016-3018 ; cornpaw Goldsrlimidt and Ern+ Ahstr., 1890,141 I).-SaZicyZ-?netirhyl7rcrzobenzoic acid, OH.CsH,*C~:N*LlH.C~H~*COOH [OH : CH =1 : 2 ; NH : COOH = 1 : 31, i s prepared frorn salicylaldehyde andmetahSdrazInebeiizoic acid ; . it, crystallises from dilute alcohol inneedles, melts a t 195", and is insoluble in water. On treatment withzinc-(lust and dilute sulphui.ic acid, ol.tholrydrox!jbenzylanzine,OH-C6H4*CH2-NH2, and metamidobenzoic acid are formed ; they maybe separated by adding a slight excess of sodium carbonate to t h eacid solution, and ext,rncting with ether ; after evaporation, theresidual amine is puri6etl by dipsolving it in benzene, and precipitatingwith lightl petroleum ; light, yellow crystals separate, which melt a0 RGANlC CHEMISTRY.51l25", and sublime at a much lower temperatnre. It is soluble inwater, alcohol, ether, benzene, and alkalis, and gives a deep violet-blue coloiir with ferric chloride. Characteristic salts are obtained beytreatment with acids. The o x d a t e crystallises in lustrous, whiteplates. The arnine may also be prepared by the reduction of salicylicoxime with sodium amalgain in dilute sulphuric acid solution.Possibility of Existence of an Asymmetrical NitrogenAtom." By F.KriAFr (Bey., 23, 2780-2i81.).-Aacording to thehypothesis of Hantzscli aiid Werner, i h is possible that nitrogen com-pounds of the genera1 formula NXYZ may exist, in two opticallyisomeric. forms, and the author has, therefore, investigated derivativesof ammonia, hydrazine, and hydroxylamine, with a view to obtainings uvh i someirides.For the ammonia derivative, ethylbeneylamine, NHEt*CH,Ph, waschosen, as it yields a crystalline tartrate. It was prepared by heatingethylamine with benzyl cliloride and a little alcohol i n a s m i e d t u h ea t 110", and forms a colourless oil which has an ammoniacnl odour,and boils a t 194" (corr.). Its pZatinochZor;de, (CqH,,N),,H,PtC1,,crystallises in prisms. I n addition to the seconrlary base, a quantityof rtl/yZil,ibe7izuZnmin~, NEt(CH,Ph)?, is also obtained ; i t is anoily liquid boiling at, W6", whose platinochloiicle, (C,,H,,N),,H,PtCl,,i R a pale yellow, amorphous precipitate. The attempt to separateethyl heiizjlamine tartrate into two isomerides both by addition ofconiine tartrate and by fi.actioiia1 crystallisation, was without success.Negative results were also obtained in the case of paratoljlhydrazinetartriite. T'lie conclusion cannot., however, be drawn from these facatsthat optical isomerides of these compounds d o not exist, for thet;Lrtrate method is not always successful even with coinpoiinds con-taining ail asymmetrical carbon atom.Thus, the autbor finds that,a-phenyletlrylnrriine, CHMe*Ph.NH,, obtained by the reduct ion ofacetophenonoxime, cannot be split up into its optical isomerides bythis met hod.Finnlly, it is shown that both benzilenximes, on reduction, yieldone and the same di phenylh y droxyeth y l amin e, NH,.CHP h*CHPh*OH,previously obtained from the a-monoxime by Polonowskn (Sbstr.,1887, 492).H. G. C.J. B. T.Action of Amines of the Benzene Series and of Phenyl-hydrazine on p-Ketonic Nitriles. By L. BOUVEAULT (Compt. veazd.,111, 572-~74).-Meth~lpropion~lacetorlitrile combines with ortho-toluidirie to form ;L well crystallised compound, which melts at 125",and dissolves in alcohol, but is insoluble in ether 0:' water. Withp-nrtphthylarnine, tho nitrile yields a compound which crystallises inneedles melting a t 121", arld dissolves in benzene, but is almostinsoluble in ether.Mesitline jields a similar product melting a t114-115". Methylaniline does not; combine with r~iethylpropio~iyl-acetonitrile, but, 011 the other hand, tlie hicher homologue of thelatter combines readily with ortliotoluidine, forniirig a liquid boilingaf; 266", but analogous to the products already described. Fromthese results, the author concludes that the aniline derivative has thee 52 ABSTRACTS OF CHEMLCAL PAPERS.constitution PhN:CF:t.CHl\iIe*CN, and he calls it pheitylimidoi,iet7zyZ-propionylucetonifrile. The reaction is general, and the nitrilesR-CO-CR' R"*CN yield derivatives of the formula R"'N:C R*CR'R"*CN.The action of plienylh-j-dt.azine depends on the constitntion ofthe nitrile; if the latter belongs to the type R-CO-CR'R''.CN, ahydrazone is foriiied, NkIl'h*N:CR.CR'R''.C~, but if it belongs to thetaype R.CO.CHR'.CN, R derivative of pyrazole is obtained.Possiblyin the secoiid case tbere i s intermediate forniation of n hydrazone.Methyl propionylacetonitrile yields p l ~ e i z y l e f h ~ ~ l ~ n e t h y l u ~ a ~ ~ ~ p ~ L 1 : 3 : 4 : 5 1, wliich crystallises in large,colourless, hexagonal prismsniclltiug a t 81", and hoilinq a t 330" wittiout decomposition. T t is verysolnlle in most of the neutral solvents, but not readily in benzene oryetrolentn. Tt is a stronger bnse than the preceding compounds, andits acetate is only partially deconiposcd by water. When heatedwith llydrochioric acid in sealed tubes a t 120", the base undergoesno change.With sodium nitrite and hydrochloric acid, it yields ayellow diazo-derivative, whicli, when boiled with alcohol, yields i hephenylethy lmethylpyraxole previously obtzlined by Claisen :I ndNeyerowitz. If water is used instead of alcohol, the correspondinghydroxFpj-razole is obtained, melthg a t 104". The diazo-derivativeforms crystallisa ble colouring matters with phenols and amines.C. H. B.Carbonylorthamidophenol and Thiocarborthamidophenol.By 8. CHELMICKI (c7. pr. Chem. [a], 42, 440-445 ; compare Abstr.,1887, 477).-When carbon~lorthamidophenol is heated with aniline in;t sealed tube a t .200--2!0", arid the product treated with sulphuricacid, decoloriserl by animal charcoal, and crystallised from alcoliol,white, brittle needles of the formula C,,Hl,N,O are obtained.Thisnew substaiice mel's, with decompohition, a t $noo, and dissolves inmost solvents exrept water ; strong hydrochloric acid a t 160" decom-poses i t into ortiiatriidophenol hydrochloride, aniline hydrochloride,a n d carbonic anhydride ; chloride of lime converts it, i n acetic acidsolution, into a chloro-delivatire, C1,HI8CI2N20, melting a t 276O. Thissu bstaiice is isomeric with Kalck ho fT 's anili docarbamido phenol (,A bstr.,1883, 1 l l O ) , :md must therefore be C6H,<E:>C:NPh.Nit,.occirbonylorthanziclophenol, [NH : 0 : NO, = 1 : 2 : 41, crystal-lises in long, yellow needles melting a t 240-241" (uiicorr. ; Bender'snitrt-L11tiydro-orthamidophenyl carbonate melts at 256", Abstr., 1887,38). When this compound is trealcd with potash, it is convertedinto nitrocatechol, [OH : OH : NOz = 1 : 2 : 411, melting a t 170"(168".according to Weselsky and Beiiedikt, Abscr., 1878, 575).OH.C6H4*NH*C SON H-C3H3,is obtained by mixing ally1 ibothiocyanate (1 mol.) with orthamido-phenol suspended in alcohol, and leaving the mixture a t rest for sometirile. It foriris white crystals whicii melt a t 99', and are more orless soluble in all the usual solvents. When i t is heated with hydro-chloric wid iit 130". it is converted into thiocarborthamidophenol.Thiocarborthainidophenol evolves Iiydrogen sulphide when heatedabove its melting point.; with awmonia act 'LOO", i t is decomposed intocarbaiu\dophcnol, carbonic ntihydr.de, arid ammonium sulphide. WlieuOi*th ohydroxypht ngllr l l y lt hiocarbwmideORGAN CC CH EN ZSTHT.53an alcoliolic solution of iodine is added t o thiocarborthaniido~~henoldissolved in sodiiim hydroxide as long as t h e iodine is decolorised,Y crystals of the bisiilphide S2(C<b>CtiH,), (Abstr., 1887, 477) areformed; this snbstance melts at 110", and dissolves in most solvents.A. G. 13.Derivatives of Carbonylorthamidophenol and of Thiocarb-orthamidophenol. By P. SKIDEL ( J . p. (Ihrm. [ a ] , 42,445--4.57).-KalckhoWs anilidocai*bamidopheiiol is more easily obtained thanChelmicki's compound (preceding abstract) ; this i u evidence th;ttcaa;bonylorthamidopheiiol is C,H,<- o>CO, for the doubly-liiikecloxygen atom might, be expected to be more difficnlt to displacethan the group -SW.T'he ethyl compound, C,H,<"T>CO, - can-not be made to react with anilirie. The crystals of carbonylortli-amidophenol 50011 lose their lustre in air, being changed to stnallneedles ; the author sugg i s t s that the unstable crystals areC6B4<;>C*OH,NHNH and the stable crystals, C,H,<-O>CO. The crystals of thiocnrb-ortliamidopheuol do not change, aild this is in accord with the generalbelief that the stable form of this compound is C,H,<O>C*SH, aformula supported by t h e fact that by trefitrnent of orthamidophenolv i t h thiocarbonyl chloride, the same thiocarborthamidophenol isobtained as that obtaiiied by the action of ca14)on bisulphicle oncarbonylortha midop henol.By the action of ethylorthamidophenol (ni.p. 107.5", not 167.5" asqiven by Fiirster, Abstr., 1880, 464) on thiocarborryl chloride: a thio-;.ar.bon!,Zethilanzid~~l~enoZ is obtained x h i c h melts a t 112", and boilsundeconiposed above 300" ; i t is different froin Chelmivki's ethylderivative (Abstr., 1887, 477). This compound is deooinpooed bystrong hydrochloric acid at! 170" into ethylorthsrmidophenolcarboiricanhydride and hydrogen sulphide, showing t h a t its constitutioii isNEt C,H,<-O>CS. By heating this derivative w i t h aniline and leadoxide, an anilide is, with some difficulty, obtained free from sulphurnnci homologous with Chelmicki's anilide (previous abstract) ; t h edifficulty with which it is obtained confirms the double linking of thesulphur.to the carbon and, therefore, t h c above formula.'I'o obtain niethSlortIiamidopheno1, orthainidophenetoii was inethyl -ated with methyl iodide in the cold, by which means the hydrioditlesof me th j - I o r t h m i do phenetoi'l, dime t h 1 I orthainidophene to'il, and or tli-a rn i do p h ene toil, and mnidophenetoi It?-imet h y lammonium iodide wereobtained. The last-mentioned crystallises in nacreous, violel,-tintedleaflets, freely soluble in hot water. The niixture of t h e throemet,hylorthamidophenetoils waA heated with strong hydrochloric acidat 1 iO", ttiicl t I ~e iiiixed nie th~lortl~itl~li~c,plrenuls thus o b h i i d wereT54 ABSTRACTS OF CHHXICAL PAPERS;.treated with thiocarbonyl chloride.This treatment' yields fhiocarh-o ~ a y l ~ i a e t h y l o r t h ~ ~ i z ~ ~ o ~ h e ~ z o l in colourless needles which melt a t 128",and boil uiidecomposed above 300" ; stilong hydrochloric acid at l i 0 "decomposes it into methylortharnidophenol, carbonic anhydride, a dhydrogen sulphide, 50 that its constitution is similar to that of thio-carbonylethylorttiamidophenol (see above).Methylorthanlidophenol crystallises i n colourless leaflets whiclisoon oxidise and become brown in air ; it melts with decompositiotiat SO".C~cyboi.tha?izido(phennZ chloyide, C6H4<E>CCl, is obtained whentliic )carborthamidophenol and phosphoyic chloride are mixed togetherand the product distilled ; thiophosphorgl chloride passes over belowl3Oo, and t h e portion t h a t distils between 13U" and 205" separatessfter a time into crystals and a n oil ; the crystals were not investi-gated.The oil is carbol.ttiarriidopheno1 chloride ; it boils a t 201-202".solidifies in a freezing mixture, and mtilts a t 7" ; i t is a feeble baseforming a we!l- crrstallised ni tml e and hydrochloride ; i t is decorrr-pnsed hj- w;Lter into cnrborthamidoplienol and hydrochloric acid.With phenol, it yields two cottipoiinds, one of mliich is a cai*bo~th-ai~iclophei~id pheny 1 etkey-, C,H,<~>C.OPIi. melting a t 56" andboiling a,t 310°, whilst the other melts a t 190" and boils at a muchhigher temperature. With aniline, ca~borthamidophenol chlorideyields Kalckhoff's anilide. Carborthamidopl~ei~ol chloride is alsop 1'0 d u ce d w h en met h y 1 and e t h y 1 t hioc arb( my 1 o 1- t 11 am i do p he ri 01 s areheated with phosphoric chloride.A. G. B.Preparation of Anhydrous Diazo-salts. By E. Kso EVKPI'AGRL(Ber., 23, 2994-29!18) .-Up to the preaent time very few-diazo-saltshave been obtained i n the arihjdrous condition, the most, irnpui-tantexceptions being diazohenzene sulphate and nitrate. The authorfinds thatl all the salts may be readily prepared in t h e anhydrons con-dition by treating the amido-compound i n acid alcoholic solution withamyl nitt ite. To prepare diaxobenzene sulphate by this method,15 grams of aniline is dissolved in 9-10 parts of absolute, or- at least95 per ctnt. alcohol, and 20 grams of concentrated sulphuric acidcarefullj added ; aniline sulphate separates a t tirst, but redissol\-es oiladding the reinaincler of the acid.When cold, 20 grams of amylnitiite itre added, and t h e mixture well c.?oled, ice being pre-ferably employed in the preparation of large quantities. After10-15 minutes, diazobenzene siilphate usually separates in beautifulneedles, the whole mass solidifying tr, a crystaliine magma, which, onfiltering and ~ a f i b i n g with alcohol and ether, yields the cL)mpouiid inail almost pure condition. If t h e sulphate does not separate after10-15 ininiites, t h e addition of a few drops of ether causes animmediate crystallisation, and a further quantity of t h e salt may beobtained by adding ether t o the mother liquoi.. The diazobenzenesnlpliate t h u s obtained has all the properties assigned f o i t by Griess,and is tnoi-e reatlily 1)repnred in this manner thrtn bj- his method.Diazobeiizene iiittate is most reildi 1)- pi*elmred by adding wt trcORGANIC CHEMISTRY.5 f5more than the theot.eticil.1 quantitg of amyl nitr:te to a cold saturatedalcoholic solution of a ~ i l i n e nitrate containing a little free nitric acid,cooling well with ice. On the addition of a small quantity of ether,diazobenzene nitrate separates in beautiful needles, which explode,when dry, very v i o l ( d y , either on heating or by percussion.Diazobenzene chloride, which h a s hitherto notl been obtained in thesolid condition, is easily prepared in a similar. manner to the nitrate ;very cai$’ul cooling is necessary on adding the amyl nitrite, as thediiizotisation of aniline chloride proceeds very rapidly. After a sho1.ttime, the salt separates in almost colourless needles, which are col-lected, washed with a little alcohol and ether, and dried over sulphuricacid in a vacuum.The yield is almost quantitative ; tjhe determina-tion of chlorine and nitrogen gave nunibem agreeing closely with tlieformula C,H,*N,Cl. Diazobeiizene chloride decomposes on heatingwith a slight explosion, but only gives a slight detonation bypercussion. It is soluble in alcohol, but insoluble in ether. benzene,aud light petroleum ; water dissolves i t with great aviditv, and itdeliquesces in moist air, undergoing considerable decomposition, b u tis fairly stable in dry air, especially in the dark.‘Yhe following diazo-compounds have also been obtained in theanhydrous condition by this method :-The diazo-sidphates of ortho-t,ol uidine, paratoluidine, paraphen e tidiii e, pitrani sidine, ai i d metarii ty-aniline ; tlte ciiazo-nitmtes of ortho- a n d lmra-ttoluidine ; the dirczo-chlor.ides of pard,toluidine, paraphenetidiue, atid paranisidine.H.G. C.Action of Alkalis on Acid Salts of Diazobenzene : EthylDiazobenxoate. By T. Cumus (Ber., 23, 303:3--30.36).-B5heating diazvbenzene sulphste wit ti th:: calculated quantity OF bariumliycl~*oxide and extracting with etter, a very volatile, feebly basiccompound is obtained whicii is volatile with steam, melts a t -3”,N Itd bas an odour resemblirig that of rose water; a1 though no evolu-tion of nitrogen could be detected, ancLlysis sliows that only 2 atomsof ititrogen are combined with 3 benzene nuclei.A correspondirtgcompound may bs prepar\d in tlie same manner from ethyl meta-cliazoberizoate sulphate. No hydrazine could be detected in themot her liquors, and only in one experiment, with duminium aridalkalis, was any formed by the reductiou of the compounci it1 eitheracid o r alkaliue solntions. Attempts to prepare tliazobenzene, bythe action of silver nitrite on di-y aniline hydrochloride dissolved insome indifferent medium, were urisuccessf ul, diazosmidobenzenebeing the sole product, and, in a similar mariner, ethyl metamido-benzoate yields ethyl diazoamidobenzoats. Diazoamidobenzene maybe prepared by mixing very dilate, cold, aqueous solutions of anilinehydrochloride and sodium nitrite ; after washing with cold water, theproduct is quite pure.The potassium and silver salts of diazo-benzene, prepared according to the met‘lod described by Griess, werefound on analysis to coritaiii only two-thirds the tlieoretical quantityof nitrogen, the proportion being 6 rttonis of earl1011 to I of nitrogen.The quantity o f nietul present agreed closely with the theory. Theauthor is unable to assign any formula, t o these compounds.J . B. T5 6 ABSTRACTS OF CHE3IIOAL PAPERS.Hydrogen Nitride (Azoimide). By T. CLTRTIUS (Ber., 23,:312:?-3O33) .-Hpdi.oyeu m'tridp, q>NH, is formed, under certain Nconditions, by the action of sodium nitrite on hydrazine hydro-chloride: the reaction is strictly anallogous io the formatSon ofnitrogen from ammonium chloride am1 sodium nitrite. To obtain itin this manner is, however, R matter of considerahle difficulty, and itis best prepared from hkppzwy Zhydyaziiae in the manner describedbelow.Renzoy Zhydi-mine, NH,*NHBz, is formed on mixing molecular pro-portions of ethyl benzoy lgClycollate and hydrazine hydrate ; it crystal-lises from alcohol in large, lustrous plates, melts at 112", redncesalkaline copper solution in the cold.and dissolves in cold water, biitis only sparingly solohle in ether. It is not) changed on boiling bitliwater., but is Iiydrolysecl by the action of dilute alkalis. The samecompound is also obtained by the action of hydrazine hydrate onethyl benzoate.Benzo!/ZbenzaZh!ldl.nzinP, NHBz*N:CHPh, is prepared by addingbcnzaldc, hyde to beuzoylhydraziiie i n molecular proportion, and istleposited from alcohol in long, colourless crystals which melt at 203",are very spariiigly soluble in ether, and insoluble in water.S p metrical di benzo y ih y draz iiae, N HRz -N HBz , is obtained byboiling benzoylhydrazine ; it CI-ystallises from alcohol in silky needlesmelting at 255O, and is hydrolysed by treatment with acids oralkalis.On heating a cold aqueous solution of benzoylhydrazine with a nequal molecular proportion of sodium nitrite, and acidifying withihcetic acid, benzoylaxim ;de (7w)rroic nifyide), I I >NBz, scparate~ as anoily liquid which solidifies after some time.It crystallises in colour-less prisms which melt a t 29-30', explodes on heating, and is volatilewith steam. Ry treatment with alkalis, it is hydrolysed, but under-goes no change on boiling with acids ; i t reduces ammoniacd silversolution, but has iio action on alkaline copper solution; it has itpowerful odour resembling that of benzoic chloride, arid rapidlyattmks the skin.Hythceiriacetic acid (amidoglycocine), NH,.NH*CH,-COOH, is p1.c-pared by acting with ethyl benzoylglycollate (1 mol.) on hydrazinehydrate (2 mols.) ; the benzoylhydrazine which firht separates i qremoved, and after. some time the acetic acid derivative is depositedfrom the mother liquor ; it, is purified by repeated recrystallisatiun fromalcohol, and forms large, lnstrous platvs, tvliicli melt a t 93", and are in-soliible in ether. It has a sweet taste, gives with alkaline copper solutioiia deep violet colour, and, on warming, a precipitate of cnprous oxide.A red colour is yiwduced with neutral ferric chloride solution, airdammnniacal solution of silver is reduced in the cold.The compoundis hydrolysed by war.ming with scids or alkalis. Benzalhydmzine-acetic acid, CHPh:N.NH.CH,.COOH, is formed by the action ofbeuxaldehyde on the previous compound, and crystallises from alcoliolin silky, lustrous ueecl1c.s nielting a t 156.:)". Hzppui yEb~r~zLcZl~~dl.azi,~e,NORG-4NIC OHEMIS'L'RY. 57NHBz-C H2*CO-XH.XH,, is prepared by adding the calculat,ed quantityof hjtlrazine hydrate to an alcoholic solution of ethyl hippurate ; itcrystallises from alcohol in coluurlcss, lustrous needles which melt a t162.5, and are sparingly soluble in ether ; the yield is 90 per cent.nlknliiie copper solution, a green colour is produced, and after sometime reduction occurs.Hi23pu1.lllbe~iznlhycll.nzil2e,N HBz.CH,*CO-NH*N:CHPh,is formed by the action of berizaldehyde on the previous compound,and crystallises from alcohol in lustrous plates which melt a t 182'.Bg the action of acetic acid and sodium nitrite a t 0" on an aqueouqsolution of hippurylhydrazine, R compound is ohtained crystallisingfrom alcohol in colouy!ess needles which melt at, 98" ; i t is probablyeither nit,.u.sohippurllZl/~d~az~ne, NHBz-C H,*CO*N( N 0)-NH,, or nitmso-hydraxifie hippzoic acid, NO.NH.PU':CPh.P\TH.CH,~~O~~ ; by treat-ment with acids or alkalis, azoimide and hippuric acid are formed ; onboiling with water, an iudifferent gas is produced, together. with avery insoluble substance that has not yet been investigated. Theni troso-conipoiind readily dissolves in alkalis or ammonia, and thesolution exhibits a beautiful blue fluorescence.On adding silvernitrate to the ainmoniwcnl solution, a nhite, explosive, silver salt isprecipitated.Azoinzide may be obtained from benzoyl hydrazine or hydmzine-acetic acid, but is best prepared from the liippuryl compound bydissolving it in dilute soda, and decomposing the boiling solutionwith dilute sulphuric auid ; the azoimide distils over with the steam,and is passed into neutral silver nitrate solutioii, the precipitated silversalt is collected, washed wit)h water.dried at 60-70", and treated withdilute snlphuric acid. By repeatirig this procsss, a solution is obtainedcontaining 27 per cent. of azoimidr; on bringing the solution intocontact with ammonia, thick, white vapours of the ammonium saltare formed. Azoimide itself is a gas, having a part,icularly nauseousodour, and resembling hydrogen chloride in its general properties.It is very soluble in water, and on distillation a concentrated solutionpasses ovey ; the distillate gradually becomes weaker until equilibriumis established, a solution of defiilite strength being obtained whichboils constantly. A piece of blue litmus p,iper held orer the solutionturns iaed.Iron, zinc, copper, aluminium, and magnesium readilydissolve in a 7 per cent. solution of the gas, hydrogen beiiig evolved.Gold and silver also al)penr t o be attacked. Azoinide is liberated bytJic action of dilute sulphuric acid on aiiy of the salts ; with coneen-tianted sulph uric acid, the azoimide is itself decomposed, Bwiu 112nitride, K6Ba, is obtained in liishrous, hard crystals which are readilysoluble in water, and explode with a green flash on heating. Silvrrnitride, NdAg, crystallises in prisms which melt at about 250" wit11 aviolent explosion. J . B. T.r 7 1 he compound rednces amnioniacal silver solution in the cold ; withAction of Acid Chlorides on Acid Amides. By A. PICTET(Ber., 23, 301 1--3016).-l3enzsnilide and acetic chloride are formedon heating bciizoic clrloridt! nncl acetanilide a t 140" ; the same result i58 ABSTRACTS 0" CHILJZICAL PAPERF.obtained if the compounds are dissolved in toluene.This reaction isf o u n d to be a general one, both for the aromatic and fattyamides aridchlorides ; and the author explain., i t by assuming that an additivecompound is first formed which then decomposes, the radicles containingthe least number of carbon atoms combining with the chlorine, whilstthe higher carbon derivatives unite with the nmide complex. Theproduction of benzanilide, for example, mould be preceded by theformation of the hypothetical compound acetobenzanilide hydro-chloride, NHPhBzAcCI. These observations confirm those of Yaaland Otten (compare Abstr., 1890, 1415).J . B. T.Action of Sodium on Acid Amides. B y T. Gun-rrus (Ber., 23,3037-3041) .--Sodium benzamidr, CO€*h.NHNa or ONa-CPliNH, isprepared by boiling a benzene solution of henzamide with rather lessthan the calculated. quantity of sodium. The operation takes about 30hours, the precipitated salt is separated, treated repeatedly with ether inan extraction apparatus, and dried over sulphuric acid and quicklime.T t is a white, crystalliiie powder, insoluble in ether, chloroform, orbenzene ; it is very readily decomposed by water, or by dissolving inalcohol, but is not hygroscopic, and on distillation, yields benzene, sod:^,amimiiia, and a little benzonitrile.Sodium diberzxamide, NBz2Na, is obtained by dissolving dibenz-amide in xylene: and boiling the solution for 30 hours with a slightexcess of sodium ; no evolution of amnioiiia occurs ; the pi oduct c r ptallises trom ether iii small, white, Iiiotious plates whicli melt a t 150":ind resolidify on heating t o 230", and then do not melt at 300".Thesolid is readily soluble in I\ ater. On distillation, sorlium dibenz-amide yields only ti*aces 9f benzene ; it, is much more stable tlian thebenzarriide salt, and a recently prepared aqueous solution gives pre-cipitates with tlie salts of many of the heavy nietnls.By tlie action of sodium or1 acetamidti, consider,ible quantities ofammonia are evolved, aiid a viscid liqiiid separates, which after sometime becomes cr)stalline ; i t contains uitrogeii, and is possibly sodiurrhd iacetuwbide, NhczNa.By the action of iodine on finely divided sodium benzamide, 01'sodium dibeiizamide suspended in ether, additive compounds arel'ornied which readily wystallise, but do not show a constant composi-tion.Benzamide and iodine give the compound NH2BzI.NH,BzI (?),crjstallising in long, slender, olive-green prisms, which exhibit pleo-chr-oism arid melt at 110-118" without deconiposition. The com-pound is stable in air, and insoln1)lc in water, but readily dissolvesin glacial acetic acid; cn shaking with mercury, beiizamide andiuermric iodide are formed, whilst by distillation, or on boiling withwater or alcohol, it is decompose+ into iodine and benzarnide.Iodine and dibenzamide give a compound, NB4Bz,12, which crystal-lises in large, green prisms melting a t 118-180" ; i t is readily solublein chloroforrri, aiid resembles the preceding s:i bstnnce i n properties.Tribenaamide, NBz,, is formed together with dibenzamide by treatingberizauiide with exuess of benzoic chloride ; it is very sparingla-soluble iu alcohol, and is deposited ill s~lky, lustrous needles 15 hiclORGXSIC C HEMISTR T.59melt at 202", sublime without decomgosition, and Iield benzoic acidand ammonia when boiled with soda. J. B. 1'.20, 172-178) .-When benzonitrile is treated with concentratedsulphuric acid (sp. gr. = 1-82), an energetic reaction takes place, anda-toliconiide (phenylacetamide) is formed. An almost theoreticalyield is obtained if the proportion of the acid used contains thequant'iiy of water t,heoretically necessary for the transformation.ChZoralp7Let/ylncetnmide, prepared by heating a mixture of anhydrouschloral and pherylscetamide in molecular proportion for half an hour,crpst,allises from alcohol in minute, nacreous scales which melt at145", and dihsolve in alcohol arid in boiling ether and benzene..Phen!/lacet~i/lhydrazine, CH,Yh*CO*NH*N HPh. - Phenylacetamidereacts w itki phenylhydrazine like fvrniarnide, acetarni(le, &c., accord-ing to Justus' equation RCONH, + NH,*NHPh = R*CONH*NHPlr + NH,.A rnixtnre of the amide and phenyllrydrazine in molecularproportion is heated at 120-130" ; the product cry~tsllises fromid~~oI~01 in colourless scales which melt a t 175-176", and are mode-rately soluble i n Wiirm alcohol.When I~henylac.etamide is heated with aniline in molecular propor-tion, at, about 150", ammonia is evolved, and the product, after repeatedpyecipi tation with water and recryst~llisntion from alcohol, yieldsnac~'eoiis scales which melt a t 116-117", and are readily soluble inalcohol.This compound seems to be identical w i t h Holmann'sa-toluylanilide.Phen ylacetylparatoluididr? is obtained by heating the smide with para-toluidine a t 160--180" uiitil the evolution of animoiiia ceases. Itcrystallises in small, transparent tables whiuli melt at, 135-126", middissolve readily in alcohol and ether.(Re,;, 23, 2917--2919).-lt has been shown that imido-ethers &reformed by the action of hydiogcn chloride on a, mixt~ure of an alcoholand a nitrile. Further exper%nents have shown, however, that certainzyomatic nitriles, in which a carbon atom, in the ortho-positioniselatjive t'o the CN group.is linked to another carbon atom, are in-capable of forming iniido-ethers. It is also found t h a t orthodicyanideRonly form moninii2o-ethers. The first of these conclusions is formedfrom a study of ort hocyanot oluene, paracj anotoluene , pai*acyano-xylene, a-cyanonapl;tbalene, and mctacyano-xyleiie [Ble : Me : CN =1 : 3 : 41, whilst the second is deduced from the investigation ofmctadicyanotoluene [Me : CH : CN= 1 : 3 : 41.compare Abstr., 1890, 496) .-Ethyl berLsa?izidylcarbu?nate,NH:CPh*NH*COOE t,is prepai-ed by the action of aqueous soda and ethyl chlorocnrbonateon benzamidine hydrochloride ; it cr-j-strtllises from alcohol in thick,Ivhite prisms which melt at 57-48', and are almost insoluble in water.Ou heating the compound to about 150", decompositioii takes place,a-Toluamide and its Derivatives.By A. PURGOTTI (G'ozzetta,S. B. A . A.Conversion of Nitriles into Imido-ethers. By A. PINNERJ. B. T.Diphenyloxycyanidine. By A. PINKER (Bey., 23, 2919-2922 r;o ABSTRACTS OF GHENICAL PAPERS.alcohol and ethyl carbmnate are eliminated, and diphenyloxgcyanidi nc(m. p. 289") is fornicii. Ug th3 action of alcoholic ammonia on thelatter substance, i t is convcrted into beiizamidine and ethyl carbamnte,whilst with aqueous aEmonia, benzamide and urethane are formed.UibensamidyZca?.Snlnide, CO (NH.CPh:NH),, is obtained by theaction of carhony! chloride on benzamidine ; diphenyloxgcyanidine isalso produced during the reaction, and tlio two compounds cannot becompletely sepwated ; it crystalli*es from alcohol in prisms which aresoluble in soda, and melt at 229" with evolution of ammonia.Thecompoud is conip1et)elj- converted into diphenylcyaiiidine on heatingabove its meltiug point. Expel-imeiits with propionarnidine were un-successful. By the action of ci~rhot~yl chloride on capronamidinec2ic~l.pr~nct1rzidi~~ebiicrct, NH(~i>.SH.C',H,,:NH>,, is obtained, crys-tallising from alcohol in stellate groups of slender, white needlesmelting a t 236". J. B. 1'.Amidines. By A. P r m E i t ( B ~ I - . , 23, 2923-2927 ; compare Abstr.,1889,1004).-Eth~nyZdip7lenl/lu~~~~~~, NHPh*CO*N:CMs*NH.CWNHPh,is for!med by the action of pheiiyl cyanate on acetamidine ; it wystal-lises from acetone in sinall, sleridthr iieedles, melts at 169", aiidyields acetylpheny1caPbanii~e on boiling with 6-8 parts of 50 percent, acetic acid solution.P~opr,nyZ~~i2Clh'n1/lurrid, N HPli*CO*N:CEvNH*CO*NHPh, is prepai-edfmm propionamiditie in a similar manner to the ethenyl derivatives,and crystallisrs from acetone i n slendor, white needles melting at169-1 7b".On distillation, i t yields diplienylcarbamide, whilst onboiling with dilute acetic acid, propionjlphenylcarbamide is formed.Actio M of A1 d eh y des o n Be71 zanz idine. -Further i lives tigat i onrenders it probable that the compound obtained by the actioiiof benzaldehyde on berizamidine (Zoc.tic.) is d i p h y l dicyaitide,CIIHIOXJ?, and not honzvlidenebenzamidine, C14HlrN2, as shted.Lophirie is also foriced in a very small quantity during the renct,ion.A yellow, amorphous product of the formula C,,H,,N,O, is obtaiiled bythe action of acetaldchyde on benzamidine ; it melts below IOG", issoluble in nlcoliol, ether, aiid chlorofor.m, but insoluble in wu6er orlight petroleum. It yields an amor.phous platinochloride, which niel tsa t about L08". On henting the base nt 130°, and treating the productwith h~.drocliloric acid and platinum chloride solution, an amorphouspZal'inorhZor*;cle is f-oimied which rrielt,s a t 1813" wit,h decomposition, andis probably R purer preparation of the above lower nieltiag corripoiind..J.B. 2'.Action of Benxamidine on the Ethereal Salts of AromaticOrthohydroxy-acids. B.y A P~NNEIL ( Ber., 23, 29:34--2941) .-Bythe action of sodium hydroxide (2 mols.) on ethyl salicylate andbenzamidiite liydrochloritle, crystals are obtained froin which benz-umidine salicylate may be separiltsed by treiitment with acetone ; it isdcposited in large prisms which melt a t 2U2", and ?re readily soluhlcin water or alcohol. The residue remaining after the extraction wii,liacetone forms slender, yellow needles melting a t 246". It is insolublein organic media or i n aqueons soda, ant3 gives a red colour withconcentrated sulphuric acid. The sariie coinpouiid may he prepareORUX-VIC: CHENISTKY. G lin larger quantity by heating an ethereal solution of benznmidinewith ethyl salicylnte at 40" for 10-12 hours ; the ether i s evaporated,wmd the residue boiled out with water. The substance has theformula CzlHliN30, and is formed by the elimination of water,alcohol, and ammonia from i mol.of ethyl salicylate and 2 mols. ofhenzsmidine. The acetyZ compound, C:21HEIPN,0*A~, is prepared bytreatment with acetic: anhydride and zinc chloride, and crystallisesfrom alc*ohol in colourless, lustrous prism.; melting a t 146-142".On adding hydrochloric acid t o the alkaline filtrate obtained afterthe separation of tlie berizuniidine salicylate, be?zzanzide salicy late isprecipitated ; it crjstallises from bol water in silky, lustrous plateswhich melt at 120". The compound had been previously prepared(compare Ahstr., 1889, l O O 4 ) , but its const,itut,ion was unknown.Hy the action of bemamidine on t,he methyl salts of the hydr-oxytoluic acids, corripoiirids are obtained corresponding in propertiesand constitution to the above salicylic acid product.The derivativeof orthoh-droxytoluic acid [COOH : OH : Me = 1 : 2 : 31 melts at214" ; that, of rnetsliydroxytolnic acid L1 : 2 : 41. a t 235' ; whilst theproduct from Farahydroxytoluic avitl [l : 2 : 51 melts a t 202". Alltlicse compoundh are insoluble in acids and alkalis, and a r e exceed-ingly difficult to burl?. Paradihydroxyberizoic acid [COOH : OH : OH= 1 : 2 : 51 also condenses with heiizaniidine; tlie com1)oiind istlrposited from benzeiie in small, nodular crystals, melting at26:) --266", with previous softetiing at 250".The formation of the above conipounds probahlj- takes place in twostages ; in the case of salicylic acid, the hypothetical interniediateproduct has one or other of the formulaeainmonin is then climinatrd, the constitubioii of the filial product beiiigrepresented by t,he forniulzOn hcating ethplphloro~lucinoltricat~boxylic acid with benz;tmidinefor two hont-s a t l:JOo, 2 mols.of carbonic anhj dride arc eliiuinated,slid a compound is formed to which the forniulitC,H@H)2<C(OH) N:cPh>N [OH: N : C = 1 : 2 : 31i s given. J. B. T.Imido-ethers. BJ- A. PISNSK ( h r . . 23, 29&--d956).-1~1uo-LTH EKS FROM 'I'RIMWHYLENE ~~ARiT)E.--TrimethylC'ile cyanide is pre-p r e d by mixing trimethylene bromide witlr 2.5 parts of 85 per cent,;llt.ohol, and adding Q part of finely divided potassium cyanide ; afterboiling for 5-6 hours, the proJuct iH filtered, the greater part of the;Ilcohol removed, the residue dissoli ed in water, and extracted wit11ether; after.distilling off the ether., the crude product is fr.actic,Il-iLteL1 ; the Sield is 85 per cent. of theorp. 7'he hyd?*ochlorides of glutar-all~itlyl ethyl ether- and glutitrumitlyl methyl e t h w are unstable. GlpttaT62 ABSTRACTS OF CHEMICAL PAPERS.amidyl i s ~ b ~ t y l ethw IiydroclrloritEe, C3H6[ C (NH ).C)*CH2.CHMe,. HCl],,is readilg soluhle in water or alcohol and crystalli~cs iu plates. Bythe action of wat >r, ammonia, is eliminated, and I : s o ~ u / ~ J Z glutartrte,C,R,(COO.CH;CHilile,),, is formed ; i t is a viscid liquid hoilinc a t270".On heating the imirlo-ether hydrxhloride, it softens at, l l O o ,and at liigher tenipwaturzs deconiposcls into glntarimide, isobutylchloride, and isobut.~larniiie iiydrochloridc. By the adion of aqueousammqnia, it, i s converted into gZictammide, C,H,(CO.NH,),, which i ssoluble iii water or alcohol, and melt., a,t 176" with evolution ofatninonia. On ti.eatment witjh alcoholic ammonia, isobiityl alcoholand ammonium chloride are eliminilted, aiid a n additive compound isformed consistirig of the hydrochlorides of glntaramidine and glutqr-imidine i n in,)lecular proportion ; on dissolving it in watei-, the iniidineis formed, b u t i t could n o t be isolated on account of its great solubility.Or1 evaporating t,lie mothei.liquor friJm t h e above additive com-pound, large rhornhic crvstals of ~ Z ~ ~ t c ~ , ~ c n ~ n i ~ ? i i i ~ hydrochlorl'dr,C,H,[C(NH)NH,,HCl], + 2H,O, are obtained, which are readilvsoluble in water or alcohol but cmnot be recrystallised ; the hy(1ratedsalt melt? at 7Y", and t,he antiyclrous compound at lt39O. The plntirho-chlo~iclr is deposited in flat, yellow prisms which melt a t 214" withdecoinposi tio I I . Gluf(r r i m i d y l ac-ttcfe, C, €3, [C( N H) OAcj2, is preparedby tlie itc:tioll o f acetic anhydride and sodium acetate on glutaramid-iiie hydrochloride, and crystallises in smal!, lustrous needles meltiirga t 210 -211".By t h e action of primnry aniines on the hydrochlorides of glutar-i [ I t ido-ethers, s u bst itnt ed glutariniidines are form?', the hyd 1'0-chlorides and platinoclilorides of which are ercrssively unstable.lei Ii y Ig lu tar inzitdi t i e plccf h o c h lo ride ( c5 H, N, E tz) ,, H,PtC 16, i s o b tai t i edin yellowish.red crystals which meit at 179".Secondary amines yieldtetra-substituted glutarimidines ; neither the free bases nor the hydro-chlorides could be obtained in a pure state.Tetramethy lglutarinaidim pl(~tinoc7doi+I~le,is deposited in dark-red, cubical crystals which darken a t 190". andmelt at 810" with decourposition. The corresponding tetrethyl com-pound crystallises in long, dark red needles, melting at 141". T'hetetncpropyl derivative forms reddish-yellow crystals meltirlg at I;$".D i byo n i o ~ e t i * a p u p y 1 y lut arint i d ine h y drob t-o ,n ide,is prepared by the action of bromine on the hydrochloride, andcrystallises in long, reddish-yellow needles which melt a t 86", and arevery sparingly soluble i n water.IMIDO-ETHERS OF HYDROXYPBOPIONI'rHILE AND PHENYI,HYDRoxY,~cETo-NITRILE.---The meth!yZ and ethyl ethers of hydroxypropiruide a r e veryunstable ; the hydrochloride of t h e prcyyl efher,0HGHMe.C (NH)OPra, HCI,forms long, colourless needles which melt a t 68--CY0 with decomposiORGANIC CHE:NISI'HP.63tion. The corrtsponding n;rn!yZ derivative is deposited in slenderneetiles melting a t 69". By the action of alcoltolic ammonia, h y d ~ o a y -ympamidiTze Iy7yoch7oride, OH*CHMeC(Pu' H).NH?,HCI, i s formed,c*rpstallising from alcohol in flat needles wbich niplt at 271".Thenitrate softens at, 78", and melts a t 84'.Uimetli y llncfninidiize Iiyrlrorhlo~ide, OH-CHMe*C(S Me)*NHMe,HCI,is prepai*rd hy tlhe action of methylamine on the iinido-am) 1 ether,and is deposited in colourless, rhombi(: crystals, melting a t 21.5".Attempts t o prepare 511 ai;ynimetricsl dimetliyl derivative by theaction of dime t1i yla mine wwe uni;n cceqs Eul.L)7:(Ice:ylpheiz~ll/beta?i/~, 7ine, OAc*CH Ph. C (KH).N Hdc, is obtainedon treating phenylhydroxyacetamidine with acetic anhydride andsodium acelate, and melts a t 210".Hy dror y he i i z 7~ ZnLe t h f j lh y dro. cyp yyirnid i 11 e,is fc)rm3(1 on mixing phenSlhyclroxyacet~midine, ethyl acetoacetate,and sodium hydroxide in molecular pi-oporfion : i t crjstallises frornamyl alwhol in long needles wllich melt a t 2;6', a,lld are sparinwl .y soluble i n water, alcohol, ether, 01' benzene, but rc:idi!y dissolve 111dilute alcoliol, alkalis, and acids.The hytll*ochl ,ride crystallises inneedles melting at 217- with pyevious softening atl 212". The picrateforms slender. vellow needles melting a t 175". The silzer salt is v wliite and sparingly soluLle.The cx.cetyl derivative, OAc*CHPh.~~~,(,,i>CH, -CMe is formedbJ the action of acrtic anhjdi idc ; i t meltr, a t liO", and yields a white,aitiorphous siZver salt. The picrute forms slender, yellow needles whichmelt a t 160" with decomposition ; the lqd~*ocl/Zoride melts a t 188",N=CMe The benzoyl derivative, 0Rz.C HPh-C< ,N.C(OB)>CH, is formed bythe action of bmzo;c chloride on the pyyimidine, and melts a t205-20t3".1'1 1 e hydrochloride crystal I ises fr( hm glacial ace tic acid instellate groups of small needles melting at 240". Hydro rybemyl-p l z e ~ i y l h ! ~ d ~ o x y p ~ r i ~ ~ z i d ; n e , OHSH Ph*C<:.ggg>CH, is preparedtrom the amidine and ethyl henzoylaceta te ; .it crystallises in fineneedles whicli melt a t 318", with previous softening a t 212". Hydroz>y-b en; y ldir I I e t h y I h y dq-ux!/py r iin i d in e is formed from e t hg 1 met h y 1 ace to-acetate and melts at 155". I t yirlds a white, amorphous silver salt.The acetate crystallises in stellate groups of lustrous needles, whichdecompose at 100". Hydrox~benzylmethyleth~jlhydrox~~py~~.irr~itline,C)H.CHi>h.C<KyCMe N C(0H) >CEt, from ethyl ethylacetoacetate, crystal-lises in small needles which melt a t 148-152".t?fJLoxybenzonitl-ilr:.OEt*C,H,*CN, is a yellow, viscid, bitter liquid, wliichboils a t 258", is volatile with steam, and miscible with alcohol, ether,O r light petroleum. The preparation of the pure imido-ether is amatter of some difficulty ; the nitrile is therefore treated with alcoholIMIDO-ETRERS FRO51 OWI'HO- AR'D PARA-Er~HOXYBENZOlr'I'1'ii1LE.--rtltoti4 ABSTRACTS OF C1-1EAlICXL PAPERS.aitd hydrogen chloride. and the product converted into ortho-pthomy-bcnzaonidiw e hi! clwch lot i d c , 0 E t* C6H,- C ( N H N H2, HC1, h y t h c) actio I tof a,lcoholic ammonia ; i t is deposi t d in bhoyt, colourlcss, hcsagonalcrystals melting at 21s". Oyfho-et hoxyphenylmethy lh!/d/.o:,.yl)!/"i?l"id;iLP,0 E t * c 6 H ~ * C < ~ .~ ~ ~ ~ , >CH, is formed from the amidiiie and ethylacetoacetnte, and melts a t 146".Para- etl/,oz!,b~w.zoii ityile i s depopited in long, yellow, rholnbic c r p t 31swhich melt at 69") boil a t 25S", and I-esemble t h e ortho-compound inpropcrtics ; tlte pi-epai-at~ion was not quitc pure. Pnrci-ethna*!/bcnz-iniidoet h y Z et h P r 1) y di.oih 1 o ~ i d r , 0 E t -C6H ,* C ( S H ) 0 I3 t , HC' 1 , vry s t dl isesin white needles which dpcompose on heating into ethyl chloyidc ant1~inl.a-cthoa?/benzclnz,ide, ON t,.C,H,*CO*NH, ; t'iis same compound is a l s oformed by the action of soda on thcb winidine Ir-jdrochloridc.and isdeposited i l l lone crystals melting at, 206". Paru-ethozyherizn?nidii~~'hyd~ocMo~ii?e, OEt.C',Hi*C( ISH).l\'H,.Hfl, is prepared by t h e actiniio f akoholic arnmonia OIL the crude im;do-ether, and is dcpositulfrom alcohol in long, hexag,ronal crystals meltiny at, 260". On treatingthe free b a s e with e t t-l y 1 R ce t oac e t ' i t e , p a /*a - e t li oxpphe rL y 1 11 i e f la y l Ii y d rox IJ -p y~iw~icJine, OE t C,H,* C <GN. c: > C H , is obtained , cry s tall is i 1 I g NC= klc, I from alcohol in short, white prisms which melt at 204'. The samecompound is formed by the action of ethyl acetonialonate on tltcaniidine, carbonic anhydride being eliminated. Pur.a-et~~on.~//)lLcizy2tli-?iieth~llLydi,o2!jpy).z?nic?;?Le, ~~~t*CsH,*~<y.c(OII), Tu'= cIMerc\ l f r , is prepaiwlfrom ethyl mc.thglacctoacct;~tt~, and crystallises from alcohol in smallprisms melting at 22 16".Ethyl ethylacetoacetate yields the correspond-formed from ethjl be117;~lacetoacetate, and crystallises from alcohol,i t 1 which i t is v e r j soluble, in lustrous necdles melting at 242". E'CCIYI-ethozydiphenylliyd~~o~~~p~r.imidi~ie, OE t*C6H,*C<N.C,oH)>CH, N x C P h f i'oiriethyl benzoyhcetate, crystallises from alcohol in broad needles wllic*hiuelt a t 2r4'. ~'arcc-ethoxyteniamidilze ptcl.a-ethuxyphe?zylhlldl.ory-~~?.i?iaidinec.al.box~late,i s formed by the action of ethyl oxylate on the amidine, and iscleposited from alcohol in long, white, lustrous crystals melting at..L@\.,", witti previons softelring at 275".Tlic: f w e acid crystallises fromalcohol in short needles which meit at 248" with decompositiorl.J. K. T.Compounds containing the Group C,N,O,. By A. F. HoLi,EMAN(Ber., 23, 2998--3001).-1n the hope of obtaining compounds re-lated to the dinitrosacyls (Abstr., 1889, 50), the author kiss examineORGAXIO CHENISTRT. 65t h e action of benzoic chloride on mercuric fulminate. The results are,however, riot so simple a s was expected, two crystalline compounds ofu uite a different constitution being formed. Mercuric fulminate,obtained amorcling to de Bruyn's method ( B e r . , 19, 1370)' andwell washed with water, alcohol, and ether, was allowed to remainquietly in a cool place with an equal weight of benzoic cllloride for5-7 days ; after that time, the fulminate had disappeared, and wasi*eplaced by a hard, gre-jish-white mass, On adding water to thel:t.tter, carbonic anhydride is evolved, and mercuric chloride passes intosolut!ion.The insoliible matter, after washing w i t h cold water, isextracted with hot water, wliich takes up a white, crystalline com-ponnd, free from mercury, but containing nitrogen and rriclting at107". The residue is for the most part solnble in acetic acid, andcrystallises o u t on cooling ifi beautiful needles which melt a t 197".a n d have the composition C1.',H12N203, as shown by the results of theanalysis and molecular weiglit determination by Raoul t's method. Onboiling wit$h alkalis, it is converted into bt nzoic acid, ammoilia, andcarbonic anhydride, and i t is therefore probably dibenzoylcarbamitde,but whether it is the sjnimetrical o r asjmmetrical compound has notyet been proved.' h e conipound melting a t 107" is also being moreclosely investigated, and it is hoped that the formation of these sub-stances may throw some light on the constitution of fulminic acid.By t,he action of benzoic chloride on pntaqsium fulminate, a cotn-pound was obtained which also melts at 197", but is riot identic:ilwith dibenzoylcarbamide. It appears to be a mixed anhydride ofbenzoic and fulrninuric acids. H. G. C.Compounds of Phthalimide with Phenols. By 0. OSTERSETZER(Monatsh., 11, 424-428) .-The author has prepared the so called'. resorcinolph thalimidesulphonic acid " of Eeese (German PatentNo.44,268, 1887) by the action of sulphnric acid on i~ mixture ofphthalimide (1 mol.) and resorciiiol ( 2 mols.). The cornpound has the!'ormula C2,H130,Nd, but does apt ear to be a sulphonic acid. It yieldsu sodium derivative, C,,H12N07SKa + 7H1,0, which, whc n precipitatedfrom its aqueous solution by means of alcohol, f0rn.s dark-colouredcrystals ; and a diacetyl compound, C,,H,,O,N;S Ac,, which is solublei l l alcohol and cblorofbrm, and may be obtained as a yel'owisli-green,C I ystalline powder, by cooling a saturated solution in acetic acid.G. 7'. M.Dihydrobenxaldehyde. By A. EICHENGRUN and A. EIKRORN( 7 j e ~ . , 23, 2870-2887 ; compare Abstr., 1887, 741).-The compoundformed by the action of alkaliac carbonates on the salts of anhydro-ecgonine dibromide proves riot to be the analogue of orthobromo-cirinamene, a s stated, but is a mixture of methyl tetrahydropyridyl-rtcetyletie and dihydrobenzaldehyde ; the small quantity of bromiitt:previously found is due to the presence of unaltered anhydroecgoninedibromide.Methylamine is also formed in some quantity during thereaction.liibromanhydl.oecgonine dibroinide hydrobromide,C,NH,Me*CHBr*CHBr.COOH,KBr,Br,Br2 [Me : CH = 1 : 21,is prepared by heating anhydroecgoniue hydrochloride with 2 parts ofVOL. LX. 6 t i ABSTRACTS OF CHEMICAL PA1 ERS.bromine on the water-hatch for 3--4 hours. It crystallises in well-developed, red, rhombic prisms, which melt a t 34.5" with decom-position, and exhibit strong pleochroism.After remainining for a,few hours, the compound gives up bromine, and i t is also decomposedby dissolving in alcoliol, glacial acetic acid, or ethyl acetate. It is in-soluble in water, ether, chloroform, and light petroleum.Anhy d roecgonine dibroni id e hydro browbid elC,NH,Me.CHRr.CH B r*C 0 0 H,HBr,is obtained by the decomposition of the previous compound in a current,of stea,m ; it, is deposited from alcohol, glacial acetic acid, or water iiilong, monoclinic prisms melting a t 18i-188" with decompnsition.From dilute aqueous solution, tetragoiial double pyramids are de-posited, which contain 3 mols. H,O and melt a t 181-182" withdecomposition. On exposure t o air, these crystals become convertedinto the anhydrous niodificatinn.An?, y clroecyonine dibyomide hydrochlo ride,C,NH,Me.CHBr*CHBr*COOH,HCI,is formed by the action of silver chloride on the hydrobromide.Itcrystallises in long, monoclhiic prisms melting a t 173-1 74" with de-composition, and also in tetraqorial octahedra, which contain water ofcrystallisation and melt at 169-170". By tlie action of alkalis ovalkaline carbonates on the salts of anh-j-droecgoriine dibromide,methylamirie, carbonic anhydride, and hydrogen bromide are elimi-nated, and dihydrobenzaldehyde is obtained. If, hnwever, the actionis allowed t o proceed in the cold, several intermediate products maybe isolated.prepared by treating a salt of the dibromide with 2 parts of a satn-rated solution of potassium cai.boriate, or by the action of ammoniumhydroxide or sodium hydroxide at 0".It is extremely scluble inwater, insolnble in absolute alcohol, and cryscallises from acetone ins m a l l , cubical crystals which meltJ at about 150" with evolution ofcarboiiic anhydride. The hydrochloride is deposited from diluteaqueous solution in tetrngonal octahedra which contain 3 mols. H,O,and melt at 197-198" with decoriiposition ; the compound ciystallisesfrom alcohol, froin glacial acetlic acid, or from conceritrated aqueoiissolution in anhydrous, monoclinic prisms which melt a t 203-204"with decomposition. The hydrobromide is also dirnorphous ; theanhydrons, nionocliiiic modification melts at 179", and the tetra gcma1form melts a t 174". The azcrochZoride, C9H,,N02Br,HAuCla + 1+H,O,crystallises from water in t u f t s of long, golden-yellow needles whichmelt, a t 211" ; on exposure to air, the crystals become anhydrous andmt>lt at 215".The lactone does not yield a methyl salt ; on boiliiigwith water, carbonic anhydride is eliminated, and a cornpound of theformula C,NH7Me*C3H3(331€3Br is formed i l l very small quantity ; itcrystallises from dilute alcohol in monoclinic prisms melting at 173".C,NH,Me-CH:CH Br,is prepared by heating a glacial acetic acid solution of the lactone inw-Bromo-1-3-4-methy lte'rtr h ~ , ~ ~ o p y I - i d y l p t h y l e n e ORGANIC CHEMlS'I'HF. 67a sealed t)ube for 5 to 6 hours at 170" ; the product is poured into water,and the solution neutralised with sodium carbonate aiid extractedwi tJh ether ; on treating the ethereal solution with hydrochloricacid and auric chloride, the aurochloride is formed ; it crystallises inshort, yellow needles which melt a t 174".On boiling with water, theauric salt of met hyltetrahydropyriclylacetylerle is formed (see below).The sane base is also obtained by the fusion of the lactone, or byboiling it f o r some time with glacial acetic acid or acetic anhydride.On boiling dibromecgonine dibromide hydrobromide with aqueouspotassium carbonate, and distilling the solution in a current of steam,a yellow, oily liquid is obtained ; this is dissolved in ether and thesolution washed with hydrochloric acid ; the acid liquid is neutrnlisedwith soda and extracted with ether ; on evaporation, methy7tetmhydro-pyr'idylacety ZenP, C,NH,Me*CiCH remains as a colour~less, basic, viscidliquid.The aumchloride crystallises from dilute alcohol in brownish-yellow cubes or flat, yellow needles which melt at 177*5-178*5".CH *CH Dihydrobenzaldehyde, CH2<cH2: iH>CCHO, is formed, togetherwith the previous compound, fromwhich i t is separated in the mannerdescribed. It is best prepared by heating an aqueous solution ofanhydroec*gonir,e dibromide hydrobromide with 0.5 part of sodirmcarbonate a t 60" ; the product is distilled in a current of steam andthe distillate extracted with ether. After washing with a few dropsof hydrochloric acid, the ether is distillcd, and the residue fraction-ated in a vacuum ; the yield is 20 per cent. of the dibromide employed.Methylamine and anhydroecgonine hydrobromide are also formed.The aldehyde is obtained as a colourless oil which darkens on expo-snre to light, and has an intensely nauseous odour; i t boils at121-122" under a pr.essure of 120 mm., and is partly decomposedon distillation at ordinary pressures ; sp.gr. = 1 . ~ 2 0 2 at 14*5O,and 1*0:-27 a t 0". It forms a crystalline compound with ammonia,reduces ammoniacal silver solution and potassium permanganate solu-tion izi the cold, and also reduces Feliling's solution on warming ; itis not oxidised on exposure to air or oxygen, but becomes slowly con-verted into a resinous mass ; concentrated sulphuric acid decomposesit in the cold. The formation of the aldehyde is explained by assum-ing that hydrox\l is substituted for the bromine i n w-bromomethvl-tetrahydropyridylethylene ; the unstable group CH:CH*OH thenchanges into the more stable complex CH2*CH0, and, by the elimina-tion of methylamine, the hypothetical compoundCII<cH2*cH2> CH-O CH.CH,*CHOis formed ; this gives up the elements of water and yields dihydro-benzaldehyde.The aldehyde forms a crystalline compound on trca t-rnent with hydrogen sodium sulphite in the cold, which is readilysoluble in water, but insoluble in alcohol or ether ; on boiling withan alkaline carbonate, it is converted into benzaldehyde. Dihydm-benzylidene pherylhydrazone is prepared by the action of phenylhydr-azine on dihydrobenzaldehyde, and is deposited from alcohol in small,yellow plates melting at 127-128" ; the crystals exhibit stroiigpleochroism.Dihydyobertzoxime is obtained by the action of hydroxjl-f ; 68 AHSTRACTS OF CHEMICAL PAPEHS.arnine on the aldehyde. The oily liquid which is formed consists oftwo isomeric compounds, which may be separated by treatment withl i g h t pet,roleum (b. p. 40-50O) ; the soluble compouiid, which istermed the p-oxime, crystallises on cooling, arid melts constantly a t4-44" ; the a-hydroxirne is insoluble in light petroleum, and docsnot crystallise.Dihydmbenzoic acid, CHz<cr3 CH2'CH>C*COOH, :CH is prepared by theoxidation of the aldehyde with an ammoniacd solut,ion of silveroxide ; it is volatile with stcam. On cooling an nquvous solution, itis deposited in feathery crystals which melt at 94-95", and are morespnringly soluble i n water than benzoic acid.The compound has anngreeable odour, and reduces aminoniacal silver solution, but doe3 not1-euct with Fehling's soliltion. it is converted into beuzoic acid onstrongly heating. The siZ?,er salt readily decomposes on exposure tolight ; like the lrad salt, it is sparingly solnble in water. The salts ofhnriurn, awrrronimn, and the nLlrcr7i metal.. 1-erldily dissolve i n water,n,nd crystallise from dilute alcohol, on the addition of ether, in silky,lustrous neecllw. The copper salt is soluble in ammonia with a gi-eenco10nr9 and is deposited in green, nodular crystals. OIL treatingdihydi obenzaltlehyde with almost any otlier oxidising agent, i t eitherremains unalterecl, or is completely dec-omposed ; with potmsiumpermangnnate, i t yields benzoic acid.By A.HANTZSCII (Ber., 23, 2776---27W).--'l'he further investigationof the oximes of pai.atoly1 plienyl ketone (Abstr., 1890, 1273) hasglhown that the a-oxime may be converted into tll;e ,&coinpound simplyby heating its alcoholic solution. Tlie transfonnation is, however,very incomplete, and a large amount of the ketone is re-formed.)getter results are obtained when the oxinie is mixed with an equalweight of hydvoxj lamine hydrochloride, hot even under tliese con-ditions a rnixtureoof tfie two oximes is always obtained. As previouslymentioned, the P-oxime is only slowly and incompletely convertedinto the benzyl ether on treatmeiit with benzyl chloride ; if, how-ever, the bromifle is emplo*yed, the readion procecds much morereadily, and a purer prodact, is obtained, which, after recrystallisationfrom amyl aJcoliol, tnelts a t 51".I t also crystallises horn etheri n sleiider, silky needles, and if pure is not acted on by hot water oralcoliol, or when 1~ydi.ogeri chloride is passed into its ethereal solution.The acetyl derivati\-e of the a-oxinie has already been described byAuwers (Abstr., 1890,503). If the8-oxime is dissolved inacetic anhydr-ide a t the ordinary tetrtperature, and the solution allowed to evaporatespontaneously, fJ-ucet!/lp"~ato7!/Z phenyl ketozir),e, CPh (N*OAc)*C;H;,crystaliises out. Tlie crystals reberlible those of the a-rxjmpourid, butare somewliat more acute. I t cannot be obtained quite pure, as itreadily passes into the a-acetyl derivative in the course of theusual processes of purificatioii, especially in alcoholic solation ; ifthe latter be warmed, t h e trirnsf'ormation is almost instantaneous andcomplete.This fact, explains why Auwers (loc. cit.) was unable t oobtain the /3-oxime, for lit: adopted this method of purification, andJ. €3. T.The Stereochemical Isomerides of Pamtolyl Phenyl KetoneORGANIC CHEMISTRY. 6 !)therefore only obtained the a-compound. Phenyl isocyanate actson Loth oximes, b u t with formation of one and the same additivecoinp~uiid, correspolrcling with the a-oxime and melting a t 180'. '1'11pisotnei-ic xcetyl det*ivatives and plienyl isocyanate addl tive conipoutitlsof par~Lbroniobeiizopirenone are much more stable than the above ;this, according to the author, is probably due to the influence oftlie methyl group.Constitution of Cumenylpropionic Acid.By 0. T;liIDaI.s ?i(Ber., 23, W i 6 - :3080 ; coinpare Ahstr , 1889).--o,-tl2(,I,,.o?t~ocuinelz!,I-UCUJZ~C acid, CHILIL.,.C,H,I~~.*C'H:CEI.G'OOH [CH:CHn/Ie:Er= 1 : '2:4],is prepared from the cqrresponding amidc-acid, but co~iltl not beobtained in r2 pure condition ; it crystallises flom dilute acetic. acid i i ilong, colourless needles melting at 154". On iduction with 113 driodic:acid and ph ospli oms, it yields orth oh ro/i/ oc 1 1 menylpwpic~ 11 ic ucitl,CHMe,.CsH,Rr.CH2.CK,.COOH, crjstiillisitig from light petroleum inlong, slendthr needles which melt at2 tp)3*50, a n d yield cunienyl propi-onic acid by the action of sodium ttm;~1gam.Crthocl~loi~oc~~rt~rnylccc~q~lic acid, CHhle,.C,H,Cl.CH:CH.COOH, crjs-tsllises from acetic acid in lusttvns plates nielting at 133-134".Hy the action of sorlinm iiitri te and 1~ydrol)roniic acid on amitloprop? I-ciniiamic acid, a conipoiiiid is obtained which melts at 128", arid oniwlnction with phospliorus ancl 11) driodic acid, yields tlie n b o ~ c:tlcscribed orthobromociinieiiSlpropionic acid (111.p. Z5.5"). An investi-gation of the orthnn~ido~~i~opylcinilamic acid showed it to bc a mixturtlof two-thirds o ~ t h ; ~ m i d o c u r ~ ~ c i ~ ~ l a c ~ i ~ ~ l i c acid (m. p. 161') mid oiie-third metamit-locnmenSlacr$lic acid. It follows, therefore, t h a t theso-called orthonitropropylcinnamic: acid is also a mixture of ortlro-atid rnPta-nitrocunienylaci.ylic acids.Cnnienylpropionic acid (ni. 13.i5.59") is thus finally proved to be an isopropyl derih ative.a. G. C.J. B. T.Perkin's Reaction. By 0. RI:WFF.ZT (Goazetfn, 20, 158-1 6 2 ) .--The conde~isation of alclehycles w i t h organic sodiuni >&Its is geiirr,~llysuirposed to take place without the acetic anhyclricle nsed taking ai1.ypart in tlie reactlion. The author finds that iu his syntllesis of' phenxl-citiiiainenj 1aci.ylic acid (Xbstr., 1S8??, 1137) from cinnam,zltlehyttc~,sodium phenylacetate ancl acetic anhydride, iE the 1-eaction is inter-rn))ted as soon as the solution l ~ n s been r;lised 10 the lmiling point, t i t i t ltlie product is thrown into cold watei..a n insoluble oil rcrriains, whi1.hlias the composition of ciwnu/i?yZidene ditrcetctfc, CHPh:CH*CH(OAc),,whilst the aqueous solution coiitttins tlie whole of tlie phenj-laceticacaitl used. l'he acerate crjstallises from alcoliol in large, colourlesh,nacreous plates, and melts a t 84-85". It is ciecorrlposed into cinnarti-alclehycle and acetic acid by distillatlion i t 1 steam, 0 x 8 by boiling w i t halkaline carbonates. It takes up 2 atoms of bromiiie forming anunstable compound, which, on steam distillatioii, yields Zincke's phenyl-/+hromacraldehyde (Ahstr., 1884, 1343). If left for a long time, i t i.;couvertecl into a yellow syrup, which smel Is of cinnniiialdehyde ant1acetic acid. 'l'he foregoiiig experinletit renders i t probable t h a t thefirst step in Perkin's reactioll is the foriiratioii of an acetate of tliealdehydic radicle.S. B. A. A70 ABSTRACT8 OF CHEMICAL PAPERS.Methylresorcinolphthaloylic Acid. By E. Q c ENDA (Gazzettn,20, 127--13~~.--~ethylr~eso~cinol~hthaloylic acid,COOH*CsH4*CO*C6H3( OH)*OMe,is obtained like the corresponding aniso'il and pheneto'il derivatives(see Grande, Abstr., 1890, 1128). A mixture of phthalic anhydride( I 2 grams) , dimethylresorcinol (24 grams), and alurninium chloride(16 grams) is heated for about three hours on the water-bath, theproduct thrown into excess of cold water, and the precipitated acidextracted with ammonium carbonate, and reprecipitated with hydro-chloric acid. It is then purified by repeated crystallisation fromtoluene and from water.l h e pure acid crystallises in light, colour-less scales, dissolves sparingly in boiling water, but readily in hottoluene and in ether. It melts at 164--165", forming a clea,r,yellom is'i-red liquid, and a t a liiglier temperature dense, white, irri-tating fumes are evolved. A neutral solution of the ammonium saltgives precipitates with soluble salts of copper, zinc, mercury, lead, &c.The silver salt, Cl5Hl1O5Ag., is obtained as a heavy, white precipitate,which is soon blackened and decomposed hy light. The barium saltcl-ystallises in anhydrous, yellowish nodules. S. B. A. A.Gallic Acid, Tannin, and Oak Tannic Acids. By C. BOTTINGICR(Anr/alen, 259, 132-136) .--The author's attempts to prepare cyan-hydrins and oximes from gallic acid and various tannins were unsuc-cessful, and 110 definite results were obtained.Action of Phenylhydrazine on Tannin Extracts.I3;y C.BOTTINGER (Annalerh, 259, 125-l32).--The true tannins combinewith phenylhydrazine, yielding amorphous compounds, which havenot been prepared in a pure condition, and which consequently havenot been analysed ; in their behaviour with acids, they show a certainresemblance to the osazones of the sugars.On boiling an aqueous solution of a tannin extract with phenyl-hydrazine, carbonic anyhydride is evolved, probably also nitrogen,and the phenylhydrazine is partially decomposed into ammoriia antiazobenzene, so that ammonia derivatives, as well as phenylhydrazinederivatives of the tannins, are formed.The following extracts wereexamined :-Sumach, vallonia, algarobilla, divi-divi, oak-wood, oak-h r k , and pine-bark.Manufacture of Decolorised Tannins : Zinc Tannate. By A.VILLON (Bull. SOC. Chim. [ 3 ] , 3, 784--786).-The liquor obtained byexhalisting the crude material in the ordinary way is cooled at 2" forhalf an hour, and after filtering off extractives and tannins insoluble inthe cold, 0.5 per cent. of zinc sulpliate is added. The tannin of the liquoris now titrated, and for each kilo. present in the s0lution~2.5 kilos.of zincsulphate, dissolved in 12.5 Iitres of water, is added, and the whole isplaced in a closed vat, furnished with a mechanical stirrer and steamcoil, into which is passed the ammonia resulting from the decompo-sition of 2.5 kilos.of animoniuni sulphate per kilo. of tannin present.After separation by a filter press of the precipitated zinc tannate, i tis decomposed by dilute sulphuric acid, and to the liq.ior bariumF. S. K.F. s. KOliQANIC CHEMISTRY. 71sulphide is Rdcled, uritil the zinc sulphate is completely precipitated aszinc sulphide and barium sulphate. On filtration, a liquor containing'L0-:30 per cent. of tannin, and almost free from colour, is obtained.1 he process is economical, siuce all the bye-products are capable ofDiphenylsuccinic Acids. By R. ANSCH~~TZ and P. BENDIX(AnnaZen, 259, 61-100) .-Diphenylmaleic: anhydride, prepared frombenzyl cyanide by Reinier's method (Abstr., 1886, 169), separatesfrotn ether in well-defiued rhombic crystals, a : b : c =0.69287 : 1 : 1.35838, boils a t 236" (15 mm.), and is readily solublein chloroform and benzene, but only spariiigly in alcohol and ether.9ttempts to convert this anhydride inlo dipheiiylf umaric acid wereunsuccessful ; when it is treated with hydrogen chloride in metliyl orethyl alcoholic solutiou, i t is partially converted into an alkyl saltidentical with tliat obtained from the silver salt' of diphenylmale'icacid, but a considerable quantity of the anhydride remains unchanged.DiphenyZrnaleGiiiZ.C,?H,,NO,, is easily obtained by heating thepreceding compouiid with aniline a t 120" ; it crystallises from alcc-holic chloroform in slender needles, melts at 174-175", and boils at2 9 3 O (14 mm.). On hydrolysis witti boiling potash, it is decomposedinto diphenylmaleic acid and aniline; the same change is broughtabout by boiling hydrochloric wid, but only very slowly.Theseexperiments show that diphenylmnleic anhydride is not converted into.diphenylfumaric acid under conditions which lead to the transforma-tion of maleic into fumaric acid ; it is douhtful whether the compounddescribed by hugheimer (hbstr.. 1886, 1698) as diplienylfuniaric acidis in reality this substance.Both a- and /3-diphenylsuccinic acids are formed when diphenyl-rnaleic anhydride is reduced with sodium amalgam in alkaline soh-tion, as described by Reimer (Zoc. c i t . ) , or with zinc and hydwchloncacid in alcoliolic solution ; the relative yield of the /%acid is greaterwhen tlie reduction is carried out with zinc and hydrochloric acid.The two acids are most conveniently separated by means of theirbarium salts.Barium a-diphenylsuccin~te, C16Hlz04Ba + 2H20, is obtained byprecipitating a solution of the ammonium salt with bariuni chloride ;it is soluble in 312 parts of water a t 17-18".A sparingly soluble>,alt containing 4 mols. of water is formed when barium hydroxide isadded to a dilute solution of the ammonium salt.Barium /3-diphenylsuccinate, Cl6Hl,,O4Ba + 7Hz0, separates in well-defined crystnls when a solution of the barium salt ot' the /?-acid isevaporated a t 100" ; it is soluble in 4.742 parts of water at the ordi-nary tempeisature.Both a- and /3-diphenylsnccinic acid form colourless silver salts,which, when dried a t loo", have the composition Cl6H~,O4Ag, ; whenflrese silver salts are treated with ethyl iodide a t IOU", they are con-verted into ethyl salts, identical with the compounds obtained byHeiiner (Zoc.cit.), by treating the corresponding acids with alcoholand sulphuric acid. The ethyl salt of the a-acid melts a t 34", that ofthe p-auid a t 140-141".1 1easy regeneration. T. G. N72 ABSTRACTS OF CEEBlICAL PAPERS.a-Diphenylsuccinic acid dissolves in cold acetic chloride with eroln-tion of hydrogen chloride, and, after evaporating the solution a t IOO",there remains an oily mixture of the anhydrides of the a- and fi-acicls,\jrhich gradually becomes crystalline ; this product separates fromether in well-defined crystals, melts a t 115--116", and boils at 240"(about 15 mm.), the dist,illate gradually solidifying.When boiledwith water, it yields about 96.5 per cent. of the a-acid, and 3.5 percent. of tlie ,&acid, even when in its preparation from t h e acid thetemperature is kept below 36' throughout the various operations ;when treated with potash, i t gives 85.8 per cent. of the a-rlcid, aiid14.8 per cent. of tlie /%acid. The same mixture of anhydrides iso't)t,ained from the barium salt of the a-acid in like manner.,!I-Diphenylsuccinic acid is not acted on by acetic chloride in thecod, but a t 100," i t yields a mixture of anhydrides which has thesame melting point and other physical properties a s that obtainedfrom the a-acid, but which, on boiling with water, gives '74.81 per ceii t.tjf the a-acid, and 18.5 to 26.1 per cent.of tlie Lj-acid. When silvei.or barium ~-diphenylsuccinate is treated with acetic chloride, amixture of the anliydrides is formed which melts a t L I O - l l l o , andon boiling with water, gives 65-70 per cent. of the P-acid, and35-40 per cent. of the a-acid.The mixture of anhydrides obtained by distilling a- or [j-diphenjl-succinic acid under reduced pressure (14 rnm.) melts a t 112-11:3"and in its behaviour with solvents, &c , it resembles that produced b jtreating the acids with acetic chloride ; when boiled with water, ityields about 90 per ceut. of the a-acid, and 10 per cent. of tbe /3-corn-pound.When the a-acid is heated ati temperatures ranging from 150 to 185",about 50 per cent.is converted into anhydride, and allout 50 per cent.into the /$acid ; tbe P-acid, on the other hand, does not lose waterbelow 185". These experiments prove the existence of two isomericdiphenylsuccinic anhydrides, but owing to the great similarity i nproperties, the two compounds cannot be separated ; the existence oftwo anhydrides proves, however, that t,he isomerism of the two acidscannot be explained by assuming, as Roser has done, that they havethe constitution I > and I respectively,and it seems more probable that the relationship between theni is thesame as th;tt which exists between the two bydrobenzo'ins.UiplLen?ll.Euccinanil, C22HliN02, is obtained when the anhydride, pix-pared either irom a- 01' P-diphenylsuccinic acid by means of aceticchloride, is lieated with aniline ; it can also be obtained by reduciiigdiphenylmaleanil.It crystallises from hot benzene in colonrlessneedles melting a t 0,26-28i0, and from glacial acetic acid in largerneedles melting at 230-231".Diphen ylsuccinnnilic acid, C22H19N03, is produced when the pre-ceding cotiipouiid is boiled with barium hydroxide ; i t crystallises fromdilute alcohol in colourless needles, and melts a t 220". I t is notchanged by warm concentrated alcoholic potash, but it is recon-verted into the ariil by glacial acetic acid, hjdrogen chloi,irie, andalcoholic sulphuric acid.CH P h. C (0 H) CHPh-COOHCHPh- GO CHPh*COOHF. S. KORGANIC CHEMISTRY. 73Crystallographic Proof of the Identity of Pyranilpyro'in-lactone and Citraconanil.By R,. ANsCiiijTZ ( J:w., 23, 2979-2981 ;see also Abstr., 1890, ll02).-By the slow evaporation of the etherealsolution of citraconanil obtained in different ways, the author hassucceeded in obtaining i t iu well developed crysta.ls. Hintze andJennsen have exarniried cryst8allogt-aphically preparations obtained( I ) from ,'3-anilidopyrotartaric acid (R'eissert's pyranilpyroi'nlrtctone),(2) from aniline and citraconic acid, (3) from pseudoitacoiianilic acid.The nieasnreirients show conclusively that the substances obtainedby all three methods are identical, the crystals belonging to themonosymmetric system ( a : b : c = 2.75i5 : 1 : 1.8152, /3 = -51" 17').The optical properties of all three were also found to be almostidentical, three corresponding plates giving the following numbers :-No.1. No. 2. No. 3.2Ha.. .. .. .. 11" 6' 11" 22' 11" 35'H. G. C.Paranitro-orthotoluenesulphonic Acid. By J. HAUSSER (BUZZ.SOC. C'him. [ 3 ] , 3, 797-799) .-Paranitrotoluene (200 grams) is slowlyadded t o sinlphuric acid containing 44 per cent. sulphuric anhydride(260 grams), the energetic reaction being modified by cooling withice, and tben completed by heating the mixture at 150". Theproduct is added to water (1500 grams), aiid after removing theexcess of sulphuric acid by calcium cai*boriate, the solution is con-centmted until the sulplionic acid cryst,~llises out, the yield being64 per cent. The autbor confirms Jennsen's researches (tois Journal,1874, 4791, and finds that the acid decomposes the sulphatcs of zincand copper forming uitrosulphonates and liberating sulphuric acid.Nitrotoluenemetasulphonic acid, which may be prepared in a similarmanner, is an analogous substance.Iodometaxylenesulphonic Acid.By C. RAUCH ( B e y . , 23,3117- 3 11 9).--The iodometaxylene~~ilphorlic acid prepared by Ham-merlich (Abstr., 1890, 1106) has the fomiula [Mez : I : SO,*H =1 : 3 : 4 : 61, sitice, on fnsion with potash, it yields a dihydroxy-deriva-tive which melts a t 146" and is identical with the compound obtainedby Wischin (compare following abstract). The sulphonamide, pre-piired after elirriiriation o f the iodine, melts at 137", and therefore hasthe formula [Me, : SOzNH2 = 1 : 3 : 41.Metaxylenedisnlphonic Acid.By R. WISCHIN (Ber., 23,3113-311 7).-ill~taxyZenedisuZ~lzon~c ac;'d, [Me,: (HSO,), = 1 : 3 : 2:4],is prepared by heating metaxylene with 4 parts of fumingsnlphuric acid a t 150" ; on pouring into water, small crystals sepa-rate which cannot be purified by crystallisation from dilute sulphuricacid. The disuZphochZoyide crystallises from ether. in needles meltinga t 129". The constitution of the compound is proved hy the produc-tion of dichlorometaxylene (b. p. 228"), on heating with I'hosphoruspentachloride a t 180". The sodium salt is readily soluble inwater. On oxidation with potassium permanganate, it yields adisuZp?iisophfhaZic acid, which is deposited from alcohol in small,T. G. N.J. B. T74 ABSTRAOTS OF GHERIIOAL PM'EHS.granular crystals melting a t 250'.The barium sulphonate crystallisesfrom water in plates. The sulplmnawzide is deposited from water iiisilky, lustrous needles which melt a t 249".Dihydroxyxylene [Me2: (OH), = 1 : 3 : 2 : 41 is obtained by fusingthe sulphochloride with potassium hydroxide, and may be purified hysublimation ; it is deposited in slender, white needles melting at 146",and is very readily soluble in water, alcohol, or ether; an intenseviolet colour is produced with ferric chloride; on heating withphthalic anhydride and dissolving the product in soda, a green fluor-escence is observed. Disu~l~airiine-iso~hthulic anhydride,is prepared by heating the disulphonamide with potassium per-manganate solution, and decomposing the resultiug potassium saltM ith sulphuric acid ; the anhydride crystallises from alcohol, melts at225", is very sparingly soluble in water, and exceedingly bitter to tlietaste.Mttaxylenedisulp'23~onethyZaniide7 from tho disulphochloride andethylstmine, crystallises from water in silky, lustrous ueedles whichmelt at 135".~ r i , ~ , ~ ~ x y l r r ~ e d i s u ~ p h o n i c acid [Mez : Br : (€€SOs), = 1 : 3 : 4 : 2 : 61is prepared by the action of fuming sulphuric acid on bromo-xylcne[Me, : Br = 1 : 3 : 41 ; both the acid and its salts crystallise withgreat difficulty.The sulphochloride is obtained from ether in long,white crybtals melting at 160". 'I'he su@horLamids is deposited fromwater in needles melting at 265".Bromodihydroxysylene, obtained by the fusion of the acid withpotassium hydroxide, forms white crystals, melts at 126', and givesa violet colour with ferric chloride.Chlo~.o-xyleneclisul~holLic acid resembles tho bromo-derivative i nproperties and constitution.The sulphocl~luride crystallises fromether in white needles melting a t 155". Ttie sulphowamide is deposit et-lfrom water in silky, lustrous needles which melt a t 270".Chlorodihydroxyxylene is obtained by sublimation in white needleswhich melt a t 10tjo, and give a violet colour with ferric chloride.J. B. T.Action of Thionyl Chloride on Secondary AromaticAmines. By A. JUICHAELIS and E. G o n c ~ a u x (Hey., 23,3019--3023 ;compare Abstr., 1890, 610).-~'hiclnyZ~iethyZuniline, SO(C&H1*NI~Me)2,is prepared by adding an ethereal solution of thioriyl chloride to amixture of aluminium chloride and methylaniline, dissolved in thesame medium ; the solution is well cooled and poured into cold water,the ether separated, and the aqueous solution filtered and treatedwith excess of soda ; the precipitate thus obtained is boiled with alco-hol, and the alcohol evaporated ; the residue is dissolved in chloroform,and, on adding light petroleum, it crystallises out in stellate groupsof colourless needles which melt at 154" and readily assume a blue tint.RiitrosothionyZnaet7yla~~ilane, SO( CsH,*NO&f e-NO),, is obtained by theaction of sodium nitrite and hydrochloric acid on the preceding comORGANIC CHEMIS'I'RY.75pound, and is deposited from alcohol in coloL~r1css needles melting at17l0.IThiornethyZaniZine, S ( CsH,NHMe),, is forrned by the reduction of thethionyl derivative with sodiurii in alcoholic solution ; it cr~stallisesfrom a mixture of ether and light petroleum in long, yellow, trans-parent needles which melt a t 60°, and are readily soluble in chloroform,ether, or alcohol.Nitrosotlrio?nethyZa~~iZine, S ( C6H1*NRlle.NO),, fromsodium nitrite and thiomethylaniline, crystallises in yellow, lustrousplates ~ h i c h melt a t 133d, and are very sparingly soluble in coldalcohol. J. B. T.New Synthesis of Indigo. By 1;. LEDERER (J. yr. Chem.[ a ] , 42, 383).-2 grams of phenylglycocine are stirred iuto 8-10grams of fused sodium hydroxide, itnd the fusion maintained untilthe colour becomes pure orange, wllen *he reaction is over.Theriielt is dissolved in much water, when pnre indigo-blue is aepa-rated. A. G. B.Synthesis of Indigo and Allied Dyes. By K. HEUMANK (Ber.,23, ;~04S-:~0$5).-Phenylqlycocine is heated i n absence of air with2 parts of potassium hydroxide a t 260" ; the fused niass becomesbrownish-orange; i t is allowed to cool, dissolved in water, and astream of air drawn through the solution ; an immediate precipitationof indigo occurs. Care must be taken not to continue tthe fusion toolong, or decomposition takes place ; small portions are therefore with-drawn from time to time and dbsolved in water, the heating beingimmediately stopped as soon as the formation of indigo is observed.Sodium hydroxide may be substituted for potassium hydroxide, butthe reaction takes place a t a much higher temperature.Kxperirnentswith other dehydrating agents were unsuccessful. The reaction mayhe explained by assuming that, by the e!irnination of water fromphenylglgcocine, pseudindioxyl, C6H4<NH> co CH,, is formed, andthat this yields indigo on oxidation. J. B. T.Desmotropy in Phenols. By J. HERZIG and S. ZEISEL (Moqzd~h.,11, 413-420; compare Abstr., 1888, 823 ; 1889, 2417 and 966). -Onheating diresorcinol (1 mol.) in alcoliolic solution with potash(8 11101s.) and ethyl iodide (8 mols.) in a reflux apparatus for severalhours, the authors obtained, as the chief producf, a viscid, brownishoil, insoluble in potash. Wheii shaken with cold alcohol, a portion oft h i s substance dissolves, and may be obtained on evaporation of thesolvent.After several recrystallisations from hot alcohol, it isobtained in scales melting coiistaritly a t 90-92", and is shown byanalysis to be ethg Zdiresorciwyl tetrethyl ether, C,,H,Et(OEt),. Onheating this ccmpound with hydriodio acid, ethyldiresorcinoZ,C12H513t(OH)4, is formed, but, owing to its instability, it cannot beobtained in a pure state. Y'etracetyZeth yZdiresoi-ci?LoZ, C12H,E tAcp, isreadily prepared by heating the product of the action of hydriodicacid 011 ethyldiresorcinyl tetrethyl ether with acetic onhyodride. Itcrystallises from alcohol in needles which melt a t 135-138 76 ABSTRACTS OF CHEMICAL PAPERS.That portion of the oil which is insoluble in alcohol consists ofdiresurcinyl tetmthyZ elhey, C,,H,(OEt),, and crystallises from hotalcohol i n scales which melt at 112-114" (compare Pukall, Abstr.,These results show that in diresorciuol two hydroxyl groups of abenzene nucleus occupy, relatively to each other, the meta-position,and that ethylation is induced by the mobility of their hydrogenatoms, i n the same way as the authors have previously shown (loc.d.) obtains in the case of other metaphenols.Diphenyldiethylene Derivatives.By 0. REHUFFAT (Gazzerfa,20, 154-157) .-L>~p~2enyEdiefhykne, CHPh:CH.CH:CHPh, synthe-tically prepared by the author (Abstr., 1883, 11 371, crystallises fromalcohol i n large, colourless, micaceous plates, melts a t 147-148", ariddistils uiialtered at, 2.50". I t is sparingly soluble in ether, but readilyin alcohol and carbon bisulphide.T~tl.abromodiphenyIdiethylene, prepared by treating an etherealsolution of the hydrocarbou with excess of an ethereal solution ofbroriiiiie, crystallises in white scales which are unaffected bg pro-longed exposure to air and light ; it blackens :tnd melts a t 230".The dib r-onzo-derivative, C HPh BrCHBi-CKCHPh, is prepared- bymixing the theoretical quantities of its constituents in etherealsolution in the cold, and allowirig t h e mixture t o I-emain. It formstufts of colourless, acicular crystals, and melts a t 147-148", decom-posing if not quite pure.It combines with some difficulty with twoatorns of' bromine forming the tetrabrominated derivative.When a solution of diphenyldiethylene in carbon bisulphide istreatsci with a solution of bromine in the same solvent in the propor-tion required for the formation of a tetrabromide, the liquid istlecolorised after some time, a small quantity of the hydrocarbonbeing deposited ; on distillation, the dibromo-derivative passes orertogether with a brominated compound, intermediate in compositionbetween the di- and tetra-bromo-derivatives.This substance crystal-lises from carbon bisulpliide in long prisms, and melts a t 158", pre-viously softening a t 190".Synthesis of Benzylcinnamic Acid. B y A. OGLIALORO (Gnzzetta,20, 162-164) .-Benzylcinnarnic Acid, C12H1402.-A mixture of sodiumhydrocirinamate and benzaldehyde in molecular proport,ion is heatedwith a'n excess of acetic anhydride for six hours a t 16C0, and theunaltered anhydride and the phenylpropionic acid are then removedby treating the product with ether and h o t water respectively.Theresidue, after being purified by extraction with boiling light petro-leum, crystdlises from absolute alcohol in large, white needles whichmelt a t 158". The iriost probable constitution for this compound isthat of a benzylcinnauic acid, CHPh:C (CH,Ph)*COOH.1887,1360-66 1).G. T. M.S . B. A. A.8. B. A. A.Naphthyl Sulphides. By F. KRAFF'I' and E. B o m ~ s o i s (Rer., 23,3045-3049 ; compare Abstr., 1890, 13 11) .--act- Dinaphthyl sulpliidemay be prepared from hromonaphthalene and the lead salt ofa-nrtphthyl mercaptitri i n the manner previously described, PhenylORGANIC CHEMISTRY.7 7a-nnphfhyl sulphidp, CloH7*SPh, is obtained in the same wayby heating a-bi-ornonaphthalene with the lead salt of phenyl mer-captan, a t 240" f w 2-3 hours ; it crystallises from alcohol in hard,coloiirless, lustrous prisms which melt at 41*5", and boil at 218" u1idc.ra pressure of 14 mm. The yield is over $1 per cent. of the lead salternployed ; on oxidation, the corr: sponding sulphone is obtained.Phemjl-[d-naphthyl sulplride, CIOH7.S1Jh, is tormed, together withdiphenyl sulphide and P/j-dinaphthyl sulphide, from monobromo-l~enzene and t'he lend salt of 6-naphthyl mereaptan ; it c r ~ s t a ~ l l i ~ e sfrom alcohol i n steliate groups of small, white needles, or in lustrousplates, which melt, a t 51*5", and boil a t 224" under a pressure of14 mm.The yield is 25 per cent. of theory, and the correspondingsulphone is obtained on oxidation. J. B. T.Action of Aromatic Bases on Naphthol Violet. I3y R. HIRSCHaiid El, KATXKHOFF (Ber., 23, 2992--2994).-A new colouring matterrelated to naphthol violet has recently been described lty Witt(Abstr., 1890, 1307), who regards it as being formed simply by theaction of heat 011 tlie last-named colouring matter. The autkiors h:tdalso previously observed that, under certain circumstances, prepara-tions of naphthol violet have an unusually blue shade. Accordingto present ideas, the colouring matkei. has the coristitutionC,,H,< >C,H,.NMe2,HC1, and is formed from nitrosodimethyl-aniline and p-naphthol according to the equationN0The h-j-drogen thus set free reduces anot'her portion of nitrosodi-methylaniline to amidodimethylaniline, and the authors regarded it asprobable that the blue colouring matter was formed by the furtheraction of the latter on naphthol violet, and they, i n fact, succeeded inthus obtaining a colouring matter identical in every respect with thatdescribed by Witt.I n place of amidodimethylaniline, other aromaticbases, and even ammonia, may be employed, well-defined colonringmatters being thus obtained. The compound from aniline cr~stallisesin brown needles which melt a t 256" and dissolvc in concentratedstilphuric acid with a violet coloration. The base from paratoluidineresembles it vevy closely, but.melts at 250", whilst that from a-naph-thy lamine has a yellowish-brown colour in sulphuric acid solution.The yield does not, a s a rule, amount to more than 50 per cent.The constitution of these colouring matters has not yet been ascer-tained, but they are probably formed in a similar manner to thequinoneanilides. H. G . C.Naphthoic Acids. By d. G. EKSTRBND ( J . pr. Chem. [2], 42,273-4043 compare Abstr., 1889, 52, 352).-This paper is largely areprint of what bas already appeared. The nitro-p-naphthoic ac!ds arebesf obtained as follows :-/3-Nnphthoic acid is gently warmed withnitric acid of sp.gr. 1.42 (two parts) until red fumes cease to appear, andthe product is washed with water, dissolved in soda, and the sodium sal78 ABSTRACTS OF' GHEMICAL PAPERS.crystallised ; the acids are then liberated from the recrystallised saltsby hydrochloric acid, dissolved in alcohol, and converted into theirethyl salts by dry hydrogen chloride ; the ethyl salts are separated bylight petroleum, in which that of the acid of m.p. 288" is sparinglysoluble, the residue from the mother liqiior being recrystallispd frombenzene, and the mixed tables (ethyl salt of acid OE m. p. 288") andneedles (ethyl salt of acid of m. p. 293") separated by hand.Nitro-p-naphthoic acid (m. p. 293", Abstr., 1885, 905) dissolves in660 parts of alcohol a t the ordinary temperatiire. The bat-ium saltcrystallises with 4 mols. H,O ; the calcium salt (with 34 mnls. H,O)dissolves in 930 parts of water a t the ordin3ry temperature.When t,heacid is oxidised by potassium permanganate, a non-nitrogenons acidis obtained which ci+ystallises in slender needles and melts a t 200" ; i thas not been identified, bnt its formation is a strong indicationthat the nitro- and carboxyl-groups are not in the same benzmenucleus. Nitro-P-naph thoic acid gives no dinitronaphthalene whentreated with nitric acid, whereas ni tro-a-naphthoic acid does. Whenamido-p-naphthoic acid (m. p. 232", Zoc. cit.) is heated with bariumoxide, a-naphthyhniine is ohtained ; thus the constitution of thenitro- acid is [NO, : COOH = 1' : 2 OY 4' : 2). Acetarnido-P-naphthoic acid crystallises in small tables melting a t 291".By the action of chlorine on amido-/3-naphthoic acid (m. p. 232")in hot glacial acetic acid in the presence of iodine, a substance in-soluble in water and alcohol is obtained, which crystallises fromglacial acetic acid in orange needles melting with inturiiescence a t235"; the analysis of this substance agrees fairly well with theformula OH-C,,H,Cl,*COOH ; if the treatment with chlorine is ccjn-tinned, the prodnct crystallises in pale-red needles which melt withintumescence a t 238".By chlorinating the amido-acid in the cold, andtreating the product with sulphurous anliydride, a substance contail)-ing less chloriiie is obtained ; it cr-ystallises in brownish tables whichmelt about 234"; when further chlorinated, it melts a t 237" ; i t sformula is uncertain, but a calcium salt (with 5 mols. H,O) has beenobtained in yellow needles.Two other chlorine derivatives, tht. onecrpstaJlising in orange-red tables and melting a t 220°, and the other,a brick-red powder meltirig at 277", have also been obtainrd.Dinitro-P-naphthoic acid (m. p. 248", Abstr., 1884, 1361) dissolvesin 61 parts of alcohol at the ordinary temperature. The am?nonium(with 1 mol. H,O), sodium (whh 4 mols. H20), barium (with 8 mols.H,O), and calcium (with 5 mols. H20) salts are described. Bytreating this acid with a large excess of hydr.Jgen sulphide in ammo-niacal solution, a dark-brown, infusible powder is obtained ; it cannotbe freed from sulphur, but it appears to be a diimido-p-naphthoicacid, COOH.C,,H,(NH), (compare Abstr., 1889,153 ; 1886, 948 ; 1887,373). From analogy with the dinitro-a-naphthoic acid (m.p. 2(;5"),the author ascribes the constitution [(NO,), : COOH = 1' : 1 : 2 01.4' : 4 : 21 to this acid.Diarrzido-[3-na~hthoic acid, obtained by reducing the above dinitro-acid with ferrous sulphnte in ammonia, crystallises in greenish-yellow iieedles which melt a t 2 0 2 O , and partially sublime ; the calciumsalt and the monohy&-ochlo?-icS;e, me1 ting above 285", were obtainedNitro-/I-naphthoic acid (m. p. 288, Abstr., 1895, 905) diswlves i n390 parts of xlcohol at t,he ordinary temperature. The ethyl saltmelts a t 121', not 122". The anzmonium, Farium (with 8 mols. H,O),and calcium (with 4; mols. H,O) salts are described. Oxidat>ion withpermanganate and treatment of the amido-acid with calcium oxidelead to the si-Lme conclusion as in the case of the /3-nitro-acid (weabove).Calcium amido-8-naphthoate crystallises with 4 mols. H,O,Acetami:do-P-naphthoic acid crystnl!ises in slender needles which meltat 258O ; the diacet!yl deri5afive melts a t 181". Nitrucetnwido-B-naphthoir, acid forms slender needltis melting a t 270". When theamido acid is treated with chlorine in glacial acetic acid in presenceof iodine, a product is obtained which crystallises in colourlessneedles and melt., with intumescence at 258" ; it would appear fromits formula, OH-C,,H4Cl4*C00H, to be a dichloride of a dichloroxy-/3-naphthoic acid. In another experiment, criloiirlew tables of theformula OH*C,,,H,CI,*COOH, and melting a t 237", were obtained.Dinitro-P-naphthoic Rcid (m.p. 22tj0, Abst'r., 1884, 1361) dissolvesin 57 parts of alcohol a t the ordinary temperature ; the amnaoniumsalt (with 1 mol. H,O) dissolves in 285 parts, and the calcium sult(with 4 mols. H,O) in 1740 pnrts of watey a t the ordinary tempern,-ture ; the barium salt (with 6 mols. B,O) is described.Nifranaido-B-n~~hthoic w i d is ohtained by treating an arnrnoniticxlsoliltion of the dinitro-acid (m. p. 226') with hydrogen sulphide,adding a c d c acid, digesting the precipitate with hydrochloric acid,and decomposing the solution thus obtained by ammonia ; it €armsshellate needles and melts a t 235" ; its hydrochloride forms slender,red needles.Diamido-/3-rLaphthoic acid is obtained by reducing the dinitro-acid(m. p. 226") with ferrous sulphate in ammonia; it melts about 230°,but with blackening, and forins small, six-sided crystals.Thecalcium salt (with 44 mols. H,O) arid the dihydrozhloride are de-scribed.The ethyl salt of a third nitro-acid remains in the mother liquorof the benzene solution in the preparation of the above nitro-acid(see beginning of the abstract). The nitro-P-naphthoic ocid corre-sponding with this ethyl salt crrstallises in stellate needle$ whichmelt, although not sharply, a t 285"; the ethyl salt melts a t 75".A. G. B.Dry Distillation of Terpenylic Acid. By C. AMTHOR and G.M ~ ~ L L E R ( J . p ~ . Chmn. [a], 42, 38.5-399).-By the dry distillation ofterpenplic acid, Amthor (Abstr., 1882, 44) obtained a syrupy acid,temcrjlic acid, a lactone boiling at 202 -204', and a lactone, C7HI2O2,boiling at 210-212" ; but Fittig and Kraft (Abstr., 1882,42) obtainedno lactone.100 parts of boiling ether dissolve 3.856 parts of terebic acid, andthe same quantity of cold ether dissolves 1.698 parts ; the Following istherefore a better method for separating this acid from terpenylicacid than that previoiis1.y adopted (loc.cit.) :-The mixed acids areheated to 8O--CO0, at which temperature most of the terebic acidremains unmeited, and is separated from the molten terpenylic acidby filtration through cotton-wool in a hot water funnel ; the terpenjlicThe authors have, therefore, reinvestigated the subject8 0 ABSTRACTS OF OHRMICAL PAPERS.acid is then crystallised from hot water, and again heated until mostof it is melted, when warm water is added and the solution filteredthrough cotton-m~ool ; some of the crystals which separate oncooling are then dried on a microscope slide, heated to 80-90", andexamined under the microwope for any still solid particles of terebicacid. The melting and solution in u-ater are repeated until no moreterebic acid is detected in the crystals exarniriecl in this way.Barium diterpenylate crystallises with 2 mols.H,O (Abst,r., 188.2,43), one of which is lost over sulphuric ;Icid, a8nd both at a hightemperature, although not with out^ partial decomposit>ion.The investigation of the products of the distillation of terpenylicacid was carried out on much the same lines as previously (Abstr.,1882,44) ; the acid was not perfectly dry when distilled, still contain-ing its water of crystallisation (1 mol.).The products isolated weretwacrjlic acid (b. p. 218O), a syrupy acid, and a very small quantity ofother acids; a very little heptalactone (?) (b. p. 210-213'); and1-aiious neutral oils, soluble and insoluble in water, among which wasan oxetone, C13H2,02.Fittig and Kraft probably overlooked the lactone produced i t 1 t h edistillation, having used too little terpenylic acid.Heptolactone boils at, 218" (Vittig and Kraft, 220" ; Anithor,202-204"). A. G. B.Methyldipyridyls. By A. HEUSKR and C. SrroEHn (J. p r . Chem. [el, 42, 429--440).-Anderson (iinnaleu, 105, 344) obtained a sub-stance, which he called parapicoline, by the action of sodium on(impure) picoline.More recently Ahrens, (Abstr., 1889, 59) obtained:L base which he called dipicolyl by tile same process, but his picolinewas not, free from higher tiornologues. The authors have obtained ttpnre product and designate it as aa-dimethSldipyridy1.ax-llimethyZdipt,ridyZ, C12H,,T4'?, is prepared by adding thin strips ofsodium (10 grams) to a-picoline (b. p. 128", 20 grams) in a flaskand gently x x m i n g the mixture, aftev 7-8 days, in a reflux appa-mtus. Water is ihen added to the reaction mass, an operationi-,>quiring great care as unaltered sodium is liable to remain enclosedi l l the mass and to cause an explosion, and the separated oil is distilled ;ammonia and unaltered picoline come off below 150", and then practi-cdly nothitig distils until 300".All that distils above 300" is redistilled,when the greater portion conies over at 303-306" ; this portion isdissolved i n absolute alcohol and converted into hydrocliloride by acarrent of dry hydrogen chloride ; the hydrochloride is recryhtallised,decomposed by aqueous sodium carbonate, and the free base extractedwith ether. This base crystallises from water in large, lustrous,white leaves, with 4 mols. H20, which are lost over sulphui,ic acid;the crystals melt at 37--38", and the anhydrous substance a t 84". Itdissolves i n most solvents ; like other pyridine bases, it is less solublein hot than in cold water, and is separated from its aqueous solutionby a l k a h ; it is specifically Ileavier than water, and has R (aharacteristicodour.I t s solutions give a yellow colour with potassium ferrocyanide,and brown-red tables gradually separate from the solution. The hydro-chloride cry stallises in cvlourless leaves, and dissolves easily in wateORGANIC CHEMISTRY. 81and sparingly in alcohol ; the picrate crystallises in sparingly solubleyellow tables, and melts with decomposition at 240" ; the stannochzorideforms prismatic, yellow needles which melt at 179-180"; the zincsalt and the platinochloride are described; the latter is sparinglysoluble ; the aurochloride €orms needles, darkens at 200°, and meltsat 209--210" (compare Ahrens, Zoc. cit.) : the mercurochloride crystal-lises in serrated leaves which darken at 210" and melt at 220".a- Methy Zd i p j ridy 1- a- carboxy lie acid, C,NH3Me*C,NH3*C 0 0 H, ob-tained by oxidising aa-dimethyldipyridyl with potassium permanga-nate, crystallises in pale yellow needles (with 5 mols.H,O) ; it isfreely soluble in hot water and alcohol, and its solutions give a red-dish-yellow colour with ferrous sulphate ; the anhydrous acid melts at193" giving off carbonic anhydride.mentioned carboxylic acid is heated with glacial acetic acid in asealed tube at 180-190" for 2-3 hours ; the acetic acid is evaporated,and the base liberated by sodium carbonate and extracted with ether.It is more soluble in water than dimethyldipyridyl, and melts at 94" ;it will be treated of in a future communication. A. G. B.a-MethyZdipyridyl, C5NH,Me*C,'NH4, is formed when the abovea-Picoline and dsobutylenepyridine.By C. STOEHR (J. pr.Chem. [ 21, 42, 420-428).-a-Picoline was obtained from animal oilby treating the hydrochloric acid solution of the fraction 128-133"with mercuric chloride and recrystallising the mercurochloride formed.It boils at 128". The platinochloride never contains any water ofcrystallisation, whatever the circumstances under which it is crystal-lised (compare Weidel, Abstr., 1880, 269; Seyfferth, J. pr. Ohern.[2], 34, 241;) ; it crystallises in monoclinic tables, a : b : G =0.6636 : 1 : 0.9078; p = 72" 46' ; it melts with decomposition at195", not 178" (Lnnge, Abstr., 1886, 256 ; and others), and is moresoluble in water than p-picoline plAinochloride. Impure a-picoline(b. p. 138-134") gives a platinoohloride which crystallises with1 mol.H20, melts at 195", and is nearly similar in crystalline form[a : b : c: = 0.9758 : 1 : 1.3270 ; p = 76" 47'1 to the platinochloridepreviously described as that of a-picoline (loc. cit.).a-Isobutylenepyridine, CSHIIN, is obtained by heating a-picoline (8grams) with acetone (5 .grams) and some zinc chloride in a sealed tiibeat 250-260'' for 10 hours ; the product is acidified with hydrochloricacid, extracted with ether, and, after heating to expel ether, distilledwith steam ; solid sodium hydroxide is then added and the liberatedbases distilled, dried by potassium hydroxide, and redistilled. Thegreater part of the distillate, boiling below 140", is unaltered a-picoline ;the rest is twice fractionated, and the portion boiling between 190--210"converted into mercurochloride, from which the isobutylenepyridine is1iberar;ed by potassium hydroxide.It boils at 2OW, is very sparinglysoluble in water, has a blue fluorescence and peculiar odour; itsaqueous solution becomes turbid from separation of the base at thetemperature of the hand, and i t is volatile with steam. Its sp. gr. at0°/4" is 0.9715. The hydrochZoride crystallises in prisms melting at140--141", and soluble in alcohol and water ; the platinochloride formsneedles or prisms (with 2 mols. H20), andbmelts, when anhydrous, atVOL. LX. 82 ABSTRACTS OF CHEMICAL PAPERS.163-164" with decomposition ; the aurochlm'de is unst,able, and meltsa t 135-137" ; the mercurochloride is sparingly soluble, and crystallisesin long, slender, lustrous needles which melt at 144-145"; thepicrate forms small, yellow needles, melts at 1 7 7 O , and is sparinglysoluble.A. G. B.Diethylmuscarinepyridine. By H. LOCHERT ( BZC ZZ. SOC. Chim.f 31, 3, 858-86 1) .-Dieth y hnuscarinep y r i d iize bro Pn ideC5NH,Br*CH2*CH( OEt),,is obtained by heating a mixture of bromacetal and pyridine, in mole-cular proportion, at 80" for 10 days ; on cooling, the compound crystal-lises out in deliquescent, nacreous scales which are very soluble in waterand in alcohol. With platinum tetrabromide, it forms a red, amorphousprecipitate, which is almost insoluble in water, completely insolublein alcohol.On treating diethylmuscarinepyridine bromide in aqueous solutionwith moist silver oxide, a colourless, strongly alkaline liquid is obtained,which neither crystallises on coilcentration nor forms crystallinesalts, concentration of the solutions yielding syrupy liquids.Di-ethyZmuscarinepyridine, OH.C,NH,.CH,.CH( GEt),, as thus obtained,precipitates the hydroxides of silver and of copper from solutions oftheir salts.Further communications on other muscarine derivatives are pro-mised, as also on the synthesis of muscarine itself by means ofhromacetal and trimethylamine. T. G. N.Tribromoquinolines. By A. CLAUS and P. HEERMANN (J. pr.Chem. [S], 42, 327-346).-The generic similarity between 3 : 4'-dibromoquinoline and the tribromoquinoline described by Claus andWelter (Abstr., 1890, 1320), and the fact that the latter can beobtained by brominating 4'-bromoquinoline, fiettles the orientation oftwo of the bromine atoms in this tribromoquinoline.The position ofthe third bromine atom is now settled, for the authors have succeededin obtaining the same tribromoquinoline by heating I : 3-dibromo-quinoline hydrobromide dibromide according to Claus' ar~d Col-lischonn's method (Abstr., 188'7, 158) ; this is therefore 1 : 3 : 4'-tribromoquiwoline. This conclusion is supported by the fact thatquinoline-3-sulphonic acid and quinoline-1-sulphonic acid both givethis tribromoquinoline when they are brominated, for it is knownthat the first bromine atom enters into the 4'-position. It is to benoted that Clam and Riittner (Abstr., 1887, 278) were not workingwith pure quinoline-1-sulphonic acid when they obtained a tribromo-quinoline of melting point 198", but with a mixture of this andquinoline-4-sulphonic acid, which by their method yielded only3 : 4 : 4'-tribromoquinoline ; that the tribromoquinoline obtained byClaus and Zuschlag (Abstr., 1890, 267), melting at 185O, is a mixtureof 1 : 3 : 4'- and 3 : 4 : 4'-tribromoquinolines; and that Lubavin's(Bedstein, 3, 749) tribromoquinoline (rn.p. 173-175") is impure1 : 3 : 4-tribrornoquinolineORGANIC CHEAIISTRY. 831 : 4 : 4'-TribrornoquiizoZine is obtained by heating the hydrobromidedibromide of 1 : 4-dibromoquinoline (m. p. 127", Abstr., 1890, 172),and fractionally precipitating the acetic acid solution of the residueby the method already given. It forms small needles when crystal-lised and large needles when sublimed; it melts at 168-168-5"(uncorr.), and dissolves in most organic solvents.Its salts with thestronger mineral acids crystallise well, but are dissociated by water.The pZatinochloride forms orange-red crystals, which are dissociatedby water and alcohol. Two nitro-derivatives, melting at 197" (uncorr.) and 157" (uncorr.) respectively,and soluble and insoluble in alcohol, respectively, have been obtained.This tribromoquinoline is also obtained by brominating 4 : I-bromo-qninolinesulphonic acid (Abstr., 1890,267) ; if too much bromine (above2 mols.) is used, a tetrabromoquinoline melting at 198" is also formed,and the constitution of this is evidently 1 : 3 : 4 : 4'-tetrabromoguinoZine.It is identical with the tetrabromoquinoline obtained by Claus andWelter (Abstr., 1890, 1320), and is perhaps the compound (m.p.198") obtained by Claus and Euttner, and described by them as atribromoquinoline (see above)Claus and Posselt (Abstr., 1890, 5221) studied the action of phos-phorm pentabromide on 1 : 4-hydroxyquinolinesulphonic acid at 130"and 160", and obtained substances which they described as a bromo-yuinolinesulphonic bromide and a tribromoquinoline, respectively.Closer investigation has now shown that both these substances stillcontain the hydroxyl group, being 1-hydroxy-? : 4-bromoquinoline-sulphonic bromide and 1-hydroxy-3 : 4 : 4'-tribromoquinoline respec-tively, and not the aforesaid compounds.1-hydroxy-3 : 4 : 4'-tribromoqzcino&ae crystallises in long, brilliant,lustrous, colourless needles, and melts at 172-173", not 168"; itsbasic properties are inappreciable, for it forms no platinochlorideor methiodide, but yields metallic derivatives with the alkalis and theheavy metals.When 1-hydroxy-? : 4-bromoquinolinesulphonic acid is treated withtin arid hydrochloric acid, the hydroxyl group is reduced, and theh ydroquinoline-4-sulphonic acid, CSNHlo*S03H, described by Lellmann,is obtained; it crystallises with 1 mol.HzO, and melts at 315"(uncorr.) ; its pofassium salt was obtained.By E. CARLTER and A. EINHORN ( Bw.,23, 2894-2897) .-2'-Quinolylacetaldehyde may be prepared by theelectrolysis of 2'-quinolyl-a-hydroxypropionic acid, or by the actionof concentrated sulphuric acid.On treating quinolylhydroxypropionicacid with a, glacial acetic acid solution of bromine, dibromoquinoZyl-acetaldehyde is formed, melting at 180". The phenylhydrasone crystal-lises from alcohol in prisms which melt at 168-169". The oairnecrystallises in white needles melting at 235-237". By the action ofphosphorus pentachloride on the aldehyde, 2'-w-dichZoroethyZquinoZine,C9NH6.CHz*CHC12, is formed, crystallising froin ether or alcohol inwhite needles which melt at 80".'L'-3'-DiquinoZyZ is prepared from orthamidobenzaldehyde andquinolylacetaldehyde ; it cryetallises from alcohol in white plates,No methiodide has been obtained.A. G. B.2'-Quinol~lacetaldehyde.a 84 ABSTRACTS OF CHENICAL PAPERS.melting at 175*5", and is identical with the compound obtained byWeidel by the action of sodium on quinoline.2'-QuinoZylucetic acid is formed by the oxidation of the aldehyde, orby fusion with potassium hydroxide ; it crgstallises from alcohol inwhite needles which melt at 275", and may be sublimed withoutdecomposition. The hydrochloride melts at 243'.The cukiunz suZtforms a white, crystalline powder; the silver salt decomposes onexposure to light, and yields quinaldine on distillation in an atmo-sphere of hydrogen; it is also formed by heating the calcium saltwith calcium oxide.2'- QuinoZyZpropionic acid, CgN*H6.CH2*CH2*COOH, is prepared bythe reduction of quinolylacrylic acid with sodium amalgam ; itcrystallises from water or alcohol in needles which melt a t 115-116".The ethyZ calt crystallises from light petroleum in needles whichmelt at 116".2'- Quinoly ldibromopro23ionic acid, CgNH6*CHBr.CHBr*COOH, isformed by the action of bromine 011 quinolylacrylic acid ; it cyystal-lises from glacial acetic: acid in white prisms which melt at 180-181".If this compound is dissolved in an alkaline carbonate solution, anddistilled in a current of steam, 2'-~z~inoZylucet~lene, CgNH6*CiCH, isformed ; this is an oily liquid, and yields 2'-qui~iolyldibro~?-~etlzylene,CgNH6*CBr:CHBr, which is deposited from ether in nodular crystalsmelting at 63-64".By the action of excess of bromine on thiscompound, a perbromide is obtained, which crystallises in prisms, andmelts at 195-196".2'- QZLirLoZy Zdihydrox~propiollic acid, CgNH6*CH( OH)*CH( OH)G 0 OH,is prepared by the oxidation of quinolylacrylic acid with a dilute solu-ticrn of potassium permanganate at low temperatures ; it crystallisesfrom water or alcohol in prisms which melt at 113" ; the ethyl saltforms prisms melting at 110.5".Nitro- and Chloro-derivatives of p-Methyl- 8-oxyquinazoline(Anhydroacetylorthamidobenzamide).By L. H. DEHOFF ( J . p.Chem. [2], 42, 346-360 ; compare Abstr., 1887, 1043).--Nitro-/3-i,zethyZ-6-oxyquiiaazoline is obtained by nitrating /3-methyl-8-oxyquin-azoline with nitric acid (sp. gr. 1.5) at the boiling point, and evnpo-rating. It crystalliscs from hot water as a white powder ; it beginst o darken at 230", but is not further changed till 28U" ; when heatedon platinum foil, it explodes feebly ; it dissolves in aqueous alcoholand alkalis, but not in ether or benzene.Its solution in ammoniagives a white silver compound when precipitated with silver nitrate,but is not precipitated by the salts of other heavy metals. It crystal-lises unchanged from hot strong hydrochloric acid. The methylc o ~ ~ p o ~ i n d forms small, slender, white needles melting at 165".No inonochloro-derivative has been obtained.Tetrachloro-/3-methyZ-B-oxyquinazoline is prod uced bey mixing theoxyquinasoline (6 grams) with phosphoric chloride (25 grams), dis-solving the mixtcre in phosphorous chloride (10 grams), and heatingfor 12 hours a t 170"; the excess of the phosphorus chlorides isdistilled off, and the residue washed with soda solution, and crystal-lised from alcohol ; the yield is 53 per cent.It crystallises in whiteNo other salts could be obtained.J. €3. TORGANIC CHEMISTRY. 85needles which melt at 124-125", and a.re insoluble in water, butsoluble in most other solvents.When the tetrachloro-derivative is evaporated with alcoholicpotash, and the residue dissolved in water, filtered, and treated withdilute sulphuric acid, a precipitate is obtained which crystallises fromalcohol in yellowish prisms melting at 206-207" ; the formula ofthis substance is C9H4CI,Nz-OH. The ethyZ compound, CgH4CI,N2*OEt,is obtained at tJhe same time, being left, undissolved by the water ; itcrystallises from alcohol in soft, lustrous, white needles melting a t75-76".The amide, C9H4C1,N2.NH2, is obtained by heating thetetrachloro-derivative wit,h alcohDlic ammonia a t 150-160" for 2-3hours; the reaction mass is washed with water, and heated withalcohol and animal charcoal ; the alcdholic solution is then precipi-tated with water. The amide crystallises in needles which blackena t 178", and melt a t 183-184"; it dissolves in dilute alcohol andbenzene, but not in ether, liyht petroleum, o r water; its h y d ~ o -chloride blackens and decompo,ces about 'LOO". A inethylaminederivative, C9H4Cl,Nz*NHMe, was obtained by heating the tetrachloro-derivative with methylamine a t 110" ; it forms white, microscopicneedles (with 1 mol. HzOj, which soften a t 149", and melt at 155".An anilide, CgH4Cl3N2*NHHh, was also obtained ; it crystallises (with1 mol.alcohol) in thick, white, rhombic tables.A consideration of the above compounds leads to the conclusionthat tetrachloro-~-methyl-6-oxyquinasoline contains one atom ofchlorine situated differentlv from the other three, and as this atom iseasily replaced, it cannot be in the benzene nucleus; the author,therefore, ascribes the formula C6HCl,< ccl:r to the tetrachloro-N r C M ederivative. The above-described ethyl and amido-compounds willthus be trichloro -P -methyl - 6- ethoxyquinazoline and trichloro - p-methyl-8-amidoquinazoline, respectively. It is, however, still an openquestion whether P-methyl-6-oxyquinazoline is really a hydroxy- oran oxy-derivative (Ahstr., 1887, 1043). When the tetrachloro-derivative is reduced with hydriodic acid, p-methyl-6-oxyquinazolineis obtained ; p-methylquinaxoline is probably formed, but oxidises a tonce to the oxy-compound.Papaveroline.By I(. KRAUSS ( J f ~ m t s h . , 11, 350-362 ; compareAbstr., 1869,166,167 ; 1887, lll6).-The hydriodide of this base hasbeen prepared by Goldschmiedt by the action of concentrated hydr-iodic acid on papaverine, in presence of amorphous phosphoriis,When a solution of sodium hydrogen carbonate, saturated withcarbonic anhydride, is added to the hydriodide, tlie free base,C16H13N04,2H20, is precipitated as an almost colourless, crystallinepowder, which, when dried in a vacuum, is perfectly stable, and con-tains 2 mols. HzO, which are given up at 100". Heated to 150°, itdarkens i n colour, and, on raising the temperature to 210°, becomesquite black, without having previously melted.The base dissolvesreadily in mineral acids, i n oxalic acid, and in alcohol, and is verysoluble in acetic acid and in glycerol. Dilute potash turns an alco-holic Bolution blue ; strong potash produces a dark-violet coloration.A. G. B86 ABSTRACTS OF CHEMICAL PAPERSThe hydrochloride, CI6Rl3NOa,HC1 + H20, crystallises in whit.eneedles, soluble in hot water ; the sulphate, ( C16H13NOa)2,H2S04 +8+H20, is only slightly soluble in water ; the oxalate,crystallises from water in spherical aggregates of needles.On distillation Tvith zinc-dust in a stream of hydrogen, the authorexpect,ed to obtain a-benzylisoquinoline. Instead of this, dibenzyldi-isoquinoline, (c16H12N)z, and a-methylisoquinoline were formed.Theformer is insoluble in dilute hydrochloric acid, dissolves readily inether, light petroleum, acetic acid, and benzene, and when crystallisedfrom alcohol, melts constantly a t 234-235"; the latter is an oil,which dissolves in dilute hydrochloric acid, and furnishes a platino-chloride, ( C,oH,N)2,H,PtC~6 + l$HzO, which, after liecrystallieationfrom water, melts at 229", and a crystalline picrate which commencesto sinter at 198", and melts at 209-210". G. T. M.Strychnine. By C. STOEHR (J. p ~ . Chenz. [2], 42, 399-415).-Most of the analyses of strychnine which have been made agree withthe formula C2,H2,N202. The author has prepared and analysedstrychnine hydrochloride (with 14 mols.HzO), of which he givescrystallographical measurements, and its platinochloride ; also strych -nine hydrobromide (with 1 mol. H20) and hydriodide (with 1 mol.H20) ; his analyses confirm the above formula for strychnine and thegenerally accepted formule for these salts. Pure commercial strych-nine melted at 265-266" ; by converting this into the hydrochloride,reconverting the latter into strychnine, crystallising from alcohol, andpulverising the crystals, a light powder was obtained which darkenedat 260°, and was a dark bl-ownish-yellow liquid at 269". Claus andGlassner give the melting point of strychnine as 284" (Abstr., 1881,747) ; Beckurts as 255" (uncorr., Abstr., 1885, 675) ; Loebish andSchoop as 268" (Monatsh., 6, 858) ; Beckurts as 265" (Abstr., 1890,1328) ; and Garzarolli-Thurnlackh as 262" (Monatsh., 10, 1).The author has again investigated the distillation of strychninewith lime (compare Abstr., 1887, 604, 682 ; 1888, 63), and has againfound that hydrogen, ethylene, ammonia, ethylamine, scatole, p-pico-line, and, probably, ethylpyridirie are produced.As the i3-picolinethus obtained seems to be identical with that obtained from othersources, it may be allowed that all /3-picolines at present known areidentical, whatever their source (compare Ladenburg, Abst'r., 1890,1432).To obtain trichlorostrgchnine (Abstr., 1887, 604) dry, powderedstrychnine hydrochloride is heated with phosphoric chloride(&5 parts) and chloroform in a reflux apparatus on the water-bathas long as hydrogen chloride is evolved ; water is then added, and thechloroform distilled off; ammonia is added, the liquid extracted withether, and the ether residue crystallised from alcohol containinghydrochloric acid. It gives much the same reaction as strychninewith potassium dichromate and sulphuric acid, and a similar colourwith nitric and sulphuric acids.When an excess of phosphoric chloride (7-8 parts) is used, ORGANIC CHEMISTRI'. 87higher chlorinated derivative is obtained ; after distilling off thechloroform, an insoluble mass is left which is extracted with benzene.This derivative crystallises in long, slender, colourless needles whenabsolute alcohol is added to the hot benzene solution ; its compositionis in approximate agreement with a pentachlorostrychnine ; it darkensand melts at 224"; it does not give the same reaction as trichloro-strychnine with nitric and sulphuric acids.Brucine.By L. BEREND and C. STOEHR (J. pr. Chern., 42,41 5-420).-De Coninck (Abstr., 1882, 739) distilled brucine withpotash, but obtained no homologues lower than lutidine.The gaseous products of the distillation of brucine with slaked limewere hydrogen, ammonia, and ethylene. The distillate was at first a,colourless liquid with a yellow oil suspended in it? but i t rapidlybecame brownish-red in air; it WHS acidified with hydrochloric acidand distilled in steam, whereby a few drops of scatole were obtained,but the bulkof the liquid did not distil. The liquid was shaken withether, and then solid potash was added t o it until all the oily baseshad separated; these were then dissolved in ether.The aqueousliquid contained ammonia and methylamine, while the bases irr theethereal solution were found to be mainly P-picoline and a lutidine,probably p-ethylpyridine, together with smaller quantities of otherpyridirie bases ; quinoline bases were absent. The ,%picoline boiledat 142-143', and was identical with that obtained from strychnineA. G. B.(previous abstract) ; its sp. gr. at 0"/4" was 0.9756 (Zanoni, 0'9771).A. G. B.Alkaloids of Veratrum album. By C. PEHKSCHEN (J. Pharm.[ 5 ] , 22, 265-269 ; from Pharm. Z e d . RUSS., 29, 339).-The rhizomeof the wild plant gives 0.57 to 0.66 per cent. of mixed alkalo'ids,whilst the cultivated rhizome yields only 0.29 per cent.Thepowdered root is macerated with dcohol during six days at theordinary temperature, and this repeated a second and third time, thelast time with the addition of acetic acid. The first alcoholic extractis faintly acid from the presence of jervic: acid. The alcoholic soln-tions are united, and the major portion of the alcohol is removed bydistillation under reduced pressure ; on the addition of 3 to 4 vols. ofboiling water, resinous substances are precipitated, which are re-moved by filtration. The remaining resinous and colouring mattersitre removed by agitation with ether. Hydrogen sodium carbonate isthen added to alkaline reaction, then ether, and subsequently chloro-form. When the ether and chloroform solutions are evaporated, themixed alkaloids are left, and these on being treated with absoluteether, give veratroidine and a minute amount of jervine in solution,whilst the insoluble portion contains jervine and a third alkaloid,pseudojervine. Veratroi'di?ze, C32H53N09, melts about 149", and charsabout 172".Atl 22.5", 1 part dissolves in13 parts of benzene, 5.9 of chloroform, and 9.09 of absolute ether. Itdissolves in alcohol in almost all proportions. Veratroidine yieldsamorphous salts with hydrochloric, hydrobrornic, sulphuric, nitric,oxalic, and acetic acids. Most of the general reagents for alkalo'idsgive with this base more or less of a precipitate, according to theIt is optically inactive88 ABSTRACTS OF UHEMICAL PAPERS.state of concentration.A hydrochloric solution of 1 : 5000 gives IZfaint turbidity with mercury potassium iodide, and a solution of1 : 3500 a turbidity with phosphomolybdic acid. With concentratedsulphuric acid, veratro'idine gives a jeliow liquid which passes throughorange-red to cherry-red, with a green fluorescencc, whilst concen-trated nitric acid produces a transient rose colour which soon passesto citron-yellow. Hydrochloric acid (11.0 per cent. is best) gives abeautiful rose coloration ; this serves to distinguish veratroldinc fromveratrine. Veratroidine, when heated at 120" with ethyl iodide in asealed tube for 40 hours, yields the compound C,,H,,NO,,'LEtI. Pseudo-jervine, CznH4,NOlz, forms large, rhombic crystals. The root does notconta,in more than 0.006 per cent.The alkalojid begins to turn yellow:it 215", and melts at 259" with blackening. It is optically inactive.At 22", 1 part of this base dissolves in 10.876 parts of light petroleum,in 372 parts of benzene, 1021 parts of absolute ether, 4.1 of chioro-form, and 184% of absolute alcohol. With phosphomolybdic acid, asolution of 1 : 10,000 gives a perceptible turbidity ; but with mercurypotassium iodide, the dilut'ion should not exceed 1 : 6000. The purebase gives no colour with either liydrxhloric, nitric, or sulphuricacids, the latter mixed with sugar or with other reagent. Whenmixed with minute quantities of jervine, it gives the colorationreactions described as characteristic of i t by Wright and Luff.Jervine, Cl4HzZNO2, crystallises from a boiling alcoliolic solution inbeautiful white needles.It melts a t 237*7", and is slightly levorotary.A t 25", 1 part of the base dissolves in 1658 parts of benzene, in268 parts of absolute ether, in 60 of chloroform, and 16.8 partsof absolute alcohol. The base is insoluble in light petroleum,and very slightly soliible in ethyl acetate, water, and carbon bi-sulphide. Beautiful rhombic crystals of the normal hydrochloride,with 0, mols. H,O, are obtained by mixing an alcoholic solution ofthe base with an alcoholic solution of hydrogen chloride ; sulphuricacid gives an acid salt under the like conditions. Jervine is cha-racterised by the violet coloraticn, passing to blue, which it giveswith sulphuric acid and sugar ; veratroydine, with this test, gives abrown coloration.J. T.Benzyl Derivatives of Piperidine, Tetrahy droquinoline, andPyridine. A New Method of Formation of Benzyleneimides.By E. LELLMANN and H. PEKRUN (ArznaZen, 259,40--6I).-Para~~itro-benzyZpiperidine, NOZ*CGH4-CH2-C5NHl0, is obtained when piperidine isgradually treated with paranitrobenzyl chloride in well-cooled alco-holic solution, the mixture then boiled for about an hour, and thehydrochloride thus produced decomposed. with water. It crystallisesfrom light petroleum in large, amber-coloured plates, inelts a t 34", andis very readily soluble in mineral acids and most organic solvents, butonly sparingly in water. The hydyochloride, ClzH16NzOz,HC1, crystal-lises from hot alcohol in light-brown prisms, melts a t 236", and isreadily soluble in water, but insoluble in ether, benzene, and lightpetroleum.The PZatinochZoride, ( C12H16NzO~),,H2PtC16, is a yellow,amorphous, unstable conipound.P a m m i d o b e ~ z y ~iperidine, C12HlsN2, is formed when the precedinORQANIG CHEMISTRY, 89compound is reduced with tin a n i hydrochloric acid ; the product is.distilled with steam and recrystallised from hot light petroleum, fromwhich it separates in colourless needles melting at 87". It is readilysoluble in most ordinary solvents except water. The hydrochzoride,CIzH18N2,2HC1, crystallises in yellow needles and is very readilysoluble in water.DimethyZanilineazobenzylpiperidine, NMe,.C6B,*N2.C6H4gCH2.C5NH10~is produced when a solution of paramidobenzylpiperidine in well-cooled concentrated hydrochloric acid is treated first with sodiumnitrite, and then with dimethylaniline. It crystallises from alcohol ingolden needles, melts a t log", and dissolves in dilute acids, yielding adark-violet solution, the colour of which changes to yellow on theaddition of water; it is readily soluble in the ordinary organicsolvents, but only eparingly soluble in water.The hydrochloridecrystallises from alcohol in small, bluish-black needles, and itsaqueous solution imparts to silk and wool a yellow coloration.ob-tained, mixed, however, with paramidobenzylpiperidine, when thebrown light petroleum mother liquors obtained i n the purification ofthe last-named compound are evaporated ; it can be purified by con-verting it into the hydrochloride.It crgstallises from light petr-oleum in colourless needles melting a t 76-76-5". The hydroch7oride,CI2H,,ClNZ,2HCl, forms yellow, well-defined, transparent crystals.Orthonitrobenzy723iperidine, Cl2HI6N2O2, prepared as described in thecase of the corresponding para-compound, is a thick, yellow oilhaving an odour recalling that of piperidine; it is soluble inmineral acids and most ordinary organic solvents. The hydrocAZoride,C12Hl,N20,,HCl, separates from hot alcohol in well-defined, yellowish-green, transparent crystals, sinters together a t 124", and melts com-pletely a t 209". The pZatinochlo~ide, ( Cl,Hl,N202)2,HzPtC16, is ayellow, amorphous compound.O r t h a m i d o b e ~ , z y ~ i e r i d i ~ e , CI2Hl8N2, crystallises from hot lightpetroleum in almost colourless, rhombic plates, melts a t 82*5", and isreadily soluble in mineral acids, alcohol, benzene, &c., but moresparingly in water.Metanit~oBenzy~iperidine, CI2Hl6N2O2, is an oil, and resembles theisomerides described above in its behaviour with solvents.Thehydrochloride separates from alcohol in yellow, rhombic crystals.The platinochZoride, ( C12Hl,N,0,),, H,PtCI,, is yellow and amorphous,Nr'etnmidobenzyZpiperidine, C,,H,,N,, ci-ystallises from light petr-oleum in colourless needles: and melts a t 112".Paranitrobenzyltetrahydi-oquinoline, N02-C6H4*CHP*CONH10, can beobtained by heating paranitrobenzyl chloride (1 mol.) with tetra-hydroquinoline (2 mols.) for 1 to d hours in alcoholic solution, anddecomposing the salt thus produced, with water ; it cr~stallises fromhot alcohol or ether in long, bright-red prisms melting at 102".Theplatinochloride, (C16~,,~z0z)2,H2PtC~,, is a sparingly soluble, yellowish-red compound. The corresponding ortho-compound crystallises inbrownish-red plates, melts at ill", and forms a yellow, amorphouspZatinochZoride. The meta-base crystallises from alcohol in short, redprisms, melts at 99", and is only moderately easily soluble in ether,Pur amidoch 1 or0 benz y lpiperidin e, NH3* C 6H 3C 1- C H2*C5NHlo, i90 ABSTRACTS OF UHEMICAL PAPERS.cold alcohol, chloroform, and dilute acids. The three nitrobenzyl-tetrahydroquinolines are only feeble bases, and their hydrochloridesare decomposed by water ; they give Konig's reaction for tetrahydro-quinoline with oxidising agents, and on reduction they yieldi thecorresponding amido-compounds, of which the meta-derivative,NH2-C6Hi*CH2*NC9Hlo, is crystalline, and melts at 82".Paranitrob enz y lp yridin P, chloride, N02*C6H4.CH2*C5NH5C1, is formedwhen paranitrobenzgl chloride is warmed with excess of pyridine. Itcrystallises from alcohol in yellow prisms, sinters together at aboutgo", melts at about 103", and is readily soluble in water, alcohol, ben-zene, and mineral acids, but only very sparingly in ether and lightpetroleum.The platinochloride, ( C12H11 N202C1)2, Pt C Ip, crystallisesfrom dilute hydrochloric acid in golden plates, and melts at 220-223"with decomposition.Paramido benz y 7p y ridin e chloride 72 ydrochloride, C12H13N2C1,HC1, isobtained in yellow crystals when the nitro-compound is reduced withtin and hydrochloric acid.It melts at 183-185", decomposes at200-202", and is only sparingly soluble in alcohol. When treatedwith alkalis, it yields a yellowish, resinous compound which does notmelt below 280", and when heated at 210-220" it is decomposed intothe hydrochlorides of pyridine and parabenzyleneimide. The platino-chloride, (C12Hl,N2C1)2,H2PtC16, is crystalline.Orthonitrobenzy ~ y r i d i n e chloride, Cl2Hl1N2O,C1, prepared by heatingpyridine with orthonitrobenzyl chloride, crystallises from alcohol andether in yellowish prisms, melts at about 76", and gradually decom-poses at a higher temperature ; it resembles the corresponding para-compound in its behaviour with solvents.The platinochloride,(C,2HllN202C1)2,PtC14, crystallises in yellow scales.Orthn?nidobenzy~~riai~ae chloride hydrochloride, C12H,,N2C1,HC1, is acolourless, semi-crystalline powder, wbich melts a t about 169" anddecomposes at a higher temperature, yielding orthobenzyleneimide ;the last-named compound is a reddish-brown powder which does notmelt below 290".Metanitro bennsy lp yridine chloride, C12HllN202CI, crys t allises fromalcoholic ether in yellow needles, sinters together at 60°, and meltsco tupletely at 100". The platinochloride, (C12HllN202Cl)2,PtC14,crystallises in small, yellow needles. Metamidobenzylpyridine chlorideir ydrochloride, C,,H1,N2C1,HC1, is a colourless powder which melts atabout 220" with decomposition.Metabenzyleneimide, C6Ha< bEi is obtained, together with pyr-idine hydrochloride, when the preceding compound is heated at230" ; it is a yellow, amorphous powder melting at 120-145". Theylatinochloride has the composition (C,H7N),,H2PtCl6.Molecularweight determinations by Raoult's method gave results which showedt h a t parabenzyleneimide is probably a, polymeride of a compound ofthe molecular formula C,H,N. F. S. K.Tropidine. By A. EINHORN (Ber., 23, 2889-2894).-By theaction of aqueous hypochlorous acid on tropidine, t w o compoundsare formed, and may be separated by recrystallisation from diluteNORGANIC CHEXISTRY. 9 1alcohol ; the one is deposited in long, lustrous prisms which melt at138" ; the second is more soluble, separates in white, nodular crystalsmelting at 108-log", and has the formula C,H,,N,HOCl.On heating tropidine with ft glacial acetic acid solution of hydro-bromic acid in R sealed tube at loo", the salts of two isomerichydrobromotropidine hydrobromides are formed, and may be sepa-rated by crystallisation from alcohol ; the more insoluble is termedthe a-compound, and the second the P-compound.a-Hydrobromo-tropidine hydrobromide, C,H14NBr,HBr, is obtained as the chief pro-duct if the heating is continued for 70 hours; it is very soluble inwater, and crystallises in transparent prisms which melt at 219-220".The f r e e base is liberated by the action of aqueous soda./3-?jdro-bromotropidine hydrobromide, CgH14NBr,HBr + H,O, is formed i f thereaction is allowed to proce'ed for only 24 hours ; it crystallises fromalcohol in lustrous, prismatic needles melting at 113-114" ; onheating to 105", the anhydrous compound is obtained, which differs,however, from the a-derivative. The frea base is formed by theaction of alkalis ; on treating it first with anhydrous sodium acetateand then with aqueous soda, a small quantity of a base is obtainedwhich yields a platinochloride melting at 200" ; tropine platinochloridenielts at the same temperature. The author suggests that the com-pound prepared by Ladenburg (compare Abstr., 1890, 1167), by theaction of hydrobromic acid on tropidine at low temperatures, is reallyideii tical with p-hy drobromotropicline.Tropidirhe &bromide, CsHr,NBr,, is prepared by treating a glacidacetic acid solution of tropidine with excess of bromine dissolved inthe same medium ; the oil which separates is washed with sulphurousacid ; on the addition of potassium carbonate, the dibromide sepa-rates.On adding water to the alcoholic solution, it crystallises out insmall, lustrous plates which melt at 66-67.5" with previous softening.On boiling the dibromide with dilute sodium hydroxide solution, a pene-trating, aromatic odour is produced which greatly resembles that. ofdihydrobenzaldehyde (compare this vol., p. 67). J. B. T.Aconitine. By A. LUIIBE (Chem. Centr., llr90, ii, 148-149 ; fromApoth. Zeit., 5, 321).-From the tubers of the Japanese plant Kusa-uzu, the author has extracted, by means of Duquesnel's method,a n alkaloid of the formula C33H44NOll,, which he considers t o be iden-t,ical with the alkaloid obtained from Aconitum napellus. Wright'sformula for aconitine is C3,Hf,,NO1,, whilst that of Jurgens is C33H47N0,2.Aconitine forms radially fibrous groups of crystds of the rhombicsystem. The crystals measured by the author had the followingfaces :-Obtained from the cold saturated solutioz, mPm, mP, OP ;from the hot saturated solution, mP, mPm, OP, Pw, P.At 110",it is partially decomposed; it melts a t 183-184"; [a]=, -34.46.The taste is not bitter, but prickly and burning. The most delicatereagents for acoiiitine are hydrogen iodide and potassium mercuryiodide. The hydriodide, even when present in very small quantity(0.02 milligram), appears crystalline under the microscope.Pseudo-aconitine could not be detected. The author finds that aconitine hasthe same physiological properties as are ascribed to i t by Lewins92 ABSTRACTS OF CHEMICAL PAPERS.acting on the extremities of certain nerves. It does not appearitself to undergo any change, nor does it in any way decompose theblood corpuscles.From the tubers of Langaard's variety, " Shirakawauzuware " ofAconitum sineme, the author obtained 0.02 per cent. of a crystallinealkalo'id and two amorphous bases. He considers the alkalo'id to beidentical with aconitine from Aconitunz napeZZus; it melts at 180.9".Pseudoaconit'ine could not be detected.J. IV. L.Hydrastine. By M. FREUND and M. HEIM (Ber., 23, 2897-29lO).-It has previoiisly been shown (Abstr., 1890, 532) that alkyl-hydrastines are formed by the action of alkalis on the additive corn-pounds of hydrastine and alkyl halo'ids ; aqueous ammonia, reacts in asimilar manner in the cold, but on boiling an alcoholic solution ofhydrastine methiodide with concentrated aqueous ammonia, a com-pound is obtained crystallising from alcohol in white, strongtyrefractive, rhombic plates which melt a t lSO", are almost insoluble 111water, and dissolve sparingly in ether, carbon bisulphide, o r benzene.The substance is a powerful base, arid decomposes ammonium salts ;it has the formula C2,H2,N206, and the author proposes to term it?nethyZh~cZrastamidL..It may also be obtained by the action ofammoiiin on methylhydrastine. The salts of the amide are somewhatdifficult to prepare, as they readily part, with the elements of water.The picrate crystdlises from alcohol in small, yellow needles. Thehydrochlode, C22H26N206,HC1 + 2H,O, is deposited in white needleswhich melt a t ll6--l1So.Meth~Zl2ydrastinaide, C22H24N205, is prepared by the action of diluteacids, or of concentrated potassium hydroxide solution, on the amide ;i t crystallises from alcohol i n slender, light-yellow needles whichmelt a t IW", and are insoluble in water. The hydrochloride,C,,H,,N,O,,HCl, crystallises from absoln te alcohol in slightly yellowneedles which melt at 227"; a hydrated salt melting a t 110-120"may also be obtained.The platinochloride crystallises from hydro-chloric acid in brown rhombohedra melting at 20.5' with decomposi-tion. The sulphate is deposited from alcohol in yellow crystals whichmelt a t 218". The nitrate, C22H2AN,03,HN0, + H20, crystallises i 3slender needles which decompose a t about 230".Hemipinimide, C,H,(o&fe)2<Co>NH, is formed by the oxida-tion of methylhydrastamide with dilute nitric acid.Ethy Zhydrastarnide, C23H2eN,06, is prepared by the action ofammonia on hydrastine ethiodide, and is more readily soluble inalcohol than the methyl derivative ; it orystullises in rhombic plateswhich melt at 140".EtAyZhydrustimide, C2:%H24N205, is obtained on treating the amidewith dilute acids ; it crystallises from alcohol in rhombohedra whichmelt at 150-151".Methylhydrastimide methiodide, C2,H24N,05,MeI + 1+H,O, is formedby the action of methyl iodide on methylhydrastanride cr methyl-hydrastimide ; it crjstallises from water in yellow, flat rhombohedrawhich melt at 240-245".cORGANIC CHEMISTRY.93The action of amines on the additive compounds of hydrastine andd k y l haloids is stlrictlg analogous to that of ammonia itself. Methyl-hydra.stometh~lamide, C23H?JYzOG, is prepared by heating hydrastinemethiodide with an alcoholic solution of methylamine in a sealedtube at 100"; it crystallises from alcohol in white rhombohedramelting at 182", and is not acted OLL b.y concentlrated aqueous potash.The hydrochzoride crystallises from alcohol in white needles whichmelt at 193".Hemipinomethylimide is formed by the oxidation of thebase with dilute nitric acid. 17lethylhydrastethylamide, C2AH30N206, isobtained by digesting hydrastine methiodide with an alcoholic solu-tion of ethylamine for several days; it forms white crystals whichmelt at 16d0, and yields hemipinethylimide on oxidation. Methyl-hydrastisoanzy7anzide, C27H36N20G, is deposited from alcohol in long,filender crystals which melt at 171". On heating this compound witha. large excess of dilute hydrochloric acid, methylh~dl.astisoamylimide isformed as an oily liquid; the platinochloride is a yellow, crystal-line powder . M e th y 1 h y d r ast a1 1 y Zanzide, Cz5H30N20 6 , cry s t allis es fro malcohol, and melts at 158'. By the action of dilute hydrochloric acid,the corresponding imida is obtained as a viscid liquid which yields acrystalline platinochloride. I n the authors' opinion, the above resultsall tend to confirm the second of the formula? proposed for methyl-hydrastine (loc.cit.) ; the action of ammonia on niethylhydrastine istherefore represented as being strictly analogous to its action onbenzylidenephthalide ; methylhydrastamide and methylhydrastimidewould consequently be represented by the formubNMez*CH,*CH,*C6H,( 0,CH,)*CH2.C0.CGH,(OMe),CO*NII,[CH, : H, : CH, = 1 : 4 : 5 : 6 ; (OMe), : CON€€, : CO = 1 : 2 : 3 : 41CO.P;IHrespec- C6Hz(oMe)2<-- C: CH*C6Hz( O,CH,)*CH,*CH,*NMe,tively. J. B. T.Hydrastine. By .M FREUND and A. PHILIPS (Ber., 23, 2910-291 7 ; compare preceding abstract) .-Hydrastine a1 l y l iodide,C?1HZlNOG, C3H.51,is prepared by treating an alcoholic solution of hydrastine withexcess of ally1 iodide ; it crystallises from water or dilute alcohol insmall, white needles which melt at 193". By the action of potassiumhydroxide (1 mol.) on this compound, allylhydrastine, CaH2JYO6, isformed, crystallising from alcohol and ether i n deep-yellow needleswhich melt at 116". Allylhydrastezne, Cz,H,:NO, + 1$H,O, is pre-pared by boiling allylhydrastine with concentrated aqueous potash,and is deposited from water in white crystals which melt at 136".AllyZhyclrastamide, C24H26N206, is formed b y the prolonged action ofaqueous ammonia on an alcoholic solution of hydrastine ally1 iodide ;i t may be recrystallised from dilute alcohol, and melts at 156".AIZylhyd~nstinvide, CzrHZ6N2Od, is preparpd by the action of diluteacids, or of ccncentrated aqueous potash, on the amide ; it is depositedfrom dilute alcohol in pale-yellow crystals which melt at 139". Th94 ARSTRACTS OF UHEMICAL PAPERS.hydrochloride is obtaiced from alcohol in pale-yellow crystals meltinga t 211". The subhate crystallises from dilute alcohol in small, deep-yellow, slender needles which melt a t 235". Allylhydrastirnide a1 1ytiodide, C27H31N2051, is formed by the action of allyl iodide on allyl-hydrastamide or ally1 hydrastimide ; it crystallises from dilute alcohol,and melts at 207'. On boiling this compound with concentratedaqueous potash, diallylamine is eliminated, and a substance of theformula C,,,H,,NO, is formed, t o which i t is proposed to apply t h eterm hy drastophthalimidine ; it is deposited in deep-yellow crystalswhich melt at 226", and is strictly analogous to the compoundspreviously described (loc. cit.) . Dibromohydrastopht?2alimidiii,e,C,,H,,NO,Br,, is prepared by treating the preceding compound withbromiue (2 mols.) ; and on the addition of light petroleum to itsbenzene solution, it crystallises in pale-yellow plates melting at 158".The constitution of the above compounds corresponds with that ofthe derivatives previously described (Zoc. cit.).Hydrobromanhydroecgonine. By A. EICHENGR~N and A.EINHOEN (Ber., 23,2888) .-Anhydroecgonine hydrochloride is heatedat 100" for 6-7 days with five parts of a solution of hydrogen brom-ide in glacial acetic acid, saturated at 0". The prodnct is allowed tocrystallise, and the crystals treated with hot water; on cooling,hydrobl.oritanhyclroec~o~ine hydrobmmide, C,H14N02Br,HBr, is depo-sited in strongly refractive prisms which melt at 250" with decorn-position, and are very sparingly soluble in water, alcohol, or glacialacetic acid. J. B. T.By E. JAHNS (Ber. 23, 2972-2978) .-The author has previously described the preparation of thetwo alkaloids, nrecolirze, C8H13N 02. and arecaihe, C,H,,NO,, from themeca nut (Abstr., 1889, 420), and mentioned also a third substance,obtained in small quantit,y, the nature of which could not tlhen beascertained. Further investigation has shown that this compound ischoline, which was identified by its pZatinochloride. The lattercrystallises from water in orange-red, anhydrous, monosymmetricplates, and not as stated by Hundeshagen (J. pr. Chem. [2], 28, 246),in rhombic crvstals. The statement of the latter, that the platino-chloride crystallises from dilnte alcohol in anhydrous, yellow octn-hedra is also partially incorrect, as the crystals thus obtained contain1 mol. H20. The anhydrous compound melts with evolution of gasst 225".When arecoline is heated in a sealed tube with hydrochloric acid,or boiled with hydriodic acid, potash, or baryta-water, a methyl groupis eliminated, and a new compound having the composition C7Hl,N0,obtained. This is isomeric with arecaiine, and may therefore betermed arecnSdine. It is most readily prepared by means of baryta-water or hydriodic acid, and crystallises from 60-70 per cent. alcoholin colonrless, four- or six-sided plates which contain 1 mol. H20. Itloses the latter at lOO", and then melts with evolution of gas at292-223", and carbonises on further heating. It is readily solublein water and dilute alcohol, almost insoluble in absolute alcohol,ether, chloroform, and benzene. Its solution is coloured red by aJ. B. T.Alkaloids of the Areca Nut.Choline aurochloride melts at 244-245"ORGANIC CHEMISTRY. 95trace of ferric chloride, and, like arecai'ne, which it closely resemblesin other respects, it is not poisonous.Its platinochzoride, (C7H,,N0,),,H,PtC16, crystallises in yellowoctohedra which melt at 208-209" with evolution of gas, and theazwochloride, C7HllN02,HAuC14, forms four-sided prisms which meltat 197-198".If finely divided areca'idine be suspended in methyl alcohol, andfthe 'tatter saturated with hydrogen chloride, arecoline is re-formed.If ethyl alcohol be substituted for methyl alcohol, arecaidine ethylether, or homarecohe, C91i,5N02, is obtained; this is a colourless,strongly alkaline liquid, miscible with water, alcohol, and ether,distils without decomposition, is volatile with steam, and haspoisonous properties very similar to those of arecoline. Its hydro-chloride crystallises in very hygroscopic needles which deliquescein the air. The other salts are also deliquescenf, and cannot beobtained in crystals. The picrate is an amorphous resinous mass, andthe aurochZoride an oily liquid, sparingly soluble in cold, readily inhot water. The pZat.inoclzloride forms an orange-red, amorphous masswhich has the composition (C9H,5N02)2,H2PtC16, and commences to.decompose at 100".The above reactions show that areca'idine is a monobasic acid, andthat both oxygen atoms are present as carboxyl. This is confirmedby the fact that no acetyl derivatives of areca'idine can be obtained,which should be readily formed it' the oxygen were present ashydroxyl. The formula for arecoline may therefore be partiallyresolved into C6HloN.COOMe. Experiments to determine the com-position of the group C,H,,N are now in progress. H. G. C.Action of Sulphurous Anhydride on Flour. By - BALLAND( J . Pharm. [ 5 ] , 22, 241--244).-The gluten of flour which has beenacted on by sulphurous anhydride loses its cohesion, so that, in placeof 28-30 per cent., not more than 6 or 7 per cent. can be obtained bythe ordinary process of washing, the remainder passing away with thewash water. The gluten is simply modified, not destroyed, as theflonr retains its nu ti-itive properties. Sulphuric and sulphurous acids,and alkaline sulphides, all affect gluten in this way, whilst certaincompounds, such as sodium chloride, alum, and copper sulphate,favour the aggregation of gluten. Perfectly sound and good breadcan be made from the sulphurised flour by mixing with fresh floiirand increasing the proportion of salt and yeast. Biscuit made fromthe defective flour is quite good. J. T.Formation of Carbamide from Albumin. By E. DRECHSEL(Bey., 23, 3096--3102).-The author has previously shown that amixture of several bases is obtained by boiling casein with con-centrated hydrochloric acid and stannous chloride ; the nitrate ofone of these bases forms with silver nitrate an additive compound ofthe formula ~6H13N302,HN03,AgN03, as the salt probably contains amolecule of water of crysta>llisation; the base, which the authorterms Zysatine or Zysatinine, is homologous with creatinine or wit96 ABSTRACTS OF CHEMICAL PAPERS.creatine, and, like the latter, it yields carbamide on boiling withbaryta-water. The author points out the physiological importance ofhis observations, which move. for the first time. that carbarnide mavbe obtained from album& by simple hydrolytic processes. .IJ. B. T

ISSN:0368-1769    

DOI:10.1039/CA8916000028

出版商:RSC    

年代:1891

数据来源: RSC

摘要:

96 ABSTRACTS OF CHEMICAL PAPERS. P h y s i o l o g i c a 1 C h e m i s t r y . Influence of Bile on Pancreatic Digestion. By S. MARTIN and D. WILLIAMS (Proc. Roy. Soc., 48, 160--165).-1n a previous communication (Abstr., 1888, SlS), it has been pointed out that i n the pig the presence of bile o r bile salts hastens the action of the pancreatic juice on starch. The same holds good for these secretions iu oxen and in the human subject.. Investigations a s d e with certain constituents of the bile and related substances gave the following results :-Sodium taurocholate hastens the pancreatic digestion of starch ; glycocholic acid arrests it ; sodium glycocholate acts like the taurocholate ; glycocine has no effect ; leucine and tyrosine both hinder the digestion to a slight extent; sodium carbonate, when present in the proportion of 0.25 per cent. and over, retards the digestion of starch by pancreatic extract ; but this retardation can be, to a certain extent, neutralised by the addition of bile salts. I n another series of experiments, it was found that the power of bile to hashen pancreatic digestion is not limited to amylolytic diges- tion, bu.t that it is equally, if not more, marked i n its influence on proteolytic digestion. This property is due to the bile salts present ; the action of the sodium glycocholate was found, however, to be less effective than the bile salts as a whole. W.D. H. Action of Nicotine on the Heart and Blood-vessels. By E. COLAS (Compt. rend. Soc. Bid. [9j, 11, 31--33).-Experiments were made on dogs in which small doses of nicotine, dissolved in water, were injected into the femoral vein.Blood pressure was taken from the carotid artery. At first the pressure falls and the heart beats irregularly ; the pressure returns to the normal level, then rises above it ; the lleart beats are very small and very rapid; i t gradually slows, however, till the normal is re-est'ablished. This action is considered to be due to the action of the drug on the intracardinc nerve centres; the accelcration is, however, probably due to its action on the cardiac muscle. I t was also noted that a rise of venous pressure occurs simuitaneously with that in the arterial system. The rise of pressure is probably tlue t o the increased tonicit,y of the heart, as the drug stimulates the vaso-dilatstor nerves, producing increased redness of the organs.W. D. H. Pigments of the Aplysiae. By R. SAINT-LOUP (Compt. rend. SOC. Bid. [9], 11, 116--117).-The green pigment of the liver of thisPHY SIOLOOICAL CHEMISTRY. 97 marine mollusc can be extracted from the organ by alcohol. The extract has an intense green colour, and shows spectroscopically the bands of chlorophyll. After saponificatiori with lime, ether or chloroform dissolves out a yellow pigment, the residue being green. The origin of the pigment is believed to be the food (Algre) of the animal. The pigment is absent in young Aplysiae which had never fed, ar,d gradually diminishes in those allowed to die of starvation. W. D. H. Liquids from Hydatid Cysts. By ROESER ( J . Pharm. [5], 22, 244-249).-The contents of a cyst, examined in 1888, measured about 1100 C.C.The liquid was slightly opaline, faintly alkaline, and had a sp. gr. of 1.0075. The solid residue of 14.7 grams per litre, on calcination, yielded 9.30 grams of ash which contained-sodium chloride, 6.95 grams ; sodium phosphate, carbonate, sulphate, 0.71 gram ; calcium phosphate, sulpllate, and carbonate, 1.26 grams ; iron, magnesia, and loss, 0.38 gram. The organic matter, corresponding with 5.40 ginms per litre, consisted of-albumin, precipitated by heat and acetic acid, 1.060 gram ; glucose, 0.585 ; fatty matter, soluble in ether, 0.260 ; urea, 0.500 ; colouring matter of bile, peptone, extractives, 2.995 grams. The nature of these extlractive substances has not been clearly determined, although the liquids of cysts have been frequently investigated.Numerous authors are quoted to show that the coniposition of the liquids is ex treniely variable. J. T. Iianolin and the Detection of Cholesterin Fats in Man. By 0. LIKBREICH (Chem. Centr., 1890, ii, 149-150 ; from Arch. Physiol., 1890, 363--365).-1n studying the question of the presence of cholesterin and similar fats in the animal epidermis, the author has applied Lieberrnann’s cholestol reaction with acetic anhydride and concentrated sulphuric acid, and aIso the pzpoperty which cholesterin fats have of emulsifying with water to the extent of 200 per ceut. I n this way, cholesterin fats were found on human skin and hair, the feathers and beaks of birds, and the hoofs of horses. In addition t o the Lieberrnann’s test already mentioned, the author has used a modification in which chloroform is used, and which is a, much more delicate test.Fnrther, a separation of the cholesterin fats has been effected by the author, by treating them with hot ethyl acetoacetate or ethyl ethylacetoacetat’e, which dissolve cholesterin much more freely than lanolin. Lanolin was found in human vernix caseosa. J. W. L. Compositjon of the Milk of Cows during Early and Late Periods of Lactation. By M. K ~ H N (Bied. Csntr., 19, 622-628; from Mibhzeit., 18, 922-926).-Experiments were made with cows in early and late periods of lactation, in order to determine the difference in the amount and quality of the milk with cows of the same kind, and of about the same weight, under the same conditions as t o feeding.The resnlts show that considerably more milk is pro- duced in early than in late periods, but that the milk of the latter contains rather more dry matter, €at and protei‘n, than that of the former. The amount of ash and lactic acid is about the same in both Y’QL. IrX. F.98 ABSTRACTS O F CHEMICAL PAPERS. ------- Water. ................ Total solids.. ............ Fat .................... Solids not fat ............ Case'in .................. Sugar .................. Mineral matter .......... cases. I n the late period, the amount of dry substance, milk-sugar, and fat, varies more than in the cnrly period, when the reverse was observed, but in less degree, regarding the other constituents. N. H. J. M. Elephant's Milk. By C. A. DOREMUS (Chern.Cerztr., 1890, ii, 209 ; from Meierei. Tidninq. Milchztg., 1890, 227) .-The following April 5t1h, morning. 67 -567 32 -433 17 -546 14 -887 14 -236" 14 -236 0 -651 analyses have been made :- April 9th, midday. 69 *286 30 '713 19.095 11 -619 3 -694 7 -267 0 -658 -- April loth, morning. 66 *697 33 303 22 '080 11 -233 2 *212 '7 -392 0 '629 The milk has a pleasant Oaste and smell, and resembles that of the cow ; no unpleasant odour is produced on warming it. J . W. L. The Passage of Naphthol into the Urine. By E. DESESQUELLE (Compt. rend. h'oc. BioZ. [ 3 ] , 11, 101--104).-Naphthol is sometimes employed as an inunction in cases of psoriasis. After its use it can b e detected as such in the urine. The residue of the ethereal extract of urine, dissolved in chloroform, treded with soda and then with sulphuric acid, gives the green coloration described by Gautrelet (Trait4 d'analyse urologique, 1889) as characteristic of naphthol.Its extreme insolubility renders its absorption slow as a, rule, and this property also justifies Bouchard's selection of the drug in cases where it is necessary to keep up prolonged antisepsis. W. D. H. Uro-phosphates and Hippuro-phosphates. By GAUBE ( Compt. rend. Soc. Biol. [9], 11, 404--405).-The salts of uric and hippuric acids in the urinc are considered to be double salts composed of two iLCidS united t o the same base, and thus so-called uro-phosphates and hiypuro-phosphates of sodium, potassium, calcium, $c.; argdescribed. W. D. H. Colouring Matter of Yellow Silk and its Relation to Vege- table Carrotene.By R. DUBOIS (Compt. rend., 111, 482-483).- Yellow silk contains several colouring matters, those actually isolated being (1) a golden-yellow compound, soluble in potassium carbonate solution, from which it is precipitated in very brilliant plates; (2) macled crystals, reddish-yellow by bransmitted light, and browii- red by reflected light; ( 3 ) a lemon-yellow, amorphous substance, which separates in rounded granules when its alcoholic solution evaporates spontaneously ; (4) lemon-yellow, octahedral crystals, resembling those * Xvidently the wrong figure has been given here.PEYSIOLOGICATI CHEMISTRY. 99 of sulphur ; and ( 5 ) a deep greenish-blue pigment, which is probably crystallistzble, but which is present only in very small quantity.The substances 2, 3, and 4 agree in many respects with vegetable carrotene ; they are yellowish-red and crystallisable, dissolve in alcohol, ether, chloroform, and benzene, giving golden-yellow so lu- tions, and in carbon bisulphide giviq; a brownish-red solution ; they alter when exposed to air and light, give a continuous absorption spectrum, and dissolve in sulphuric acid with production of a blue coloration which changes to green, and disappears on addition of water. Yellow silk owes part, at any rate, of its colour to a substance show- ing very close analogies to the colouring matter recently extracted from Dictptomus denticornis by R. Blanchard, who regards it. as carrotene of animal origin. C. H. B. Poisoning by Hydrocyanic Acid applied to the Surface of the Eye.By N. GR~HANT (Cornpt. rewd. Hoc. Biol. 191, 11,64-65) .- It was demonstrated that the statement of the older writers that an animal may be poisoned by hydrocyanic acid absorbed through the mucous membrme of the eye is quite correct. Dogs or rabbits are killed in this way in the course of a few minutes. The animals were tracheotornised, and care taken that no poisoning took place from fumes of the drug entering the respiratory cavity. Physiological Action of Potassium Ferroeyanide. By CON- 3EMALE and DUBIQUET (Compt. rend. BOG. Biol. [9], 11, 169-172).--- Potassium ferrocyanide is not t’oxic even when given to animals in doses of 2 grams per kilo. of body weight. In those animals which do not vomit (for instance, the cobaye), there is a diuretic action even after small doses, three hours after its administration.In dogs this is not the case. Repeated doses of the salt, however, cause in- testinal troubles in the dog, vomiting being produced if the amount given exceeds 80 centigrams per kilo. of body weight. In its passage through the system, the ferrocyanide is changed into the ferricyanide, which is eliminated in the urine. Its dinre tic action appears to be connected with this transformation, and the simulta- neous forniation of diuretic potassium salts. Physiological Action of the Soluble Salts of Strontium. By J. V. LABORDIG (Compt. rend. SOC. Biol. [9], 11, 453-459).- Strontium appears to be quite innocuous. In the dog, the only notice- able feature after the administration of the chloride is slight diuresis It thus differs from barium salts, which are very toxic, producing cessation of respiration. Soluble salts of potassium, especially the chloride, lactate, and snlphate, are also poisonous, producing emesis and diarrhoea, and in larger doses slowing of the heart and death from asphyxia.Calcium salts, like those of strontium, are apparenf’ly harmless . W. D. H. W. D. H. W. D. H- Physiological Action of Guaiacol. By P. MARFORI (Ohem. Centr., 1890, ii, 155-156; from Ann. chim. farm., 11, 304--327).-TEe 8 2f 00 ABSTRACTS OF CHEMICAL PAPERS. physiological value of guaiacol was pointed out by Seidel in 1880, since then one difficulty met with in using it has been the absence of distinctive tests of its purity. The author finds that one part of guaiacol should dissolve in (i0 parts of water, the presence of im- piirities rendering it more soluble.Its boiling point is 200--202". One drop of pure guaiacol mixpd with a few drops of concentrated sulphnric acid gives a beautiful permanent purple-red coloration, which is interfered with by even a trace of impurity. The general action of guaiacol consists in first exciting and then paralysing the nerve centres. The paralytic effects are the feebler the higher the animal subjected to its influence. In small doses, gaaiacol does not affect the pulse, in larger doses i t is quickened. The temperature is reduced. After death from the effects of guaiacol, the anthor has observed, in the case of dogs, that the heart is not affected by electric stimulus, although the other muscles are.Its action is similar to that of phenol or catechol, and it is ejected from the system in a similar condition ; i t is, however, not so poisonous as these. J. W. L. Substances which Favour Infection. By G. H. ROGER (Compt. rend. SOC. Riol. [9), 11, 307--310).---There are certain materials, such as lactic acid, which, when introduced simultaneously with microbes into an animal, favour the development of the bacteria. The bacillus of symptomatic anthrax is innocuous to the rabbit,, but is fatal when there is a simultaneous injection of the materials formed by the activity of certain other micro-organisms (B. prodigiosus, 8iaplylococcu.s aureus, &c.). The substance in the cultures that acts thus is soluble i n glycerol but inpoluble in alcohol, and therefore resembles the soluble ferments ; it is, however, not the same substance which liquefies the gelatin in the culture tubes, as it is not destroyed by a temperature of even 130".Similar interactions between other bactvesia are de- scribed; and the fact is thought worthy of note, as it may furnish bad eriologists with a means of re-establishing the virulence of micro- organisms which have become attenuated by prolonged cultivation through the bodies of a long series of animals ; and also that it may help to explain why some vegetable poisons like yapayn and jequirity, which are free from microbes, yet produce a condition of the body in which it Swarms with numerous bacteria which normally are harmless, or only harmful to a slight, degree. W. D. H.96 ABSTRACTS OF CHEMICAL PAPERS.P h y s i o l o g i c a 1 C h e m i s t r y .Influence of Bile on Pancreatic Digestion.By S. MARTINand D. WILLIAMS (Proc. Roy. Soc., 48, 160--165).-1n a previouscommunication (Abstr., 1888, SlS), it has been pointed out that i nthe pig the presence of bile o r bile salts hastens the action of thepancreatic juice on starch. The same holds good for these secretionsiu oxen and in the human subject.. Investigations a s d e with certainconstituents of the bile and related substances gave the followingresults :-Sodium taurocholate hastens the pancreatic digestion ofstarch ; glycocholic acid arrests it ; sodium glycocholate acts like thetaurocholate ; glycocine has no effect ; leucine and tyrosine bothhinder the digestion to a slight extent; sodium carbonate, whenpresent in the proportion of 0.25 per cent.and over, retards thedigestion of starch by pancreatic extract ; but this retardation canbe, to a certain extent, neutralised by the addition of bile salts.I n another series of experiments, it was found that the power ofbile to hashen pancreatic digestion is not limited to amylolytic diges-tion, bu.t that it is equally, if not more, marked i n its influence onproteolytic digestion. This property is due to the bile salts present ;the action of the sodium glycocholate was found, however, to be lesseffective than the bile salts as a whole. W. D. H.Action of Nicotine on the Heart and Blood-vessels. By E.COLAS (Compt. rend. Soc. Bid. [9j, 11, 31--33).-Experiments weremade on dogs in which small doses of nicotine, dissolved in water,were injected into the femoral vein.Blood pressure was taken fromthe carotid artery. At first the pressure falls and the heart beatsirregularly ; the pressure returns to the normal level, then rises aboveit ; the lleart beats are very small and very rapid; i t gradually slows,however, till the normal is re-est'ablished. This action is consideredto be due to the action of the drug on the intracardinc nerve centres;the accelcration is, however, probably due to its action on the cardiacmuscle. I t was also noted that a rise of venous pressure occurssimuitaneously with that in the arterial system. The rise of pressureis probably tlue t o the increased tonicit,y of the heart, as the drugstimulates the vaso-dilatstor nerves, producing increased redness ofthe organs.W. D. H.Pigments of the Aplysiae. By R. SAINT-LOUP (Compt. rend. SOC.Bid. [9], 11, 116--117).-The green pigment of the liver of thiPHY SIOLOOICAL CHEMISTRY. 97marine mollusc can be extracted from the organ by alcohol. Theextract has an intense green colour, and shows spectroscopically thebands of chlorophyll. After saponificatiori with lime, ether orchloroform dissolves out a yellow pigment, the residue being green.The origin of the pigment is believed to be the food (Algre) of theanimal. The pigment is absent in young Aplysiae which had neverfed, ar,d gradually diminishes in those allowed to die of starvation.W. D. H.Liquids from Hydatid Cysts.By ROESER ( J . Pharm. [5], 22,244-249).-The contents of a cyst, examined in 1888, measuredabout 1100 C.C. The liquid was slightly opaline, faintly alkaline, andhad a sp. gr. of 1.0075. The solid residue of 14.7 grams per litre,on calcination, yielded 9.30 grams of ash which contained-sodiumchloride, 6.95 grams ; sodium phosphate, carbonate, sulphate, 0.71gram ; calcium phosphate, sulpllate, and carbonate, 1.26 grams ; iron,magnesia, and loss, 0.38 gram. The organic matter, corresponding with5.40 ginms per litre, consisted of-albumin, precipitated by heat andacetic acid, 1.060 gram ; glucose, 0.585 ; fatty matter, soluble in ether,0.260 ; urea, 0.500 ; colouring matter of bile, peptone, extractives,2.995 grams. The nature of these extlractive substances has notbeen clearly determined, although the liquids of cysts have beenfrequently investigated.Numerous authors are quoted to show thatthe coniposition of the liquids is ex treniely variable. J. T.Iianolin and the Detection of Cholesterin Fats in Man. By0. LIKBREICH (Chem. Centr., 1890, ii, 149-150 ; from Arch. Physiol.,1890, 363--365).-1n studying the question of the presence ofcholesterin and similar fats in the animal epidermis, the author hasapplied Lieberrnann’s cholestol reaction with acetic anhydride andconcentrated sulphuric acid, and aIso the pzpoperty which cholesterinfats have of emulsifying with water to the extent of 200 per ceut.I n this way, cholesterin fats were found on human skin and hair, thefeathers and beaks of birds, and the hoofs of horses.In addition t o the Lieberrnann’s test already mentioned, the authorhas used a modification in which chloroform is used, and which is a,much more delicate test.Fnrther, a separation of the cholesterin fats has been effected bythe author, by treating them with hot ethyl acetoacetate or ethylethylacetoacetat’e, which dissolve cholesterin much more freely thanlanolin.Lanolin was found in human vernix caseosa.J. W. L.Compositjon of the Milk of Cows during Early and LatePeriods of Lactation. By M. K ~ H N (Bied. Csntr., 19, 622-628;from Mibhzeit., 18, 922-926).-Experiments were made with cowsin early and late periods of lactation, in order to determine thedifference in the amount and quality of the milk with cows of thesame kind, and of about the same weight, under the same conditionsas t o feeding.The resnlts show that considerably more milk is pro-duced in early than in late periods, but that the milk of the lattercontains rather more dry matter, €at and protei‘n, than that of theformer. The amount of ash and lactic acid is about the same in bothY’QL. IrX. F98 ABSTRACTS O F CHEMICAL PAPERS.-------Water. ................Total solids.. ............Fat ....................Solids not fat ............Case'in ..................Sugar ..................Mineral matter ..........cases. I n the late period, the amount of dry substance, milk-sugar,and fat, varies more than in the cnrly period, when the reverse wasobserved, but in less degree, regarding the other constituents.N.H. J. M.Elephant's Milk. By C. A. DOREMUS (Chern. Cerztr., 1890, ii,209 ; from Meierei. Tidninq. Milchztg., 1890, 227) .-The followingApril 5t1h,morning.67 -56732 -43317 -54614 -88714 -236"14 -2360 -651analyses have been made :-April 9th,midday.69 *28630 '71319.09511 -6193 -6947 -2670 -658--April loth,morning.66 *69733 30322 '08011 -2332 *212'7 -3920 '629The milk has a pleasant Oaste and smell, and resembles that of thecow ; no unpleasant odour is produced on warming it.J . W. L.The Passage of Naphthol into the Urine. By E. DESESQUELLE(Compt. rend. h'oc. BioZ. [ 3 ] , 11, 101--104).-Naphthol is sometimesemployed as an inunction in cases of psoriasis.After its use it canb e detected as such in the urine. The residue of the ethereal extractof urine, dissolved in chloroform, treded with soda and then withsulphuric acid, gives the green coloration described by Gautrelet(Trait4 d'analyse urologique, 1889) as characteristic of naphthol. Itsextreme insolubility renders its absorption slow as a, rule, and thisproperty also justifies Bouchard's selection of the drug in cases whereit is necessary to keep up prolonged antisepsis. W. D. H.Uro-phosphates and Hippuro-phosphates. By GAUBE ( Compt.rend. Soc. Biol. [9], 11, 404--405).-The salts of uric and hippuricacids in the urinc are considered to be double salts composed of twoiLCidS united t o the same base, and thus so-called uro-phosphates andhiypuro-phosphates of sodium, potassium, calcium, $c.; argdescribed.W.D. H.Colouring Matter of Yellow Silk and its Relation to Vege-table Carrotene. By R. DUBOIS (Compt. rend., 111, 482-483).-Yellow silk contains several colouring matters, those actually isolatedbeing (1) a golden-yellow compound, soluble in potassium carbonatesolution, from which it is precipitated in very brilliant plates;(2) macled crystals, reddish-yellow by bransmitted light, and browii-red by reflected light; ( 3 ) a lemon-yellow, amorphous substance, whichseparates in rounded granules when its alcoholic solution evaporatesspontaneously ; (4) lemon-yellow, octahedral crystals, resembling those* Xvidently the wrong figure has been given herePEYSIOLOGICATI CHEMISTRY.99of sulphur ; and ( 5 ) a deep greenish-blue pigment, which is probablycrystallistzble, but which is present only in very small quantity.The substances 2, 3, and 4 agree in many respects with vegetablecarrotene ; they are yellowish-red and crystallisable, dissolve inalcohol, ether, chloroform, and benzene, giving golden-yellow so lu-tions, and in carbon bisulphide giviq; a brownish-red solution ; theyalter when exposed to air and light, give a continuous absorptionspectrum, and dissolve in sulphuric acid with production of a bluecoloration which changes to green, and disappears on addition ofwater.Yellow silk owes part, at any rate, of its colour to a substance show-ing very close analogies to the colouring matter recently extractedfrom Dictptomus denticornis by R.Blanchard, who regards it. ascarrotene of animal origin. C. H. B.Poisoning by Hydrocyanic Acid applied to the Surface ofthe Eye. By N. GR~HANT (Cornpt. rewd. Hoc. Biol. 191, 11,64-65) .-It was demonstrated that the statement of the older writers that ananimal may be poisoned by hydrocyanic acid absorbed through themucous membrme of the eye is quite correct. Dogs or rabbits arekilled in this way in the course of a few minutes. The animals weretracheotornised, and care taken that no poisoning took place fromfumes of the drug entering the respiratory cavity.Physiological Action of Potassium Ferroeyanide. By CON-3EMALE and DUBIQUET (Compt. rend. BOG. Biol. [9], 11, 169-172).---Potassium ferrocyanide is not t’oxic even when given to animals indoses of 2 grams per kilo.of body weight. In those animals whichdo not vomit (for instance, the cobaye), there is a diuretic action evenafter small doses, three hours after its administration. In dogs thisis not the case. Repeated doses of the salt, however, cause in-testinal troubles in the dog, vomiting being produced if the amountgiven exceeds 80 centigrams per kilo. of body weight.In its passage through the system, the ferrocyanide is changed intothe ferricyanide, which is eliminated in the urine. Its dinre tic actionappears to be connected with this transformation, and the simulta-neous forniation of diuretic potassium salts.Physiological Action of the Soluble Salts of Strontium.By J. V. LABORDIG (Compt.rend. SOC. Biol. [9], 11, 453-459).-Strontium appears to be quite innocuous. In the dog, the only notice-able feature after the administration of the chloride is slight diuresisIt thus differs from barium salts, which are very toxic, producingcessation of respiration. Soluble salts of potassium, especially thechloride, lactate, and snlphate, are also poisonous, producing emesisand diarrhoea, and in larger doses slowing of the heart and deathfrom asphyxia. Calcium salts, like those of strontium, are apparenf’lyharmless . W. D. H.W. D. H.W. D. H-Physiological Action of Guaiacol. By P. MARFORI (Ohem. Centr.,1890, ii, 155-156; from Ann. chim. farm., 11, 304--327).-TEe8 f 00 ABSTRACTS OF CHEMICAL PAPERS.physiological value of guaiacol was pointed out by Seidel in 1880,since then one difficulty met with in using it has been the absence ofdistinctive tests of its purity. The author finds that one part ofguaiacol should dissolve in (i0 parts of water, the presence of im-piirities rendering it more soluble.Its boiling point is 200--202".One drop of pure guaiacol mixpd with a few drops of concentratedsulphnric acid gives a beautiful permanent purple-red coloration,which is interfered with by even a trace of impurity.The general action of guaiacol consists in first exciting and thenparalysing the nerve centres. The paralytic effects are the feeblerthe higher the animal subjected to its influence. In small doses,gaaiacol does not affect the pulse, in larger doses i t is quickened.The temperature is reduced. After death from the effects ofguaiacol, the anthor has observed, in the case of dogs, that the heartis not affected by electric stimulus, although the other muscles are.Its action is similar to that of phenol or catechol, and it is ejected fromthe system in a similar condition ; i t is, however, not so poisonous asthese. J. W. L.Substances which Favour Infection. By G. H. ROGER (Compt.rend. SOC. Riol. [9), 11, 307--310).---There are certain materials, suchas lactic acid, which, when introduced simultaneously with microbesinto an animal, favour the development of the bacteria. The bacillusof symptomatic anthrax is innocuous to the rabbit,, but is fatal whenthere is a simultaneous injection of the materials formed by theactivity of certain other micro-organisms (B. prodigiosus, 8iaplylococcu.saureus, &c.). The substance in the cultures that acts thus is solublei n glycerol but inpoluble in alcohol, and therefore resembles the solubleferments ; it is, however, not the same substance which liquefies thegelatin in the culture tubes, as it is not destroyed by a temperatureof even 130". Similar interactions between other bactvesia are de-scribed; and the fact is thought worthy of note, as it may furnishbad eriologists with a means of re-establishing the virulence of micro-organisms which have become attenuated by prolonged cultivationthrough the bodies of a long series of animals ; and also that it mayhelp to explain why some vegetable poisons like yapayn and jequirity,which are free from microbes, yet produce a condition of the bodyin which it Swarms with numerous bacteria which normally areharmless, or only harmful to a slight, degree. W. D. H

ISSN:0368-1769    

DOI:10.1039/CA8916000096

出版商:RSC    

年代:1891

数据来源: RSC

摘要:

1.00 ABSTRACTS OF CHEMICAL PAPERS. Chemistry of Vegetable Physiology and Agriculture. The Soluble Ferment of Urea. By P. MIQUEL (Compt. rend., 111, 397-;599) .-The soluble urea ferment described by Musculus has not been isolated by subsequent observers. It can, however, readily be obtained in the following way :-Peptone solution mixed with 2 to 3 grams of ammonium carbonate per litre is sterilised byVEQETABLE PHYSIOLOGY AND AQRIOULTURE. 101 filtration through porcelain, and is then inocnlnted with one of the active bacillian ferments of urea, which the author has previously described (Ann. Micro., 1 and 2). After some days, the liquid becomes turbid, and contains the diastase in question. It is necessary that t h e cultivations of bacilli be quite pure, for other organisms may develop to the exclusion of the microbes, or may destroy the diastase as fast as i t is formed.The quantity of soluble ferment obtained in this way per litre of peptone solution is sufficient to convert 60 to 80 grams of urelb into ammonium carbonate in less than an hour. The temperature at which this change takes place most rapidly is 50" to 55", but even at 30" in contact with air, the diastase undergoes profound alteration, and it is completely destroyed after three or four hours. At st tem- perdure near 0", however, the solutions of the diastase in the peptone solution can be kept for several weeks without alteration. At 75", the ferment is conipletiely destroyed in a few minutes, and at 80", in a few seconds. On the other hand, the organisms which secrete the ferment often resist a moist temperature of 95" for two or three hours. The author has caltivated 14 species of micro-organisms, exclusive of Mucedince, which are capable of producing ammoniacal fermenhtion of urea, and which present perfectly distinct morphological characters, and different degrees of activity.All these microbes secrete the soluble ferment when they are grown in proteid cultivation fluids free from urea, and the author concludes that the destruction of urea a t the ordinary temperature in the absence of chemical reagents is due to the action of this soluble ferment. Urea itself has very little nutritive power for lower organisms, and it would seem that the ammonirtcrtl fermentation of urea is not due directly to an act of nutrition, but that the microbes secrete the soluble ferment, and the latter acts on the urea.C. H. B. Nitrification and Denitrification in Soils. By T. LEONE (Gazzetta, 20, 149-151). The author has previously shown (Abstr., 1890, 1453) that the plienomena of nitrificat?ion and denitrification in waters are due to the activity of bacteria and occur in alternation, according to the amount of nutriment present; thus, when an abund- ance of nutritive matter is at hand, the rapid development of the germs is accompanied by the oxidation of tho proteids, partly at the expense of the oxygen in the nitrates present, ammonia and nitrites being formed. On the other hand, nitrificstion commences as soon as the decomposable azotised products are either assimilated or con- verted into ammonium compounds. If ilitrification and denitrifi- cation are determined by similar conditions in soils, the effect of manuring would be in the first iiistance to susQend the ordinary process of nitrification, and to convert part, of the nitrates present into nitrites, nitrification only recommencing when the organic matter was decomposed, and the formation of ammonia had attained a maxi- mum.The following experiments show that, this is actually the case. Two samples, A and B, of 10 kilos. each, of garden mould were placed in cylinders through which air could freely circulate ; with one of these, B, 300 grams of fresh manure (fowl's dung) was mixed. The mould contained 250 milligrams of N2O6 per kilo., and102 ABSTRACTS OF UHFXICAL PAPEXS. an appreciable quantity of nitrous acid, but no trace of ammonia.It was, therefore, in the last stage of nitrification when ammonia had disappeared, but small quantities of nitrites still remained. The sample A (not manured) showed a gradual increase in the quaDtity of nitric acid up to 282 milligrams of nitric anhydride per kilo., when the whole of the nitrous acid had disappeared. In the manured sample, B, the nitric acid decreased in two days to 230 milligrams of nitric anhydr- ide per kilo., in four days to 190 milligrams, and so on. In the initial period, nitrous acid was formed, but subsequently disappeared ; after 15 days, no trace of either nitric or nitrous acid remained ; the quantity of ammonia, on the other hand, increased regularl_~- and attained a maximum on the 29th day, after which it remained constant, for five or six days.On the 35th day, nitrification recommenced, nitrous acid reappearing and the ammonia beginning to decrease ; the transforma- tion of the ammonia into nitrous acid and of the latter into nitric acid continued during three months, after which no trace of either ammonia or nitrous acid could be found, only nitric acid remaining in the soil. The manuring of mils, therefore, gives rise to a cycle of phenomena, nitrification being first arrested and the nitrates and nitrites reduced until a maximum formation of ammonia is attained, when nitrification again commences. The destruction of the nitrates and nitrites in the soil is complete or partial, according as the supply of manure is abundant or otherwise.S. B. A. A. Reducing Power of Micro-organisms. By T. LEONE (Gazzetta, 20, 152-154).-The author criticises the methods and results of De Blasi and Travali (Abstr., 1890, p. 1453), and maintains that nitrifica- tion is a biological phenomenon taking place under the conditions described (see preceding abstract and 1890, 1453). The reduction of nitrates in the presence of rapidly developing germs takes place simaltaneously with the oxidation of the organic compounds present, and is due to the abstraction of oxygen from the nitrates for that purpose. S. R. A. A. Biogenesis of Hydrogen Sulphide. By DEBRAPE and LEGRAIN (Compt. rend. SOC. Biol. [9], 11, 466-468).-1t is well known that certain bacteria produce hydrogen sulphide from albuminous materials. The number of microbes that act thus is by no means limited, and by appropriate means nearly all of them can be made to produce the gas in cultures in which the action is anagrobic.The formation of the gas appears to depend on the amount of the nascent hydrogen present. W. D. H. Chlorophyllic Assimilation by Trees with Red Leaves. By H. JIJMELLE (Compt. rend., 111, 380-382).-The relative activity of green and other leaves was compared by exposing theu to sunlight under comparable conditions in a closed atmosphere contaiuiag a known quantity of carbonic anhydride, and determining how much carbonic anhydride was decomposed ; the weights of the dried leaves being ascertained a t the end of the experiment. The results show that in t'rees with red or coppery leaves, the chlorophyllian assimilation is always lower than in the same trees with green leaves, a resultVEGETABLE PHYSIOLOGY AND AGRICULTURE. 103 which explains the well known fact t h a t trees of the former clam increase in size much more slowly than those of the latter.In some cases the differences are very great ; the assimilation of the green beech is about six times as great, as that of the copper beech, and there is the same difference between the ordinary and the purple sycamore. C. H. B. Sugars in Mushrooms. By E. BOURQUFLOT (Compt. rend., 111, 534-536 and 5i8-580).--Lactarius piperatus Scop., when exanlined immediately after i t is gathered, contains b considerable quantity of trehalose, but very little mannitol. If, however, it, is dried and then treated with water, no trehalose is obtained ; mannitol alone is present.The same phenomenon is observed if the mushrooms are merely kept for a few hours aftAer being gathered, and hence the disappearance of the trehalose is a result of the continuance of the vital processes of the mushroom. This conclusion is confirmed by the fact that if the mushrooms are kept in a vessel filled with chloroform vapour, the trehalose remains, although the mushrooms become dark-brown and exude a lai-ge quantity of liquid. Examiuation of various species of mnshrooms at different stages of growth shows that when young they contain trehalose and no mannitol, in the middle period they contain both, and when mature they contain mannitol only. Amanita mappa is an exception, since in all stages it contains mannitul and no trchalose.The conversion of trehalose into mannitol is a process of reduction, and is probably connected with the formation and maturation of the spores. I n many species the phenomena are complicated by an increase in the amount of glucose that they contain, and in others by the appearance of glucose which is not present in the earlier stages of their growth. Loss of Sugar in Beetroot. By G. MAREK (Bied. Centr., 19, 619-622 ; from Deut. Landw. Pre.cse, 17, 310--311).-The loss of sugar in beetroot is closely connected with the amount originally contained. Roots were examined in December, 1888, and in March 1889, the sugar being determined by the polarisation of the juice and by extraction with alcohol. The loss in all cases was very considerable. The loss is greatest with roots containing most sugar ; the kind, soil, and manuring have less t o do with it, and everything which raises the amount of sugar in the roots increases the liability to lose sugar.It is also shown that the higher the temperature at which the roots are kept, the greater is the amount of sugar which is lost. When roots which originally contain equal amounts of sugar lose unequally, the greatest loss will be in those which contain the greatest amount of non-saccharine substances. This fact is of importance in the selec- tion of roots for seed. Comparative experiments were made with nitrogenous and phosphatic manures, the results of which show that phosphoric acid has no unfavourable effect on the durability of the roots, as is frequently stated.In the manufacture of sugar, those roots which contain most sugar should be used first. C. H. B. N. H. J. M.104 ABSTRACTS OF CHEMICAL PAYERS. Behaviour of Tannin in Plants. By M. BUSGEN (E’orsch. Gebiete agrile. yhysik., 13, 305 ; from Jena. Zeit. Naturwiss., 24).--Experi- ments were made to determine whether a disappearance of tannin in any parts of plants can be shown to take place. Microchemical methods were employed. Kraus makes a distinction between ‘( primary ” tannin, which is produced with, and “ secondary ” tannin, which is formed without, the intervention of light. In certain cases both were found to disappear. Tannin was found to disappear from cells which were on the point of dying as well as from cells possess- ing more vitality.The author doubts whether the tannin is again used in building up. Direct proof of the production of tannin from sugar was obtained i n a manner similar to that of the formation of starch from sugar. Portions of shade-leaves of various plants were placed with the upper side on a 10 per cent. solution of grape-sugar, the chief veins having been cut to facilitate the entry of the solution. Portions of the same leaves were similarly placed on water as a control experiment-a necessary precaution, as in many leaves the amount of tannin increases after they are cut o f and kept in tbe dark. After four to six days, the leaves showed a considerable increase in the amount of tannin. It has still to be shown what intermediate compounds are formed, and also whether other substances besides grape-sugar will produce tannin.N. H. J. M. Cultivation of Wheat in a Sterile Siliceous Sand. BS PAGNOUL (C‘ompt. rend., 111, 507-509) .-Calcium sulphate and natural phosphates were mixed with the sand; soluble salts were added by watering the experimental pots with solutions of definite strengths. Phosphates are indispensable ; a yield of 46 quintals per hectare with a complete manure fell to 12 quintals in absence oi soluble phosphate, and to ‘2 quintals when no phosphate was added at all. The ratio of grain to straw also depends oa the mpply of phos- phate, and the suppression of phosphoric acid retards the maturing of the wheat by 10 days. Presence or absence of nitrogen is not of such vital importance, probably because the wbeat can obtain a certain quant.ity from the air.Absence of nitrogen reduced the yield from 46 to 11 quintals per hectare. In a complete manure, nitric nitrogeii has only a slightly greater efficiency than ammoniacal nitrogen, but in absence of potassium, the yield with the former is double the yield with the latter. It follows that the presence of potassium is essential when ammoniacal manures are used. The proportion of nitrogenous compounds in the grain increases with the quantity of nitrogen placed at the disposal of the plant. It fell to 8-9 per cent. with a non-nitrogenous manure, but rose to 20 per cent., which is higher than the ordinary maximum, when the quantity of nitrogen supplied was greater than that existing in the most fertile soils. Nitric nitrogen was never found in appreciable quantity in plants stinted of nitrogen, but rises to 0.2 per cent., especially in February and Marcb, in those plants which had received nitrogen either in the form of ammonia or nitrates.In absence of potassium, the quantityVEQETABLE PHYSIOLOQY AND AGRICULTURE. 105 of nitric nitrogen is very small, and traces of ammoniacal nitrogen are present. C . H. B. Examination of Potato-Spirit Liquor. By M. K ~ H N (Bied. Centr., 19, 628 ; from Milchzeit., 18, 926).--The followirig numbers show the percentages in the sample of the liquor which was used as cattle food :- Non-nitrogenous Sand in Fat. Protein. Pure ash. Crude fibre. extractives. pure ash. 0.13 2-61 1.20 0.43 3.50 0.44 The Behaviour of Sandy Soil towards Superphosphate. By A. THOMSON ( B i d Centr., 19, 585--588).-The absorptive power of pure sea-sand for phosphoric acid was determined as well as that of the same sand containing known amounts of orthoclase, of calcium carbonate, of ferric and aluminum hydroxides, of calcium carbonate and ort,hoclase, and of calcium carbonate and the mixed ferric and aluminium hydroxides.The effect of sodium chloride and potassium nitrate on the process of absorption was also studied. Pure sand offers no resistance to the extraccion of the phosphoric acid of superphosphate by pure water, or solutions of sodium chloride and potassium nitrate. The addition of orthoclase is without effect. Calcium carbonate combines quickly with the soluble phosphoric acid ; and the hydroxides of iron and aluminium are very active in retaining phosphoric acid, especially when used in conjunction with calcium carbonate.1 or 2 per cent. solutions of sodium chloride extract from snperphosphate rather less phosphoric acid than distilled water ; but in presence of calcium carbonate and ferric and aluminium hydroxides, the dilute salt solution extracts more phosphoric acid than water alone. Dilute potassium nitrate sohtions diminish the absorptive power of all the substances employed more than sodium chloride. The results point to the conclusion that the full benefit of manuring with superphosphate (in a sandy soil) will only be attained when large amounts of lime or smaller amounts of lime and ferric and aluminium hydroxides are well distributed in the soil, and when t h e soil does not contain too much nitrate.I n absence of these con- ditions, the application of superphosphate should be avoided. The methods of experimenting and the apparatus employed are described in detail in the original paper (Inaug. Diss. Dorpat, 1890). Composition of Bone-meal. By J. STOCKLASA (Chenz. Zeit., 14, 1-2, 21, 32-33).-The author has examined bone-meal obtained by different metiiods. Tn the first series of expeiimcnts, bones were digested for six hours in soft water, at 95", by which they yielded 2 3 per cent. of fat, and lost, 0.53 per cent. of nitrogen; they were then steamed, either under a pressure of 2.5 atrnospheres for 75 minutes (Itesults A), or under 1.5 atmospheres for 60 minutes (Results B), or under 0.5 atmosphere for an hour (Results C), dried at 40°, pulverisod, and the meal and grit analysed, with the results given in the table.In the second series of experiments, it was sought to N. H. J. M. pu'. H. J. M.106 ABSTRAOTS OF CHEMIOAL PAPERS. E. -- 31 -24 6 -42 48 -93 8.41 4 -36 extract the fat by means of light petroleum :-Results D were obtained from meal prepared from bone containing 9.2 per cent. of f a t ; the extraction was conducted under 1.2 atmospheres, the residual petroleum expelled with steam, the extracted bones dried at 45", and pulverised. For Results E, the bones containing 8.8 per cent. of fat were extracted without pressure, and treated like D, but dried at 36". Results F: Bones containing 8.7 per cent. of fat, extracted under 1.3 atmo- spheres, then steamed under 2 at,mospheres pressure for 20 minutes, &c.Results G: Bones containing 8.9 per cent. of fat, extracted under 1.2 atmospheres pressure, then steamed undcr 3 atmospheres for 30 minutes, &c. Organic non-fatty matter .... Fat ....................... Inorganic matter. ........... Water .................... Nitrogen .................. 26 -38 5 *51 56 -24 11 *8 3 -77 - B. 34.25 9.06 47.87 8'82 4.96 27 *82 9 -38 52.43 10 '37 4 -05 - 26-34 2-85 61-69 9-12 3.94 - C. - 29 *54 11 -32 50 -43 8 9 1 4 *25 - D. 33 -67 7 -84 49 *35 9 -14 4 *83 1 F. 1 G. .)-I- Steaming, when the pressure is sufficiently great to remove fat, also removes much nitrogen. By the second method of extraction, less nitrogen is lost, the coarse crushed bone makes it saperior granular charcoal, and the gelatin from the bone grit is excellent, whilst the fat contains less calcium and ammonium oleates, palmitates, and stearates.For agricultural purposes, the fat impedes decompo- sition, both of the nitrogenous matter and the phosphate. The frag- ments of bone containing most fat are more brittle ; hence the meal is found to contain more fat than the grit, and so on up the scale of coarseness. The author gives results showing this. He regards finely pulverisrd bone meal deprived of fat as an excellent manure, superior to basic slag, and not even second to precipitated phosphate in action, its apparent failure, hitherto being attributed to want of attention to the points now set forth in the present paper. D. A. L. Amount of Fat in Bone-meal. By J. MERZ (Chent. Zeit., 14, 95) .-Xeferring to Stocklasa's communication (preceding abstract), it is considered that justice is not done to the extraction method in the results quoted ; therefore the author of the present note calls attention to three experiments of his own, wherein the fat in bones was reduced to 0.32, 0.28, and 0.26 respectively, in from six to seven and a half hours, by extraction with petroleum without pressure, the latter not being regarded as a factor in the extraction of fat on a large scale any more than it is on a small scale in laboratory fat estimation. In fact the more the former operation is made to resemble the latter, the greater is the yield of fat, and the better the quality of the bone- meal. D.A. L.1.00 ABSTRACTS OF CHEMICAL PAPERS.Chemistry of Vegetable Physiology and Agriculture.The Soluble Ferment of Urea.By P. MIQUEL (Compt. rend.,111, 397-;599) .-The soluble urea ferment described by Musculushas not been isolated by subsequent observers. It can, however,readily be obtained in the following way :-Peptone solution mixedwith 2 to 3 grams of ammonium carbonate per litre is sterilised bVEQETABLE PHYSIOLOGY AND AQRIOULTURE. 101filtration through porcelain, and is then inocnlnted with one of theactive bacillian ferments of urea, which the author has previouslydescribed (Ann. Micro., 1 and 2). After some days, the liquid becomesturbid, and contains the diastase in question. It is necessary that t h ecultivations of bacilli be quite pure, for other organisms may developto the exclusion of the microbes, or may destroy the diastase as fast as i tis formed.The quantity of soluble ferment obtained in this way perlitre of peptone solution is sufficient to convert 60 to 80 grams of urelbinto ammonium carbonate in less than an hour. The temperature atwhich this change takes place most rapidly is 50" to 55", but even at30" in contact with air, the diastase undergoes profound alteration,and it is completely destroyed after three or four hours. At st tem-perdure near 0", however, the solutions of the diastase in the peptonesolution can be kept for several weeks without alteration. At 75", theferment is conipletiely destroyed in a few minutes, and at 80", in a fewseconds. On the other hand, the organisms which secrete the fermentoften resist a moist temperature of 95" for two or three hours.The author has caltivated 14 species of micro-organisms, exclusiveof Mucedince, which are capable of producing ammoniacal fermenhtionof urea, and which present perfectly distinct morphological characters,and different degrees of activity.All these microbes secrete thesoluble ferment when they are grown in proteid cultivation fluids freefrom urea, and the author concludes that the destruction of urea a tthe ordinary temperature in the absence of chemical reagents is due tothe action of this soluble ferment. Urea itself has very little nutritivepower for lower organisms, and it would seem that the ammonirtcrtlfermentation of urea is not due directly to an act of nutrition, but thatthe microbes secrete the soluble ferment, and the latter acts on theurea.C. H. B.Nitrification and Denitrification in Soils. By T. LEONE(Gazzetta, 20, 149-151). The author has previously shown (Abstr.,1890, 1453) that the plienomena of nitrificat?ion and denitrification inwaters are due to the activity of bacteria and occur in alternation,according to the amount of nutriment present; thus, when an abund-ance of nutritive matter is at hand, the rapid development of thegerms is accompanied by the oxidation of tho proteids, partly at theexpense of the oxygen in the nitrates present, ammonia and nitritesbeing formed. On the other hand, nitrificstion commences as soon asthe decomposable azotised products are either assimilated or con-verted into ammonium compounds.If ilitrification and denitrifi-cation are determined by similar conditions in soils, the effect ofmanuring would be in the first iiistance to susQend the ordinaryprocess of nitrification, and to convert part, of the nitrates presentinto nitrites, nitrification only recommencing when the organic matterwas decomposed, and the formation of ammonia had attained a maxi-mum. The following experiments show that, this is actually the case.Two samples, A and B, of 10 kilos. each, of garden mould wereplaced in cylinders through which air could freely circulate ; withone of these, B, 300 grams of fresh manure (fowl's dung) wasmixed. The mould contained 250 milligrams of N2O6 per kilo., an102 ABSTRACTS OF UHFXICAL PAPEXS.an appreciable quantity of nitrous acid, but no trace of ammonia.Itwas, therefore, in the last stage of nitrification when ammonia haddisappeared, but small quantities of nitrites still remained. Thesample A (not manured) showed a gradual increase in the quaDtity ofnitric acid up to 282 milligrams of nitric anhydride per kilo., when thewhole of the nitrous acid had disappeared. In the manured sample, B,the nitric acid decreased in two days to 230 milligrams of nitric anhydr-ide per kilo., in four days to 190 milligrams, and so on. In the initialperiod, nitrous acid was formed, but subsequently disappeared ; after15 days, no trace of either nitric or nitrous acid remained ; the quantityof ammonia, on the other hand, increased regularl_~- and attained amaximum on the 29th day, after which it remained constant, for fiveor six days.On the 35th day, nitrification recommenced, nitrous acidreappearing and the ammonia beginning to decrease ; the transforma-tion of the ammonia into nitrous acid and of the latter into nitric acidcontinued during three months, after which no trace of either ammoniaor nitrous acid could be found, only nitric acid remaining in the soil.The manuring of mils, therefore, gives rise to a cycle of phenomena,nitrification being first arrested and the nitrates and nitrites reduceduntil a maximum formation of ammonia is attained, when nitrificationagain commences. The destruction of the nitrates and nitrites inthe soil is complete or partial, according as the supply of manure isabundant or otherwise.S. B. A. A.Reducing Power of Micro-organisms. By T. LEONE (Gazzetta,20, 152-154).-The author criticises the methods and results of DeBlasi and Travali (Abstr., 1890, p. 1453), and maintains that nitrifica-tion is a biological phenomenon taking place under the conditionsdescribed (see preceding abstract and 1890, 1453). The reduction ofnitrates in the presence of rapidly developing germs takes placesimaltaneously with the oxidation of the organic compounds present,and is due to the abstraction of oxygen from the nitrates for thatpurpose. S. R. A. A.Biogenesis of Hydrogen Sulphide. By DEBRAPE and LEGRAIN(Compt. rend. SOC. Biol. [9], 11, 466-468).-1t is well known thatcertain bacteria produce hydrogen sulphide from albuminous materials.The number of microbes that act thus is by no means limited, and byappropriate means nearly all of them can be made to produce the gasin cultures in which the action is anagrobic.The formation of the gasappears to depend on the amount of the nascent hydrogen present.W. D. H.Chlorophyllic Assimilation by Trees with Red Leaves. ByH. JIJMELLE (Compt. rend., 111, 380-382).-The relative activity ofgreen and other leaves was compared by exposing theu to sunlightunder comparable conditions in a closed atmosphere contaiuiag a knownquantity of carbonic anhydride, and determining how much carbonicanhydride was decomposed ; the weights of the dried leaves beingascertained a t the end of the experiment. The results show that int'rees with red or coppery leaves, the chlorophyllian assimilation isalways lower than in the same trees with green leaves, a resulVEGETABLE PHYSIOLOGY AND AGRICULTURE.103which explains the well known fact t h a t trees of the former clamincrease in size much more slowly than those of the latter. In somecases the differences are very great ; the assimilation of the greenbeech is about six times as great, as that of the copper beech, andthere is the same difference between the ordinary and the purplesycamore. C. H. B.Sugars in Mushrooms. By E. BOURQUFLOT (Compt. rend., 111,534-536 and 5i8-580).--Lactarius piperatus Scop., when exanlinedimmediately after i t is gathered, contains b considerable quantity oftrehalose, but very little mannitol. If, however, it, is dried and thentreated with water, no trehalose is obtained ; mannitol alone is present.The same phenomenon is observed if the mushrooms are merely keptfor a few hours aftAer being gathered, and hence the disappearance ofthe trehalose is a result of the continuance of the vital processes ofthe mushroom.This conclusion is confirmed by the fact that if themushrooms are kept in a vessel filled with chloroform vapour, thetrehalose remains, although the mushrooms become dark-brown andexude a lai-ge quantity of liquid.Examiuation of various species of mnshrooms at different stages ofgrowth shows that when young they contain trehalose and nomannitol, in the middle period they contain both, and when maturethey contain mannitol only. Amanita mappa is an exception, sincein all stages it contains mannitul and no trchalose.The conversion of trehalose into mannitol is a process of reduction,and is probably connected with the formation and maturation of thespores. I n many species the phenomena are complicated by anincrease in the amount of glucose that they contain, and in othersby the appearance of glucose which is not present in the earlierstages of their growth.Loss of Sugar in Beetroot.By G. MAREK (Bied. Centr., 19,619-622 ; from Deut. Landw. Pre.cse, 17, 310--311).-The loss ofsugar in beetroot is closely connected with the amount originallycontained. Roots were examined in December, 1888, and in March1889, the sugar being determined by the polarisation of the juice andby extraction with alcohol.The loss in all cases was very considerable.The loss is greatest with roots containing most sugar ; the kind, soil,and manuring have less t o do with it, and everything which raisesthe amount of sugar in the roots increases the liability to lose sugar.It is also shown that the higher the temperature at which the rootsare kept, the greater is the amount of sugar which is lost. Whenroots which originally contain equal amounts of sugar lose unequally,the greatest loss will be in those which contain the greatest amountof non-saccharine substances. This fact is of importance in the selec-tion of roots for seed. Comparative experiments were made withnitrogenous and phosphatic manures, the results of which show thatphosphoric acid has no unfavourable effect on the durability of theroots, as is frequently stated.In the manufacture of sugar, those roots which contain most sugarshould be used first.C.H. B.N. H. J. M104 ABSTRACTS OF CHEMICAL PAYERS.Behaviour of Tannin in Plants. By M. BUSGEN (E’orsch. Gebieteagrile. yhysik., 13, 305 ; from Jena. Zeit. Naturwiss., 24).--Experi-ments were made to determine whether a disappearance of tanninin any parts of plants can be shown to take place. Microchemicalmethods were employed. Kraus makes a distinction between‘( primary ” tannin, which is produced with, and “ secondary ” tannin,which is formed without, the intervention of light. In certain casesboth were found to disappear. Tannin was found to disappear fromcells which were on the point of dying as well as from cells possess-ing more vitality. The author doubts whether the tannin is againused in building up.Direct proof of the production of tannin fromsugar was obtained i n a manner similar to that of the formation ofstarch from sugar. Portions of shade-leaves of various plants wereplaced with the upper side on a 10 per cent. solution of grape-sugar,the chief veins having been cut to facilitate the entry of the solution.Portions of the same leaves were similarly placed on water as acontrol experiment-a necessary precaution, as in many leaves theamount of tannin increases after they are cut o f and kept in tbe dark.After four to six days, the leaves showed a considerable increase inthe amount of tannin.It has still to be shown what intermediatecompounds are formed, and also whether other substances besidesgrape-sugar will produce tannin. N. H. J. M.Cultivation of Wheat in a Sterile Siliceous Sand. BSPAGNOUL (C‘ompt. rend., 111, 507-509) .-Calcium sulphate andnatural phosphates were mixed with the sand; soluble salts wereadded by watering the experimental pots with solutions of definitestrengths. Phosphates are indispensable ; a yield of 46 quintalsper hectare with a complete manure fell to 12 quintals in absence oisoluble phosphate, and to ‘2 quintals when no phosphate was added atall. The ratio of grain to straw also depends oa the mpply of phos-phate, and the suppression of phosphoric acid retards the maturing ofthe wheat by 10 days.Presence or absence of nitrogen is not of suchvital importance, probably because the wbeat can obtain a certainquant.ity from the air. Absence of nitrogen reduced the yield from46 to 11 quintals per hectare. In a complete manure, nitric nitrogeiihas only a slightly greater efficiency than ammoniacal nitrogen, butin absence of potassium, the yield with the former is double theyield with the latter. It follows that the presence of potassium isessential when ammoniacal manures are used.The proportion of nitrogenous compounds in the grain increaseswith the quantity of nitrogen placed at the disposal of the plant. Itfell to 8-9 per cent. with a non-nitrogenous manure, but rose to20 per cent., which is higher than the ordinary maximum, when thequantity of nitrogen supplied was greater than that existing in themost fertile soils.Nitric nitrogen was never found in appreciable quantity in plantsstinted of nitrogen, but rises to 0.2 per cent., especially in Februaryand Marcb, in those plants which had received nitrogen either in theform of ammonia or nitrates.In absence of potassium, the quantitVEQETABLE PHYSIOLOQY AND AGRICULTURE. 105of nitric nitrogen is very small, and traces of ammoniacal nitrogenare present. C . H. B.Examination of Potato-Spirit Liquor. By M. K ~ H N (Bied.Centr., 19, 628 ; from Milchzeit., 18, 926).--The followirig numbersshow the percentages in the sample of the liquor which was used ascattle food :-Non-nitrogenous Sand inFat. Protein.Pure ash. Crude fibre. extractives. pure ash.0.13 2-61 1.20 0.43 3.50 0.44The Behaviour of Sandy Soil towards Superphosphate. ByA. THOMSON ( B i d Centr., 19, 585--588).-The absorptive power ofpure sea-sand for phosphoric acid was determined as well as that ofthe same sand containing known amounts of orthoclase, of calciumcarbonate, of ferric and aluminum hydroxides, of calcium carbonateand ort,hoclase, and of calcium carbonate and the mixed ferric andaluminium hydroxides. The effect of sodium chloride and potassiumnitrate on the process of absorption was also studied.Pure sand offers no resistance to the extraccion of the phosphoricacid of superphosphate by pure water, or solutions of sodium chlorideand potassium nitrate. The addition of orthoclase is without effect.Calcium carbonate combines quickly with the soluble phosphoricacid ; and the hydroxides of iron and aluminium are very active inretaining phosphoric acid, especially when used in conjunction withcalcium carbonate.1 or 2 per cent. solutions of sodium chlorideextract from snperphosphate rather less phosphoric acid than distilledwater ; but in presence of calcium carbonate and ferric and aluminiumhydroxides, the dilute salt solution extracts more phosphoric acidthan water alone. Dilute potassium nitrate sohtions diminish theabsorptive power of all the substances employed more than sodiumchloride.The results point to the conclusion that the full benefit of manuringwith superphosphate (in a sandy soil) will only be attained whenlarge amounts of lime or smaller amounts of lime and ferric andaluminium hydroxides are well distributed in the soil, and when t h esoil does not contain too much nitrate.I n absence of these con-ditions, the application of superphosphate should be avoided. Themethods of experimenting and the apparatus employed are describedin detail in the original paper (Inaug. Diss. Dorpat, 1890).Composition of Bone-meal. By J. STOCKLASA (Chenz. Zeit., 14,1-2, 21, 32-33).-The author has examined bone-meal obtained bydifferent metiiods. Tn the first series of expeiimcnts, bones weredigested for six hours in soft water, at 95", by which they yielded2 3 per cent. of fat, and lost, 0.53 per cent. of nitrogen; they werethen steamed, either under a pressure of 2.5 atrnospheres for75 minutes (Itesults A), or under 1.5 atmospheres for 60 minutes(Results B), or under 0.5 atmosphere for an hour (Results C), dried at40°, pulverisod, and the meal and grit analysed, with the results givenin the table.In the second series of experiments, it was sought toN. H. J. M.pu'. H. J. M106 ABSTRAOTS OF CHEMIOAL PAPERS.E.--31 -246 -4248 -938.414 -36extract the fat by means of light petroleum :-Results D were obtainedfrom meal prepared from bone containing 9.2 per cent. of f a t ; theextraction was conducted under 1.2 atmospheres, the residual petroleumexpelled with steam, the extracted bones dried at 45", and pulverised.For Results E, the bones containing 8.8 per cent. of fat were extractedwithout pressure, and treated like D, but dried at 36".Results F:Bones containing 8.7 per cent. of fat, extracted under 1.3 atmo-spheres, then steamed under 2 at,mospheres pressure for 20 minutes, &c.Results G: Bones containing 8.9 per cent. of fat, extracted under1.2 atmospheres pressure, then steamed undcr 3 atmospheres for30 minutes, &c.Organic non-fatty matter ....Fat .......................Inorganic matter. ...........Water ....................Nitrogen ..................26 -385 *5156 -2411 *83 -77-B.34.259.0647.878'824.9627 *829 -3852.4310 '374 -05 -26-342-8561-699-123.94-C. -29 *5411 -3250 -438 9 14 *25 -D.33 -677 -8449 *359 -144 *831 F. 1 G. .)-I-Steaming, when the pressure is sufficiently great to remove fat,also removes much nitrogen. By the second method of extraction,less nitrogen is lost, the coarse crushed bone makes it saperiorgranular charcoal, and the gelatin from the bone grit is excellent,whilst the fat contains less calcium and ammonium oleates, palmitates,and stearates. For agricultural purposes, the fat impedes decompo-sition, both of the nitrogenous matter and the phosphate. The frag-ments of bone containing most fat are more brittle ; hence the meal isfound to contain more fat than the grit, and so on up the scale ofcoarseness. The author gives results showing this. He regardsfinely pulverisrd bone meal deprived of fat as an excellent manure,superior to basic slag, and not even second to precipitated phosphatein action, its apparent failure, hitherto being attributed to want ofattention to the points now set forth in the present paper.D. A. L.Amount of Fat in Bone-meal. By J. MERZ (Chent. Zeit., 14,95) .-Xeferring to Stocklasa's communication (preceding abstract), itis considered that justice is not done to the extraction method in theresults quoted ; therefore the author of the present note calls attentionto three experiments of his own, wherein the fat in bones was reducedto 0.32, 0.28, and 0.26 respectively, in from six to seven and a halfhours, by extraction with petroleum without pressure, the latter notbeing regarded as a factor in the extraction of fat on a large scaleany more than it is on a small scale in laboratory fat estimation. Infact the more the former operation is made to resemble the latter, thegreater is the yield of fat, and the better the quality of the bone-meal. D. A. L

ISSN:0368-1769    

DOI:10.1039/CA8916000100

出版商:RSC    

年代:1891

数据来源: RSC

摘要:

ANALYTICAL CHEMISTRY. 107 A n a l y t i c a l Chemistry. Estimation of Hydrogen Chloride in Solutions of Hydroxyl- amine Hydrochloride. By J. A. MULLEK. (Rzill. Xoc. Chim. [ 3 ] , 3, 605).-Phenolphthalei'n is unaffected by solutions of hydroxylamine hydrochloride, and the amount of acid present may be estimated by means of a standard solution of sodium hydroxide, free from carbon- ate, using phenolphthalein as the indicator. Pyridine, picolines, and lutidines behave similarly. T. G. N. Estimation of Sulphur in Inorganic Sulphides. By L. BLUM (Zeit. anal. Gem., 29, 411412).--The method publiahed by Jannasch (Abstr., 1889, 1244, and 1890, 1187) is not new, having been already brought forward by Sauer, in 1873 (Abatr., 1873, 939). M. J. S. Estimation of Nitrogen by the Schultze-Tiemmaam (Schloesing's) Method.By F. COGHIUS and T. MOELLER (Chern. Zeit., 14, 3%).-Low results are obtained by this method, especially in the examination of explosives. This is attributed by the authors to the addition of too much water, and to the want of proper relation- ship between the size of the apparatus used and the quantity of mate- rial employed. In some test experiments they used a long-necked 350 C.C. flask, a measuring tube of 150 C.C. capacity, ferrous chloride solution containing 70 grams in 100 grams of water, hydrochloric acid of about 37 per cent., and employed 0-3-0.4 gram of potassium nitrate, 5-15 C.C. of the ferrous chloride solution, and twice the quantity of the hydrochloric acid. The ordinary course of operation was followed, avoiding unuecessary boiling to drive out the air.When 25 to 50 C.C. of water was added, the analysis lasted 30 to 40 minutes, and the results varied between 13.76 and 13.86, mean 13.81, whilst with 80 to 150 C.C. of water the variation in the results was from 13.05 to 1339, mean 13.21, and the analysis lasted 70 to 90 minutes. D. A. L. Estimation of Nitrogen in Sodium Nitrate. By 0. FOERSTER (Chem. Zeit., 14, 509-510 ; compare Ahstr., 1889, 547, 746).-Two or three grams of the nitrate is dried at 150" or by heating to inci- pient fusion, weighed, and repeatedly evaporated to dryness on a water- bath in a tared crucible, with 25 C.C. of about 19 per cent. hydro- chloric acid. After about the third evaporation, the nitrate is com- pletely converted into chloride, which is dried at 150°, ignited slightly, and weighed, and the nitrogen calculated from the difference. The method yields satisfactory results, but only in the absence of other substances, which would be attacked by hydrochloric acid.D. A. L. Estimation of Nitric Nitrogen as Nitric Oxide. By F. SCHEIDING (Chem Zeit., 14, 635-637).-For estimating nitric nitrogen as nitric oxide, the author has devised and employs the apparatus shown in the drawing, which is provided with a measuring tube108 ABSTRAOTS OF CHEMIOAL PAPERS. having a globular expansion, a glass tap H with a small funnel at the top, and a special arrangement intimately attached by india-rubber tubing or fusion to the bottom. In operation, tube L is connected in a suithble manner with a, movable reservoir containing sodium hydroxide, sp.gr. 1.25, with which the apparatus is charged to the level of 4 by raising the reservoir, and clip 4 is closed. The substance is placed, along with a little water, in a 200-250 C.C. flask, to which the stopper and tubes are fitted, connections made, and to expel the air through tubes 2 and 3, the water in the flask is boiled until the water into which tube 3 dips is caused to boil by the issuing steam, clip 5 is then closed, and the air still in tube 1 driven into the mea- suring tube by opening clip 4, which is again closed, and the flame removed from below the flask. The measuring tube is filled to the top with sodium hydroxide, and tap H is closed. 20-25 C.C. of cold saturated ferrous chloride, and then 8-10 C.C. of concentrated hydro- chloric acid are carefully drawn into the flask through tubes 2 and 3, which are then washed with water in the same way; the flask, suspended a few cm.above the wire gauze, is now heated, and asANALYTIGA L OHEMISTRY. 109 soon as a, pressure i R indicated in the india-rubber tube at 4, that clip is opened, t,be nitric oxide passes into the measuring tube, and by the time the liquid has yolatilised in the flask, all the nitric oxide is con- chided to be in the measuring tube. The temperature in the jacket tube surrounding the measuring tube is made to correspond with that i n the vicinity of the bulb, and the level in the reservoir being adjusted to that in the measuring tube, the volume is read off, and after the necessary corrections are made, the percentage of nitrogen is. calculated therefrom.The saucer under the measuring apparatus is filled with water to keep the tubes immersed in it cool. For substances which might be deromposed by boiling with water, a tap funnel is fitted to the flask, and is used for charging it. D. A. L. Estimation of Nitrogen in Organic Substances by means of Alkaline Permangmate. By R. L. WAGNER (Chem. Zeit., 14. 269). -The autbor some years ago recognised the possibility of oxidising nitrogenous organic substances by means of alkaline permanganate, without the formation of ammonia. In his experimcnts he mixed 0.5 to 1 gram of substance with 25-30 times its weight of potassium permanganate, and 5 C.C. of 25 per cent. potassium hydroxide, placed the mixture in a tube closed at one end, terminating at the other in a capillary for the escape of oxygen, warmed in a water-bath to aid admixture, and theu heated at 150-170" in an air-bath for two to two and a half hours. The conQents of tbe tube were turned into a porcelain basin, the excess of manganate reduced with manganese sulphate and sodium carbonate, and the nitric acid deteimined in the clear liquid by a modification of Eder's method ; but irregularity of combustion and breaking of tubes rendered the method practically useless, except, perhaps, for substances soluble in alkalis.Non-vola- tile nitro-derivatives and ethereal nitrates can be safely oxidised by alkaline permanganate in a porcelain dish, excess of permanganate being subsequently reduced with alcohol, and the diluted filtrate treated with ferrous sulphate, zinc-dust, and hydrochloric acid ; the nitrogen is then estimated as ammonia, by any of the usual distilla- tion methods.Carbon bisulphide and thiophen can be oxidised by similar treatment, and the sulphur estimated in them; they are enclosed in thin glass bulbs, and placed in tubes containing the alkaline permanganate ; the tube is sealed up, the bulb broken, and tbe digestion proceeded with. D. A. L. Detection of Foreign Raw Phosphates in Powdered Basic Slag. By L. BLUM (Zeit. anal. Chem., 29, 408--411).-The relative superiority of basic slag as a fertiliser over natural phosphatic minerals, owing to its ready absorbability, and the high price which i t has in consequence atkained, have led to its falsification with other raw phosphates.Only such are likely to be used as, from their low percentage of phosphoric acid, cannot profitably be worked a p as superphosphate, and these in most cases contain much calcium carb- onate. Fresh basic slag is almost absolutely free from carbonates, and even ou long exposure to air, absorbs very little carbonic acid110 ABSTRAOTS OF OHEMIOAL PAPERS. (2.47 per cent. was found in an extreme case), so that the presence of much carbonate i n a specimen would be enough to throw suspicion on it. A low percentage of iron and manganese might furnish an additional indication, since tlhese metals are rarely present in natural phosphates. In estimating the carbonic acid by decomposition with an acid, some chromic acid should be added, to prevent evolution of hydrogen aulphide from the sulphides present, but a simple estima- tion of the loss on ignition would generally allow an opinion to be formed.M. J. S. Estimation of Water in Superphosphates. By J. STOKLASA (Zeit. anal. Chem., 29, 390--397).-Pure monocalcium tetrahydrogen phos- phate, CaH4(P04)2 + HzO, loses its water of crystallisation at loo", but only completely after 40 hours. It may be kept at 105" for 20 hours with but little change, but on longer heating at the same temperature begins to show decomposition. At higher temperatures, the amount of change is dependent not alone on the temperature, but also on the time of drying. The statement of Drewsen (Abstr., 1881, 465) that drying even at 300" does not diminish the proportion of soluble phosphate, but merely reduces it to a soluble pyroyhosphate, cannot be confirmed for pure or nearly pure monocalcium phosphate.I t might be true for a superphosphstc in which free phosphoric acid constituted 80 per cent. of the total soluble phosphoric acid. On drying for one hour at ZOO", one-half of the monocalcium phosphate undergoes decomposition, thus :-4Cs€&( PO,), = Ca?,P207 + Ca(P03), + CaH2P207 + 2H3POa + 4H20. At lower tempera- tures for the same length of time, the proportion decomposed is smaller, but if the time is prolonged, a further decomposit'ion takes place ecen at 150", and less free phosphoric acid is fouud in the soluble part. A temperature of 200" sufficiently prolonged results in the following decomposition : 4 C a H 4 ( PO& = 3Ca(P03)2 + CaH2P207 + 7H20, whilst at 210", there remains nothing but insoluble, glassy calcium metaphosphate.I n presence of free phosphoric: acid, the contrary action may on heating take place, thus: ChP,O, + 2H,PO, = 2CaH2P207 + H,O, and thus the soluble phosphoric acid actually undergo increase. M. J. S. By R. FRESENIUS (Zeit. anid. Chem., 2 9 , 4 1 3 4 3 0 ; see Abstr., l890,924).-A11 attempts to Qbtain complete separation by niems of chvomic acid in a single pre- cipitation resulted in failures. The seemingly satisfactory separation obtained by Frerizhs and by Russmann (next abstract) resuited from the accidental compensation of opposite errors, since they washed the barium chromate wibh acetic acid, in which it is distinctly soluble, and weighed it after drying a t 110", at, which temperature it still retains some moisture.In a solution containing alkaline acetate and dichromate, barium chromate is, however, quite insoluble. It can also be rendered anhydrous without decomposition by ignition at a dull red heat, even the portion adhering to the filter reoxidising after temporary reduction. By double precipitation of the barium, a com- plete separation can be effected even when the proportion of Separation of Barium from Strontium.ANALYTICAL CHEMISTRY. 111 strontium is large. The solution of the chlorides is feebly acidified with acetic acid, and diluted until it contains not more than 0.5 per cent. of the bases, then precipitated hot with a n excess of ammonium chromate, which has been carefully neutrahed with ammonia, After cooling €or an hour, the precipitate is washed by decantation with very di1ut.e ammonium chromate until the washings no longer give a precipitate with ammonium carbonate, and then further with warm water until the washings are scarcely coloured by silver nitrate.The precipitate is then dissolved in the smallest possible quantity of nitric acid, and the solution again diluted and heated. Ammonium metate is added in sufficient quantit-v to displace the free nitric acid by acetic acid, and then ammonium chromate until the odour of acetic acid bas completely disappeared. After an hour, the liquid is poured through a filter, the precipitate is digested with hot water, cooled, filtered, and washed thoroughly with cold water. It is then free from strontium, whilst the filtrates contain no barium.Double precipita- tion from neutral or alkaline solutions has not been successful. M. J. S. Separation of Barium, Strontium, and Calcium. By A. RUSSMANN (Zeit. anal. Chent., 29, 447-454; from Tnaug. Diss. Berlin, 1887).-Barium cannot be satisfactorily estimated by Frericbs’ method (precipitation from an acetic acid solution by normal potassium chromate), since the filtrate always contains traces of barium, and some potassium chromate is carried down by the preci- pitate. The precipitate will also contain strontium, if the proportion of the strontium in the solution exceeds 30 parts per 100 of barium. Calcium is not so precipitated. The simplest way to ascertain the weight of the barium chromate, is to dissolve it in dilute hydrochloric acid, add potassium iodide, and immediately tit rate with thiosulphate.Diehl’s method for separating barium and calcium by digesting the sulphates with sodium thiosulphate solution is complicated by so many sources of error that it cannot be recommended. Fresenius’ method of separating barium and calcium by dilute sulphuric acid in a solution acidified with hydrochloric acid is thoroughly satisfactory. The method of Sidersky (Abstr., 1883, 509) for separating strontium and calcium only yields approximate results. For separating barium and calcium, it is, however, serviceable. Bloxam’s method (Abstr., 1886, 920) is not suitable for quantitative separations, as the strontium sulphate carries down with it considerable quantities of ccLlcium, and the calcium ammonium arsenate cannot readily be brought into a, form for weighing in which i t contains a constant proportion of calcium.Fleischer’s method for separating barium and calcium by digestion with 3 parts of potassium sulphate and 1 part of carbonate, followed by titration of the calcium carbonate in the weighed precipitate gives good results. Lastly, Leison’s met.bod for the estimation of the individual alkaline earths, by precipitation with oxalic acid and alcohol, and titration of the oxalic acid in the precipitate by permanganate, is accurate. The barium oxalate must be dissolved by hydrochloric acid, as it is not completely decomposed by. sulphuric acid. Strontium and calcium oxalates can be decomposed by sulphuric acid. The solutions must not be filtered throngh paper,112 ABSTRACTS OF CHEMIOAL PAPERS.and must be highly dilute. Ignition of the oxalates is, however, as a rule, the quicker process. Estimation of Cadmium in the Products of Zinc Manu- facture and in Calamine. By W. MINOR (Chem. Zeit., 14, 4, 34, and 348-349) .-The material is dissolved in hydrochloric acid, treated with hydrogen sulphide, and the precipitate washed with hot, water, dissolved in hydrochloric acid, heated to boiling, and poured into dilute sodium hydroxide likewise heated to boiling. This preci- pitate, after washing with hot water, is ignited in a current of oxygen, and weighed as cadmium oxide. Material containing but little iron, such as “ pure cadmium,” is dissolved in hydrochloric acid, and preci- pitated directly with the sodium hydroxide.This method of precipitation may also be used to separate zinc and cadmium i n t,he ordinary method of examining calamine ; the ammoniacal solution containing the zinc and cadmium is rendered slightly acid and poured hot into the hot hydroxide, &c. In the method described in the last of the three papers, the material is dissolved in hydrochloric acid, filtered from undissolved lead, precipitated with hydrogen sulphide, the precipitate, containing zinc and an inconsiderable amount of arsenic, is washed, dried, weighed, dissolved in dilute hydrochloric acid, and treated with sodium hydroxide in excess. The cadmium hydroxide is filtered off, and the zinc titrated in the filtrate with sodium sulphide, calculated . to zinc sulphide, and deducted from the weight of the cadmium sulphide precipitate.I n another method (requiring the absence of other metah precipitated by sodium hydroxide) after removal of iron with ammonia, the solution of zinc and cadmium is nearly neutralised with hydrochloric acid, and then treated with sodium hydroxide. The precipitate of cadmium hydroxide i R dissolved in dilute hydrochloric acid, evaporated to dryness, dissolved in water, and titrated with standard sodium hydroxide, using litmus or sodium sulphide papers as indicators. Good results have been obtained by both methods, the first being the more suitable in the presence of much zinc and vice versc2. D. A. L. M. J. S. Estimation of Cadmium as Sulphide by Precipitation with Sodium Sulphide Solution. By W. MINOR (Chem. Zeit., 14, 439-440) .-The material is dissolved in hydrochloric or nitric acid, and the lead separated by sulphuric acid ; the solution is then treated with soda, and the precipitate digested with ammonia.The ammoniacal solution is free from lead, zinc, and iron, but contains all the cadmium, which can then be determined by means of sodium sulphide solution, either volumetrically by tit ration, nsing ferric hydroxide as indicator, or gravimetrically by precipitating, and weighing the precipitate after drying for some hours at 140-145O. D. A. L. Volumetric Estimation of Zinc and Copper. By E. DONATR and G. HATTENSAUR (Chenz. Zeit., 14, 323--325).--Various experi- ments have been made by the authors. They find that for titrating zinc by Schaffner’s method, it is better to use sodium hydrosulphideANALYTICAL CHEMISTRY.113 (prepared by adding a known volume of dilute sodium hydroxide to an equal volume of the same solution previously saturated with hydrogen sulphide) than a solution of the crystalline sulphide of commerce ; howerer, in using this reagent in solutions containing tartaric acid and ammonia, the iron commences to precipitate before all the zinc is converted into sulphide. The estimation of zinc by using excess of ferrocyanide, after the removal of the iron, and titrating back with permanganate does not answer, since in the cold a clear solution cannot be obtained, whilst if warm, decompositions occur which cause irregularities. It is noticed that ferrocyanide precipitates zinc bu h not iron in the presence of tartaric acid and ammonia, and that the excess of either of these substances does not seriously disturb the relative quantity of 1 mol.ferrocyanide to 2 atoms of zinc ; therefore 1 C.C. of a solution containing 33.5 grams of potassium ferrocyanide per litre corresponds with 0.010 gram of zinc. As small an excess of ammonia as possible, and a hot solution, are favourable to the preci- pitation. The zinc precipitate is not decomposed by acetic acid; therefore, by placing drops of this acid and the solution under exami- nation in contact, in the presence of iron, a coloration indicates complete precipitation of' the zinc. The following method it; based on these considerations :--3 t o 4 grams of material is dissolved in hydro- chloric acid with some nitric acid, diluted to a definite volume with water, an aliquot part filtered, treated with 20-25 C.C.of concen- trated tartaric acid solution, a slight excess of ammonia added, and the liquid warmed to about 80". The ferrocyanide is now run in until the precipitation of the zinc is complete, as indicated in the manner described above. The proportion of iron to zinc ili the solution under examination should be the same as that present in the solution used for standardising the ferrocyanide. Under similar circumstances, copper is precipitated in a like manner, but the precipitation is greatly influenced by ammonia ; fherefore the solutio~r for titration should be neutral or nearly so. The ferrocyanide is standardised from a solution of copper of known strength, and cannot, be approximated to by the weight of fcrrocyauide employed, inasmuch as the composition of the copper precipitate is uncertain.Copper and zinc may be estimated in the same solution by this method ; first both are titrated, then the copper is precipitated out of another portion of solution, and the zinc alone titrated, &c. D. A. L. Estimation of Lead by Phosphomolybdic Acid. By H. BEUF (Bull.. Soc. Chinz. [3], 3, 852--855).-To the boiling neutral solution of the metal, an aqueous solution of phosphomolybdic acid is added until the supernatant liquid is coloured yellow by the excess of reagent used. After washing, the precipitate is dried at 90-100° and weighed. It forms a dense, white powder which is insoluble in water (1 in 500,000) and aqueous ammonia, but dissolves in nitric and in acetic acids ; it contaiiis 54.8 per cent.of lead, and corresponds with the formula Mo,Pb2,P2H,,0,,,; at a high temperature it loses 7 mols. H20. By decomposition of the precipitate with dilute sulphuric acid and einc at a gentle heat, a brown liquid is obtained, wbich may be YOL, LX. i114 ABSTRACTS OF CHEMIUAL PAPERS. titrated for lead by a solution of permanganate which has been previously standardised against a solution resulting from tho similar treatment of a known weight of a lead salt. The phosphomolybdic acid is made by evaporating to dryness a solution of ammonium phosphomoly bdate in nitric acid. Iron is eliminated by a previous treatment with sodium hydroxide, copper, potassium, and ammonium by washing the mixed pbosphomolybdates with ammonia-water, but the presence of zinc or arsenic vitiates the estimation.T. G. N. Separation of Copper from Arsenic by the Electric Current. By L. W. MCCAY (C‘laem. Zcib., 14, 509).-Under the influence of the current from four to six Meidinger elements, alkaline arsenates remain in solution, whereas copper is completely and quantitatively precipitated, and has been estimated wikh good results. Moreover, t h e copper is quite free from arsenic, and the solution may be safely employed for the determination of the original amount of the latter metal. D. A. L. Estimation of Aluminium in Commercial Aluminium. By 0. KLEMP (Zeit. anal. Chsm., 29, 388--390).-The prccess employed for zinc (Abst , 2890, 1190) cannot be applied to aluminium since, always evolved, but bv dissolving the aluminium in potash, and burn- ing the hydrogen in Fi=eserlins’ apparatus, a very accurate estimation cam be made.About 1 gram of the metal in filings is placed in a 150 c c. flask with a little vaselin to prevent frothing, and the potash solution (35 grams of KOH in ‘LOO c.c.) is added gradually, with warming towards the close. Estimation of Alumina in Bread, &c.; Solubility of Alu- minium Phosphate in Acetic Acid. By W. C. YOUNG (dnalyst, 15, 61-63 ; 83-S4).-1n Duprk’s process, the aluminium is precipi- tated as phosphate from an acid solution containing ammonium chloride and acetate, and is collected after remaining all night in the cold. Test analyses, with weighed quantities of alum, show that under these conditions the resalts are much below the truth.The best result (from a mixture of alum, sodium phosphate, and acetic acid) was obtained by boiling the mixture both before and after the addition of ammonium acetate, and filtering immediately. The amount of ammonium acetate must not be too small, nor that of acetic acid too large. For 0.1 gram of potash alum, there mas used 1 gram of ammonium acetate and 5 C.C. of ordinary acetic acid. The presence of ammoriiuni chloride has little effect when the liquid is filtered immediately after boiling, but lowers the result i E the pre- cipitation is performed iu the cold, or the mixture is allowed to cool before filtering. M. J. S. Estimation of Iron Oxide and Alumina in Phosphates. By R. JONES ( C h e w Zeit., 14, 269--271).-The author criticises the methods employed until recently, and recommends as the best the following Combination of Glaser’s method, slightly modified, with even with big ;i; ly dilute alkali and a large excess of iodate, hydrogen is The operation takes about 45 minutes.M. J. S.ANALYTICAL CHEMISTRY. 115 part of Stutzer's method. The phosphate is dissolved in hydrochloric and nitric acids, made up to a definite volume, an nliquot part taken and treated with ft quarter of its volume of sulpluric acid of sp. gr. 1.84, and its om11 volume of 95 per cent. alcohol, making up to definite volume with the alcohol ; after 12 honrs, the gypsum is collected, and when weighed, gives good results for calcium i n absence of much magnesium. The alcohol is driven off from the filtrate, which is rendered alkaline with ammonia and boiled to completely drive off the ammonia.The precipitate may be weighed, and half the weight taken as iron oxide and alumina, which gives good results, or it may be treated with molybdic solution, the phosphoric acid 'separated in the usual way, the iron and alumina precipitated wlth dilute ammonia, redissolved in hydrochloric acid, reprecipitated, &c., and weighed. Titration of Chromates, Barium Salts, and Sulphates. By P. SOLTPIEN (Clteni. Centr., 1890, ii, 217-218 ; from Pharm. Zeit., 35, 372) .-The titration of solutions of barium salts with potassium &chromate, and inversely the titration of chromates with barium salts, may be readily performed with either hzematoxylin or logwood extract as indicator. A solution of barium chloride is prepared equal to one of potassium dichromate, and for the determination of barium salts, potassium dichromate is run in from the burette until a drop placed on a warmed porcelain plate with a drop of haematoxylin just shows the formation of a blue-black coloration. The solution to be titrated must be neutral, and may not contain more than the merest trace of either acetic acid or ammonia.Chlorides and nitrates do not in- terfere with the reaction, nor does rosolic acid, which latter may be used a s an indicatlor for the titration of soli~tions of salts of barium. If the solution of a chromate contains sulphat,es, the titration with barhim chloride gives the total qnaritity of the two salts, from which must be deducted the amount of the latter as determined gravimetrically.For the determination of the combined snlphuric acid, an excess of barium chloride solution is added, and the excess determined by titration with pot.assium dichromate. Salts of aluminium, copper, and iron must be removed from the solutions. J. W. L. Estimation of Antimony by Marsh's Method. By A. VAN BYLERT (Ber., 23, 2968-2971 ; compare Kuhn and Saeger, Abstr., ISYO, 1187).-For the estimation of antimony in alloys of tin, silver, and antimony, the author recommends the following process :- A three-necked Woulffe's bottle is connected on the one hand with an npparatus for evolving carbonic anhydride, and on the other with thu usual calcium chloride tube and hard glass tube. The central neck of the Woulffe's bottle is fitted with a wide tube reaching to the bottom of the flask.About 0.5 gram of the alloy is dissolved in 20 C.C. of mercury at 60", and poured, after cooling, into the fiask. 100 C.C. of 10 per cent. sulphuric: acid is then added through one oLc the side tubes, and the air expelled from the apparatus by carbonic anhydride. A freshly prepared sodium amalgam, obtained by dis- solving 5.5 grams of sodium in 25 c . ~ . of mcrcury, is then aclded dro]~ D. A. IJ. i;L116 ABSTRACTS OF CHEMICAL PAPERS. by drop through the wide tube. The sublimate of antimony quickly appears in the heated tube ; the apparatus is then periodically shaken, care being taken that no liquid is allowed to pass into the central tube. After the evolution of gas has ceased, carbonic anhydride is again passed tbrough the apparatus t o expel all the hydrogen and hydrogen antimonide. The mercury solution is then poured off, dried with filter-paper, and divided into two equal portions, one of which is returned t,o the cleaned and dried apparatus, and covered with 75 C.C.of a 10 per cent. sulphuric acid, whilst the other is mixed with 3 grams of sodium, and added drop by drop through the central tube as before. The results obtained are fairly accurate, but might possibly be improved by employing lirdrogen in place of carbonic anhydride for driving out the air. Another soiirce of error is the oxidation which takes place in the manufacture of the alloy, and during its solution in the mercury. H. G. C. Estimation of Hardness of Natural Waters. By E. JJ. NEUGE- JMJER.(Zeit. anal. Chem., 29, 399-401 ).-The author proposes the following modifications of Clark's test. The standard water is a mixture of 8 vols. of calcium sulphate solution of 12" of hardness with 2 vols. of a 12" magnesium sulphate solution. Of this mixture, 100 C.C. is used. The soap solution is of such strength that 12 C.C. is required for the 100 C.C. of standard water. The following new table has been drawn up from titrations of the standard water diluted to the required degrees :- Hardness.. .......... 0" lo 2" 3" 4" 5" 6" C.c of soap solution . . 0.6 1.7 2.8 3.9 4.9 5.9 6.9 Hardness.. .......... I 8" 9" 10' 11" 12" C.c of soap solution ,. 7.8 8.7 9.6 10.4 11.2 1200 F O and a, special burette (titanometer) constructed, the readings of which give a t once the degrees of hardness.The Analysis of Sulphurous Waters. By D. VITALI (Chem. Cen.fr., 1890, ii, 166 ; from L'Orosi, 13, 73-778).-Thiosulphates may be detected by the addition OE potassium nit,rite and a mineral acid or acetic acid. Nitric oxide is liberated, and the solution is thereby coloared yellow ; later, sulphur is precipitated, and the liquid becomes milky. 'Ibis reaction is extremely delicate, 0.0001 per cent. of thio- sulphate being detectable. I n testing for nitrites in presence of thio- sulphates with potassium iodide and starch, this reaction of the tbio- sulphate may prevent the formation of the blue iodide of starch, a yellow coloration being produced instead. In testing for iodine, in presence of thiosulphates, with potassium nitrite and an acid, it is better to evaporate the water to dryness after neutralising with sodium carbonate, and then to extract the residne with absolute alcohol, which dissolves the iodide, leaving the thiosulphate undis- solved.In the case of waters containing large quantities of calcium snlphnte, it is recommended to first precipitate the calcium as calcium carbonate before determining the silicic anhydride. Xu order to prevent tho precipitation of sulphur during the evaporatior of water M. J. S.ANALYTICAL UHEMISTRY. 117 for determination of the total solid residue. the author recommends that a current of hydrogen should be passed through the water. J. W. L. Examination of Water for Contamination by Gas Works, By F. DICKMAEN (Zeit. miat. Cirem., 29, 398--399).-1n a specimen of water from a brook which had suffered contamination from a neigh- bouring gas works, and by which poultry had been poisoned, tho author detected traces of a substance giving the reactions of di- pbenylamine.Owing to the stability of this compound and the sensitiveness of its reaction with nitric acid, its presence might be used as a proof of contamination by tar-water, if i t should be found to be a constant constituent of that liquid. Detection and Estimation of Organic and Inorganic Poisons in Corpses. By A. SEYDA (Chem. Zeit., 14,31--32, 51-53,128 -129, 181-184, and 198-200) .-The author describes his system of examining corpses. The chemical examination proper is preceded by a preliminary examination of the blood, urine, and contents of the stomach and accessories.The blood, when not too decomposed to show the absorption bands, is examined spectroscopically ; if dry, it is dissolved in water, and made very slightly alkaline with sodium hydroxide ; the two oxyhaemoglobin bands amd the intermediate haemoglobin band merge into one con- tinuous band in partially decomposed blood; the faint band in the red is attributable to methaemoglobin in alkaline material or to hmmatin in acid blood. In the former case, fiwther examination is only made under exceptional circumstances, such 8s the presence of hydrogen sulphide not emanating from ordinary putrefactive pro- cesses ; but, in the latter case, the red band being due to hsematin, is regarded as indicating the presence of other reducing agents, or of acids, potassium chlorate, ferricyanides, nitroglycerol, or nitro- benzene, which are tested for in the urine and in parts of the body.Other isolated lines in the red are carefully noted, and carbonic oxide is sought for ; the presence of hsmatin, already reduced or otherwise, indicates the absence of carbonic oxide poisoning ; carbonic oxide haemo- globia is recognised in presence of oxyhEmoglobin and hEmoglobin by the mere displacement of the absorption band towards the red part of the spectrum when ammonium sulphide is added ; chemical tests with sodium hydroxide with or without calcium chloride are con- sidered of little value. In the urine :-Notes are taken of the quantity, colour, odour, of re- actions as to the presence of blood, albumin, and sugar, of the action in alkaline copper solutions, of the behaviour toyvards barium chloride before and after treatment with hydrochloric acid, and of the occur- rence of balsams, alkaloids, soluble metallic poisons, and of such salts as potassium chlorate, iodide, or bromide.The contents of tlie stomach are examined in the dark for phosphor- escence, which is only due to phosphorus in acid mixtures, otherwise fungoid growth may cause it. The, udour of the contents of the stomach may be acid, alkaline, like decayed cheese, or they may have a specific odour, or be putrid ; sometimes they are well preserved, and M. J. S.118 ABSTRACTS OF OHEMICAL PAPERS. have a sweetish, repulsive odour, observed by the author in cases of ar.ienical poisoning. Food iizagmas and vomits are carefully sampled, treated with alcohol and then with ether, and examined macro- and micro-scopically.The alcoholic extract is examined for oxalases and foreign bases and acids ; matters found in the folds are also examined. The arsenic test is applied, and an aqueous extract of the magma is examined f o r soluble poisons. For the chemical examination proper, parts of organs, finely divided, arc heated with water in a boiling water-bath for several hours, acidified q-ith tartaric acid, and distilled with steam. Two fractions are made: the first will contain the more volatile matters, such as alcohol, aldehyde, acetone, chloroform, nitrobenzene, ethereal oils, turpentine, camphor, amines, and their volatile corn binations ; the other, the remains of these more volatile products, and any less volatile substances, such as fatty acids, phenol, hydrocyanic acid, &c.A plain distillation of alkalilie material is required at times ; if, how- ever, the presence of chloral bydratc or hydrocyanic acid and ferro- cyanides is suspected, the finely divided orgaris are first moistened with potash or with hydrogen sodium carbonate respectively. A steam distillation from alkaline solution, when necessary, is best ejfected, not directly, but with the liquid obtained by extraction with water and tartaric acid. The residue from the acid distillat'ion is employed in testing for alkaloids. The odour, colour, opdesceiice, quantity, &c., of the first fraction of the acid distillate are noted. I t is tested with silver nitrate, both in nitric acid and in ammoniacal solution, with sodium nitroprusside, potash, and acetic acid ; with alkaline permanganate ; with iodine and potash (iodoform reaction) ; with zinc-dust and hydrochloric acid for nitrobenzene ; with hydrochloric acid and alcoholic phloroglucinol for otheyeal oils (a reaction frequently takes place, but too much depend- ance is not to be placed on it; it is better to examine the urine for some of these substances, also for altered camphor). The reagents for tur- pentine oil, in tangible quantities, are a mixture of fresh guaiacum alcohol and fresh citronella oil.Resorcinol and potash are better reagents for detecting chloroform than the isonitrile test. A quantita- tive examination for these substances is seldom possible, with the exception of alcohol, but this cannot be estimated by distillation in the presence of amines ; therefore it is oxidised to acetic acid as follows.A portion of the distillate is redistilled, the first portions collected are dried with potassium carbonate, distilled again, treated with sodium dichromate and sulphuric acid, rendered alkaline with potash, boiled t o eliminate amine bases, then acidified, steam distilled, and the distillate, containing the acetic acid, titrated ; any sulphuric acid, if accidentally present, being estimabed and allowed for. The author at,taches great importance to the estimation of alcohol, especially in the case of children. Various parts of corpses of persons addicted t c alcohol yield distillates containing alcohol, but not pure ethyl alcohol ; therefore such distillates reduce alkaline permanganate, &c., give the iodoform reaction, and yield an inflammable distillate on redistillation from potassium carbonate.Alcohols readily evaporate from corpses, the more volatile disappearing first.ANALYTICAL CHEMISTRY. 119 Passing on to the second fraction from the acid distillation, phenol, as n normal product of the decomposition of nlbuminoids, is frequently detected by Millon's reagent, less readily by bromine-water. Large quantities of phenol are estimated by filtering the fraction containing it from the fatty acids, extracting with ether, drying the ethereal residue over sulphuric acid, and weighing, taking precautions against the phenol creeping over the edge of the evaporating dish. As regards hydrocyanic acid, the distillate is tested with copper sulphate and guaiacum, and if the reaction is noticed, i t is confirmed by some other test, and the acid determined as silver cyanide.Phosphorus is generally recognised by the phosphorescence, but if this does not occur phosphorous acid must be tested f o r and estimated in the residue. I n examining the distillate for phosphorus, it is redistilled, using an upright bulbed tube, the distillation being continued for an hour after phosphorescence has ceased to appear; the new distillate is treated with silver nitrate, &c., and also is tested for phosphorus by oxidising with chlorine-water and adding ammonium molybdate. I n examining for alkaloids, special care must be taken not to mistake ptomaines for other alkalo'ids, and to allow for the impure form of the latter.The material is treated with alcohol containing tartaric acid, the extract filtered, evaporated, dissolved in water, filtered, neutra- lised with potash, concentrated, treated with alcohol, separated from the potassium tartrate, and the neutral aqueous fiolution is tested with alkaloid reagents (a preliminary test with tmtaric acid and iodic acid being made for morphine) and examined systematically if required. A portion is rendered alkaline, and steam-distilled for nicotine, coniine, miline, &c. I n the absence of these volatile bases, another portion is extracted with ether successively when neutral, acid, and alkaline, ehen with chloroform while still alkaline, and finally is made ammoniacal and extracted with aniyl alcohol. The t8hird portion is reserved for the direct confirmatory examination of any alkaloid icdicated in the other portions.The aqueous residue is tested for narceine and curarine, whilst the various extracts are examined separately. The residue from the dkaline-ether extract is tested with phosphoric acid for aconitine. Vitali's atropine reaction is liable to be hidden by xaiithoprotcin colour reactions. For strych- nine, a double test is made: first., a drop of vanadic acid solution is mixed with the Gesidue, dissolved in sulphuric acid, which is subse- quently diluted with concentrated sulphuric acid, and then solid ammonium vanadate is dusted over another portion of the same solution. Attention is called to the fact that colocynthine gives reactions with both vanadic and chromic acids, which resemble those of strychnine with the same reagents. The atuyl alcohol extract, after purifying, serves for confirming the presence of morphine.Another portion of the original extract is examined for metallic poisons soluble in alcohol. The examination for metallic poisons generally is made with the residue from the first distillation or that, from the alcoholic extraction ; in the latter case the alcohol is expelled by warming. The residue is heated with hot water, potassium chlorate, and hydrochloric acid until the organic tissue is destroyed a r d all chlorine driven off, the magma is treated with tartaric .acid, then120 ABSTRAOTS OF OHEMIOAL PAPERS. largely diluted with water and, after 24 hours, filtered.Tho insoluble portion is treated (if required with more chlorate and hydrochloric acid, then) with alcohol, and with ether to extract fat, and is ignited, The ash is treated with very dilute hydrochloric acid, and the residue dried, ignited, weighed, and proved conclusively to be silica by fusion with sodium carbonate ; or is examined for silver, lead, barium, and strontium. The soluble portion is marde up to a definite volume, and must be free from chlorine and chloric acid. For mercury, a portion is nearly nentralised by means of potash, and is digested with brass wool €or 15 minutes a t 70" ; if the brass is visibly amnlgnmatecl, the presence of mercury is confirmed by heating in a test-tube, &c. ; but when the presence of niercury is not so evident, the brass wool is burnt with copper oxide in a current of air in a tabe 25 cm.long, drawn out to a doubly bent capillary, in which any mercury is accumulated, and identified with iodine. To estimate mercury, the hot hydrochloric solution is treated with hydrogen sulphide, the precipitate collected on an asbestos filter (or if arsenic is present, i t is first digested with yellow ammonium sulphide) washed with hydrochloric acid, dissolved in nitric acid, filtered through some asbestos, and the washings and filtrate diluted and treated with phos- phorous acid. After 24 hours, the calomel is filtered off, washed with, water, alcohol, and ether, and weighed on a tared filter. Tbi*oughout the estimation, high temperatures and contact with organic matter are to be avoided.To detect antimony, some of t,he liquid partly neutralised with ammonia is placed in a bright platinum dish with a piece of zinc for six hours ; the brownish-black antimony flakes obtained in this manner being more trustworthy than Marsh'R test. This test does not answei- in the presence of tin ; but by fusing the mixed oxides wit11 sodium hydroxide, most of the tin can be separated. To estimate antimony, hydrogen sulphide is passed through the slightly acid, and at first boiling, solution until it has cooled down ; after three days, most of the hydrogen sulphide is driven off by carbonic anhydride, the preci- pitate washed with an acetic acid solution of ammonium acetate, treated and washed with a solution of sodium sulphide, containing hydrogen sulphide, the solution treated carefully with hydrochloric acid, warmed, and then boiled.After 24 hours, the precipitate is col- lected, treated with an acetic acid solution of ammonium acetate, then carefully with nitric acid, evaporated, the residue moistened with sodium hydroxide, intimately mixed with dry sodium carbonate, dried, introduced by small quantities at a time into fused sodium nitrate in a, silver crucible, and the mass, when cold, treated with water. After 24 hours, the precipitate is washed with 45 per cent. alcohol, contain- i n g soda, digested with il hot solution of tartaric and hydrochloric acids for half an hour, filtered, and washed with a dilute solution of tartaric a d hydrochloric acids. The filtrate and wasbings combined are concentrated in a water-bath, the excess of acid reduced with ammonia, and the antimony precipitated by hydrogen sulphide as a pure orange-coloured sulphide which is converted into oxide by Bunsen's method.The purity of the antimony is ultimately confirmed by its volatility.ANALYTICAL CHEMISTRY. 121 To detect arsenic, mercury and antimony being absent, various obvious precautions are observed in applying the Marsh test to some of the liquid, and when a mirror is obtained, the tube containing i t is divided by a diamond into four parts, of which one is used for the odour test, another for solubility in freshly-prepared sodium hypo- chlorite, a third for dissolving in nitric acid arid testing with silver nitrate, whilst the fourth is dissolved in nitric acid, and converted into arsenic sulphide by colourless ammoniuin sulphide.To estimate arsenic, hydrogen sulphide is passed through the warm hydrochloric solution for 12 hours, and after remaining three to five days in a closed flask, most of the hydrogen sulphide is driven off by a current of carbonic anhydride ; the procedure then resembles that described in the antimony estimation, but various points are to be observed :- 1. Ammonia or ammonium carbonate are the only solvents used for arsenic sulphide on the filter. 2. The fusion is conducted in a porcelain crucible with fusion mixture and potassium nitrate. 3. The arsenic is always weighed as magnesium pyroarsenate. 4. The alkaline solution is not precipitated directly with magnesia mixture, but is first Rub- mitted to the following treatment :-Neutralisation with nitric acid, expulsion of carbonic anhydride and nitrous acid, precipitation with hydrogen sulphide, and conversion into arsenic acid.5. The ammo- nium magnesium arsenate is redissolved in hydrochloric acid and re- precipitated by ammonia. 6. Small quantities of magnesium arsenate are converted into pyrosrsenate by dissolving in very dilute nitric acid, evaporating in a porcelain crucible over a water-bath, and carefully and gradually igniting the residue ; the method is susceptible of great accuracy ; as little as 0.0093 to 0.0077 gram of arsenic in a portion of a dead body has been estimated. 7. Large quantities of pyroarsenate are preserved as such for reference ; small quantities aro converted into metallic arsenic in a Marsh’s apparatus, and are preserved in EL sealed tube.In the absence of mercury, antimony, and arsenic, the hydro- chloric acid solution is made alkaline with soda, acidified with acetic acid, hydrogen sulphide passed in at the boiling point of the liquid and until cold, sodium carbonate added to distinct alkalinity, and the whole allowed to remain corked up until clear. The solution serves for de- tecting and estimating tin. The precipitate is washed with sodium sulphide containing hydrogen sulphide, oxidised with nitric acid, evapo- rated, moistened with sodium hydroxide, mixed with fusion mixture, dropped into molten nitre in a silver crucible, extracted with water, supersaturated with hydrochloric acid, filtered, and the hydrochloric acid solutions submitted to the ordinary methods of analysis, weighing any metal isolated in a definite form. The separation of iron, alumina, and zinc in the presence of calcium and magnesium phosphates is effected in the following manner :-The hydrochloric acid filtrate from the hydrogen sulphide precipitate is concentrated on the water-bath, treated with chlorine-water, evaporated, the residue dissolved in very dilute hydrochloric acid, filtered, the solution supersaturated with am- monia, excess of the latter nearly expelled on the water-bath, the pre- cipitate removed, the solution acidified with acetic acid, and hydrogen sulphide passed into the boiling hot liquid until it gets cold.The zinc122 ABSTRACTS OF CHEMICAL PAPERS. sulphide is weighed. The ammonia precipitate is dissolved in nitric acid, treated in a platinum dish with tin, which by repeated and careful treatment with nitric acid is converted into stannic oxide, and with i t the phosphoric acid into insoluble stannic phosphate, from which the alumina is washed out by yery dilute nitric acid, and estimated in the solution by precipitating with ammonia, igniting the precipitate, fusing the ignition residue with sodium carbonate, extracting with water, filtering, &c.The alkaline filtrate from the hydrogen sulphide precipitate is examined for tin :-It is acidified with hydro- chloric acid, boiled, hydrogen sulphide passed through until it is cold ; after remaining for 24 hours in a warm place the precipitate is collected, washed with an acetic acid solution of ammcinium acetate, and ignited with the filter.The residue is moistened with nitric acid, evapo- raked, ignited, and to get rid of the iron present it is washed into a silver crucible, dried, and treated for I.~df-nn.hour with molten sodium hydroxide, extracted with water, filtered, the filtrate acidified with hydrochloric acid, and the tin obtained in the usual manner. I n concliision, it is pointed out that not only are potassium, sodium, calcium, magnesinm, iron, and niaiiganese noimally present in the human body, but that aluminium, copper, and zinc are always met with, and less frequently tin and lead. These extraneous metals are derived from food, cooking utensils, medicine, &c. ; aluminium comes from various sources, and even after death may be introduced iii the dust, when the post-mortem takes place i n the countr-y.The authoi* in advo- cating his employment of a solution prepayed directly froin the corpse inaterial for the detection of arsenic, points out that consideriiig the sensitiveness of the arsenic reaction a concentrrttion of the solution is not necessary, that the “brown speck” on the porcelain lid referred to by Otto cannot interfepe in his method, which, more- over, obviates any chance of vitiation through arsenical hydrogen sulphide. It is also shown that the presenceof chlorides and nitrates does not stop the formation of gaseous hydrogen arsenide, provided that the zinc and hydrochloric acid are in excess and the evolution of hydrogen is allowed to proceed snfficiently long ; but the presence of free nitric acid stops the evolution temporarily. It is still doubtful whether solid hydrogen areenide is converted into the gaseous modi- fication by zinc and hydrochloric acid.Ordinarily only one poison is found in a corpse, but nevertheless i t should he borne in mind that there is the possibility of more than one being present. Detection of Paraffin in Beeswax. By H. HAGEI~ (Zeit. anat. Cliem., 29, 480481 ; from Pharrn. Centi-allmlle, 30, 565).-A few grams of the substancs in fine, air-dried shavings is gradually heated in a small, porcelain capsule, until fumes begin to rise. A half-litre wide-mouthed bottle is then inverted upon the capsule, and when filled with white vapours is closed and set aside until the fumes bave condensed upon its walls. The sublimate is then dissolved in 3 C.C.of chloroform, the chloroform evaporated in a test-tube, and the residue boiled with 4 C.C. of soda solution. If paraffin was present, it, will after cooling be found floating on the clear solution. A drop of D. A. L.ANALYTICAL CHEMISTRY. 123 the chlorofoi*m solution niay also be evaporated on a slip of glass and examined microscopically. The fumes from pure beeswax are not so whiteas from paraffin, and are only obtained at a higher teinpe~ature (300-320"). The sub- limate gives a coloured solution with chloroform, and a coloured and turbid solution with soda. The residue from the chloroEorm solution is a dnll film ; paraffin on the contrary gives separate grains in a clear field. M. J. S. Condition of the Sulphuric Acid in Plastered Wines, and a Method of Distinguishing between Plastered Wines and Wines mixed with Sulphuric Acid.By L. Roos and E. THOMAS (Compt. reitd., 111, 573--577).-Wines which have been mixed with calcium sulphate do not contain potassium hydrogen sulphate. The liberated tartaric acid interacts with the organic potassium compounds in the wine, and forms a new quantity of potassium hydrogen tartrate. Direct experiment shows that when calcium sulphate is added to a solution of potassium hydrogen tartrate, and an acetate, malate, citrate, or succiaate, the liquid contains no free sulphuric or tartaric acid, but acetic, citric, malic, or succinic acid is liberated. No potas- sium hydrogen sulphate could be detected i n plastered wines by the following method, which will detect the addition of 0-25 gram of sulphuric acid per litre. 'l'he proportion of chlorine and the total sulphuric acid in the wine are estimated.50 C.C. of the wine is mixed with a small quantity of ammonium acetate, and exactly procipitated with a standaiad solution of barium chloride. The filtrate is evaporated to dryness, heated gently, and the chlorine in the residue is estimated. If only normal potassiuni sulphate is present, the reaction is &SO, + BaC'I, = BaSOl + 2KC1, and the chlorine in the residue should be equal to the chlorine of the barium chloride, plus the chlorine originally present in the wine ; i f the acid sulphate i s present, the reaction ia KHSO, + BaCl, = BaSOp + HC1 t KC1, and the free hydrogen chloride is cxpelled i n the process of evaporation, the loss increasing with the quantity of hydrogen-sulphate present.Estimation of Dissolved Solids in Wine. By E. L ~ S Z L ~ (Chem. Zeit., 14, 438, 455).--Results are quoted, showing t,he unsatisf'nctsry character of estimations of " extractives " made by drying residues for 2$ hours. The author suggests determining the alcohol both by distillation and by an alcoholometerat 15" ; the difference between t.he two observations being due to the "extractives" present may be utilised as a measure for them, and he finds that miiltiplying this difference by 0.32 gives numbers for the quantity of dissolved solid matter in 100 C.C. of wine concordant with actual determinations. 'l'he alcoholometer should not have a greater range than lo", or at the outside 12", and f o r wines of sp.gr. greater than 1.000, a saccharo- ueter showing volume percentages is emplcyed. Detection of Methylated Nitrous Ether. By J. MUTER (Analyst, 15, 48).-Much of the sweet spirits of nitre in commerce is prepared from- methylated spirit instead of from pure ethyl alcohol C . H. B. D. A. L.124 AliSTRAOTS OF CHEMICAL PAPERS. as prescribed in the pharmacopceia. The two may be discriminated by dissolving a fragment of solid potash in a sample. The methylated ether darkens, the colour varying from deep-yellow to orange-red, while the odour of methylated spirit becomes very distinct. The ether from pure spirit loses its odour of ethyl nitrite, and retains only that of ethyl alcohol, and it does not dnrkeu beyond the faintest straw colour. On treating with Hubl’s reagent the dis- tillate obtained after digestion with potash, tho methylated sample will absorb 0.4 to 0.7 per cent.of iodine, but that from pure spirit none. Analysis of Carbolic and Sulphurous Disinfecting Powders, By J. MUTER (AnaZyst, 15, 63--68).-The author calls attention to tbe ambiguities in the usual forms of specification for disinfecting powders. Whilst the contracts are nominally for “ carbolic acid,” i t is commonly understood that the powder may contain chiefly cresol and other high-boiling tar phenols. There have, however, been cases where the supply of the more costlyabsolute phenol has been insisted on. The omiesion of the word “ available ” before “ sulphurous acid” some- times renders a literal compliance with a specification impossible.For the estimation of the phenols, the author still employs his own process (Abstr., 1888, 92), with the single modification that 150 C.C. of a 10 per cent. solution of sodium hydroxide is now used instead of 200 C.C. of a 5 per cent. solution. The cresol, measured in contact with brine, retains about 5 per cent. of water. Since anhydi-ous cresol increases in volume by about 5 per cent. when shaken with 3 volumes of brine, whilst that containing water does not increase o r may even diminish, this furnishes a rough but ready test for t h e presence of water. For more accurate work the water must be dis- tilled out. Naphthalene, which is usually present in commercial cresol, may be estimated as follows :-50 C.C. is shaken with 200 C.C. of a 10 per cent.solution of sodium hydroxide. The phenols dissolve, leaving the naphthalene floating. The solution is removed, the naphthalene washed with a 5 per cent. soda, solution, then rapidly filtered off. It is rinsed from the filter with water and again collected on a pair of filters. After drying as far as possible by pressing between blotting paper, the filters are separated and the inner one with its contents is weighed, using the outer one as a tare. For estimating the available sulphurous acid, 2 grams of the powder is washed 011 a filter with dry ether until the phenols and tarry matters are removed. As soon as the ether has evaporated, the contents of the filter are thrown into a bottle containing 50 C.C. of N/10 iodine solution, and after half an hour the residual iodirie is titrated by thiosulphate.This method is unsatisfactory when the basis of the powder is lime. I n sulphurous powders which have undergone osidation, the amount of original sulphurous acid cannot be ascertained if the mixture had consisted of gypsum and calcium sulphite, but where the basis is silica, the sulphates present may be regarded as oxidised sulphites, and where sodium hydrogen sulphite has been mixed with gypsum, the estimatiou of calcium, sulphuric, and sulphurous acids in an aqueous extract will give the necessary data. M. J. S. M. J. S.ANALYTIOAL OHEMISTRY. 125 Arabinose. Milligrams. 17 -0 18 *6 20 '3 21 -9 23.5 25 -1 26 *7 28.3 29.9 31 *5 33.1 --- Detection of Diresorcinol as an Impurity in Synthetically Prepared Phloroglucinol.By J. HERZIG and S. ZEISEL ( J h a t s h . , 11, 421-423) .-The presence of diresorcinol, as an impurity in phloro- glucinol, scarcely affects its melting point, or the nnmbere obtained on estimating carbon and hydrogen. It may be best detected by dissolving a few milligrams of the sample in about 1 C.C. of concen- trated snlphuric acid, adding 1-2 C.C. of acetic anhydride, and warming the mixture for a few minutes i n a water-bath. If diresor- cinol-or its tetrethyl ether or tetracetyl derivative-be present, a bluish-violet colour, which disappears on the addition of much water or of an excess of alkali, will be produced. By this means, the presence of 0.4 per cent. of diresorcinol may be clearly shown, and the delicacy of the test is probably much greater.G. T. M. Estimation of Sugars by means of Copper Potassium Carbonate Solution. By H. OST (Bey., 23, 3003-3011 ; compare Abstr., 1890, 103l>.-A solution cmtaining 23.5 grams of crystallised copper sulphate, 250 grams of potassium carbonate, and 100 grams of hydrogen potassium carbonate per litre has the following advantages over Fehling's solution for the gravimetric determination of sugars :- (1) It is unchanged by keeping. (2) Its action on cane-sugar is relativcly slight. (3) After 10 minutes boiling, the precipitation of cuprous oxide is practically complete, and thus more concordant results are obtained. (4) The monosaccharoses precipitate almost twice asmuch cuprous oxide from this solution as from Pehling's solution. ( 5 ) The quantity of precipitate obtained from different kinds of sugars varies considerably, thus rendering it possible to determine the composition of mixtures.The solution may also be employed for Folumetric estimations, as the end reaction is sharp ; the time required for boiling, is, however, longer than with Fehling'H solution. For gravimetric determinations, 30 C.C. of the copper solu- tion is mixed with 25 C.C. of the sugar solution, water is added and the liquid boiled for 10 minutes, filtered through an asbestos filter, and the cuprous oxide reduced in a stream of hydrogen. The follow- ing table shows the quantity of copper precipitated by different sugars :- Copper. Xilligmins. 50 55 60 65 70 75 80 85 90 95 100 ---- Invert-sugar. Milligrams. 15 *2 16 *6 18'0 19 *4 20.8 22-3 23-7 85 *2 26 *6 28 *1 29 ' 5 -- Dextrose.Milligrams. 15 *6 17 *O 18 '5 19 '9 21 '4 22 *9 24 -4 25.8 27 -3 28 68 30 -3 --- Levulose. Milligrams. 14 *7 16 '1 17 * 5 18 *9 20 '3 21 -7 23.0 24 -3 25 -7 27 -1 28 -5 &lac tose . Milligrams. 17 '4 19 *1 20 *8 22'5 24 *2 25'9 27 -6 29 -3 81 '1 32 -8 34 -5 --ABSTRACTS OF CHEMICAL PAPERS. Copper. Milligrams. 105 110 115 120 125 130 135 140 115 150 155 160 165 170 175 180 186 190 195 200 2c5 210 215 220 225 230 235 240 245 250 255 260 265 270 275 280 285 290 295 298 -7 CI- v Invert-sugar. Milligrams. 31 '0 32 *4 33 -9 35.3 36 -8 38 *2 39 *7 41 '1 42 *6 44-0 45 -5 47.0 48 -5 50 '0 51 -5 53 -0 54.5 56 -0 57 -5 59-1 60 *7 62 '41 84 *1 65 -8 67 *5 69 *3 71 -1 7s -9 74 -8 76.7 78 *6 80 -5 82 -5 84.7 87 *I 89.7 92 -3 95 -1 98 '0 103 '0 -- Dextrose.Milligrains. 31'8 33 -3 34 *8 36 '3 37'8 39 '3 40 *s 42.3 43-s 45 -3 46.8 48.3 4g9 * 8 51 -4 52 *9 54'5 56.0 57 *c; a9 -2 60 *8 62 *4 64 '1 65.8 67.8 69 *2 70-9 72'7 74 *5 76 *4 78 -4 80 -5 82.8 85.1 87'5 89.9 92.4 94 -9 97.6 100 '4 102 *8 -- Levulose. Milligrams. 29 -8 31 -2 32.6 34.0 35.4 36 *8 38 *2 3'3.6 41 -0 42.5 43 .9 45-3 46.7 48'1 49.5 61 -0 52 -5 54 -0 55 *5 57 -0 58 fi 60.2 61 .S 63.5 65.2 6G 9 68 -7 70 *G 72 -5 74 -4 76 -5 78 *8 81 '1 83 -5 85 -9 88 6 91 '3 94 '2 97 -2 99 '0 ~ Galactose. I'Jilligrams. 36 '2 38 -0 39 -7 41 '4 43 -1 44 *8 46 5 48 -3 50.0 51 *8 53.6 55 *4 57.2 59 *o 60.8 62 *7 64 -5 66 '4 68 -3 70 *3 72 '3 74 *3 76 *3 78 -3 80 *3 82 -4 84 -5 86 -6 88.9 91.2 93.5 95 -9 98.3 1GO * 7 103 -3 106 *l 109 -0 112 -0 115'1 117 *O -- Arabinose.Milligrains. 34 -7 36.3 37 *9 39 *5 41 1 42 -8 44.3 46 '0 47'6 49 '3 50 '9 52 *G 54 '3 55 .9 57 *5 59 -2 60 9 62 -7 61 '4 66 *2 68.0 69.8 71.6 73 -5 75 4 77 -3 79 *3 81 -3 83.4 85 -5 87 -6 89 -8 92 -2 94 -6 97 *I 99 '6 102 -3 105 *1 107 -9 109 -5 -- In the case of lactose, the factor copper/l~ctose = 1.31 to 1.57 for solutions containing from 125 to 198 milligrams of sugar. For volumetric work, a n indicator must be employed; after 20 minutes boiling, 198 milligrams of lactose precipitate 190 milligrams of copper, Ra5ose, C,H,Ola + 5H20, does not affect the copper solution,ANALYTICAL CHEMISTRY. 127 but after hydrolysis, it has the highest reducing power, 50 milligrams precipitating 150 milligrams of copper. Estimation of Sugar in Milk.By M. KUHN (Bied. Centr., 19, 628 ; from 3IiZc*hzeit., 18, 926) .-Results obtained by Tollens’ method agree better with those obtained by Soxhlet’s method, when only so much serum solution is employed that the colour is bluish after boiling. If so much sugar solution is used that the liquid is greenish after reduction, results will be obtained which are 0.1 to 0-15 per cent. too low. The phosphotungstic acid method is not rccornmended. If Soxhlet’s method is not used, the lead acetate method should be employed. Estimation of Ash in Raw Sugar. By W. MINOR (Chenz. Zeit., 14,51O).-Stammer objects to the use of oxygen, and recommends air for the incineration of raw sugay in estiniations of ash. The author has investigated the point, and sees no reason for disqualifying oxygen nor any special virtue in the atmospheric nitrogen, and as burning the charred sugar in oxygen takes 25 minutes, whilst corn- biistion in air, with the aid of mechanical agitation, requires from 6 to 15 hours, he considers the oxygen method is distinctly to be recommended.11. A. L. J. B. T. N. H. J. M. Estimation of Starch. By 0. REINKE (Zeit. anal. Cl2etn., 29. 472-475 ; froin Zed. XpiritiiLdusf.) .-The author divides the processes hitherto proposed into those with and without high pressuw, and recommends the following as the best of the respective methods :- With high pressure : 3 gi-arns of the finely ground substance is stirred with 25 C.C. of a 1 per cent. solution of lactic acid and 30 C.C. of water in a metallic beaker, then covered and heated for 24 hours in a digester (Soxhlet’s or Lintiier’s) a t 3-& atmospheres pressure, then mixed with 50 C.C.of hot water and, after cooling, made up to 250 C.C. and filtered. 200 C.C. is then inverted by cohobating with 15 C.C. of hydrochloric acid (1.125 ~ p . gr.) for Z& hours, then neutralised with soda, made np to 500 c.c., and 25 C.C. of it titrated with Febling’s solution. Without high pressure : 3 grams of the substance is boiled with 50 C.C. of water, and then digested for au hour a t 62.3” with 0.05 gram of Lintnep’s diastase. It is then cooled, mads up to 250 c.c., and 200 C.C. inverted with acid 8s above. For the preparation of Lintner’s wade diastase, I part of green malt is extracted for 24 hours with 2 to 4 parts of 20 per cent. alcohol. The extract, filtered by suction, is precipitated with twice, or at most 2$ times, its volume of absolute alcohol.The upper liquor is poured off and the precipitate thrown upon a pressure filter, then rubbed down with absolute alcohol in a mortar, again filtered and washed with absolute alcohol and then with ether, and finally dried in a vacuum over sulphuric acid. For the purification of this raw product, the precipi- tation and digestion with alcohol, washing with ether, and drying are repeated. By this means, fclbuminoiid impurities are rendered insoluble and dextrino’id ex tractive matters removed. The dried product is a loose, yellowish-white powder, which has no action on128 ABSTRACTS OF CmMICAL PAPERS. Fehling’s solution either before or after boiling with hydrochloric acid, and which does not turn brown when its solution is evaporated on the water-bath. M.J. S. . A New Application of Molisch’s Reactions. By G, COLASANTI (Gazzetta, 20, 2C39--%05) .-Molisch (Abstr., 1886, 923) found that, the merest traces of sugar or glucosides (O*OOOOl per cent.) could be detected by the addition of one or two drops of an alkaline solu- tion of a-naphthol or thymol (15 to 20 per cent.), together with an excess of coiicentrated sulphuric acid. Molisch further derived from this reaction a confirmation of the alleged presence of sugar in normal urine. The author finds that extremely dilute solutions of potassium or sodium thiocyanate, treated ih the same manner, show first a green band and, on agitation, an iiiiense violet coloration resembling in all respects that obtained from solutions of sugar.On cooling the liquid, a, compound containing the naphthalene nucleus and the sulphonic group separates in a mass of long, slender needles. The solution of thiocyanate or thiocynnic acid must be very dilute, or on addition of sulphuric acid a brown coloration is produced, and hydrogen sulphide is evolved. Urine must similarly be diluted before treatment with a-naphthol, and altogether fails to give the thymol reaction. As urine has been found to contain thiocyanic acid, Molisch’s reaction affords no confirmation of the presence of sugar in khat fluid. Reaction of Thiocyanic Acid. By G. COLASANTI (Gazzetta, 20, 306--308).-1f a few drops of a solution of auric chloride (&th per cent.) made alkaline with a saturated solution of sodium carbonate or a 5 per cent..solution of potash are added to a few C.C. of a dilute solution of a thiocyanate (0.01 per cent.), a deep violet coloration is obtained, and a precipitate of metallic gold gradually separates. The thiocyanic acid in urine does not give the reaction, the liquid merely acquiring a reddish coloration. Schneider’s Method €or the Estimation of Malic Acid in Wine. Uy IS. NIEDERHAIJSER (C’hem. Centr., 1890, ii, 172; from Pharm. CentraZhaZZe, 31, 378-379) .-lo0 C.C. of t3he wine is neutral- ised with decinormal alkali, evaporated, incinerated, and the carbonic anhydride in the ash determined. From t,his amount, the quantity of carbonic anhydride equivalent to the total tartaric acid present is deducted, the difference being then calculated into malic acid.Since, however, wines usually coiitain other substances (tannic, succinic, acetic acids), all of which rieutralise alkalis, and would when incinerated produce carbonates, the author considers the method valueless. J. W. L. It exhibits great hydrolytic activity. S. B. A. A . S. B. A. A. comparison between Methods for Estimating Tartaric Acid. By J. T ~ T H (Chem. Beit., 14, 63-64).---To compare the three rival methods for the estimation of tartaric acid, the “ original Goldenberg ’ 9 method, the “ Ilorenz-Goldenberg” method, and the ‘( modified Goldenberg ” method, the author made simultaneous and duplicateANALYTICAL CEEMISTttY. 129 estimations in crystalline calcium tartrate, in wine lees, in argol, and in tartaric acid, following rigidly the directions laid down in each method ; the numbers obtained are tabulated, and from the results i t is concluded thstt the Lorenz modification of the Goldenberg method is the best method, and is applicable in all cases, a specially valuable factor about it being the introduction of one-third normal soda for the titration. With regwd to Roessneck's suggested method, the author shows that the amount oE antimonious oxide taken up by the calcium tartrate is not + a mol.for 1 mol., but is a variable quantity, which seems to depend on the amount of free tartrate in solution. D. A. L. Estimation of Tartaric Acid. By J. WOLFMANN (Ohem. Zeit., 14, 320 ; compare T6th, preceding abstract).-The author considera the use of litmus tincture unsatisfactory in deeply colonred tartaric solutions ; he has noticed neutralisation of alkali by humus in such solutions, and does not regard the question of the estimation oE tartaric acid as solved bay the Lorenz method, in fact, looks with greater favour on the Goldenberg-Geromont results.He himself endeavoured unsuccessfully to determine tartaric acid by titration with permangnnate. 1). A. L. Estimation of Tartaric Acid in the Crude Products of Tartaric Acid Factories. By J. TELRISZ (Crhem. Zeit., 14, :347).- In consideration of results recently published by T6th (see above), the author has made several estimations of tartaric acid in various samples of calcium tartrate and dried wine lees, applying, with much precision, both the " original '' and " modi6ed " Goldenberg-Geromont, and also the Lorenz method; the results are tabulated, and in his hands the latter method yielded undoubtedly higher results than the first two methods, and he agrees with Wolfmann (preceding abstract) in considering tbe modified Goldenberg-Geromont method the most trustworthy, up to the present time.Variations as great as 7-10 per cent., noted by Tdth, in different estimations of the same sample by this method, have not been obaerved in the preseut experiments. D. A. L. Estimation of Citric Acid in Parts of Plants. By E. Cr,AAssEN ( Z e i t . anal. Chern., 29, 468--469).-The plant is extracted with very dilute ammonia and ammonium csrbonate, the liquid somewhat con- centrated, precipitated with lead acetate, and filtered. The dried precipitate is boiled out with strong alcohol, then suspended in water, and decomposed by hydrogen sulphide.The filtrate is evaporated to zt thin ~yrup, mixed with ammonium chloride, excess of ammonia, and calcium chloride, and 3 volumes of alcohol added. The precipi- tate is filtered, washed with 75 per cent. alcohol, dried, and dissolved in hot dilute hydrochloric acid. After cooling, it is filtered, treated with excess of ammonia, and again filtered, and evaporated on the water-bath to dryness. The residue is %taken up with boiling ammoniacal water, and the insolkble calcium citrate collected on a weighed filter. Traces of citrate in the filtrate may be recovered by repeating the evaporation. M. J. S. VOL. r,x. k130 ABSTRACTS OF CHEMICAL PAPERS. Amount of Volatile Fatty Acids in Rancid Butter.By P. C o m E w A (Chern. Zed., 14, 406).--8amplen of fresh butter were taken and examiried on the 16th of Febriiary for volatile fatty acids ; they were then exposed in vessels covered with psper, and again examined on April 3rd, when, in all cases, a reduction in tbe quantity of volatile fatty acids was observed ; in a subsequent examination on April 30th, no further change was noted, but a final test, on AuguHt gth, indicated a still further falling off in these acids. The disappear- ance of T-olatilc fatty acids in the rancid buttJer, although progressive in these experiments, was in no instance very considerable, and in no case could volatile fatty acids be washed from the rancid butter either by water or sodium hydrogen carbonate.Butter and Margarine. By C. VIOLETTE (Compt. rend., 111, 345-347).--'l'he acids resulting from the saponification of 50 grams of pure, dry butter by aqueons potash are distilled in a current of ateam, and the successive portions of the aqueous distiliste (the total volume of which should not be less than 10 litzes) are titrated with normal sodium hydroxide, using phenolphthalein as an indicator. The volatile acids, which solidify, and tho non-volatile acids also, are weighed, after being dried in a vacuum and melted. A table i s given showing the results obtained with various butters and with margarine. It is assumed, on t,he evidence of Duclaux's results, that the ratio between butyric and caproic acids in genuine butter remains constant, and equal to 1.645. In ordinary butters the mean proportion of volatile acids is 7.6 per cent., wit,h a minimum of 7.0, and the proportion of non-volatile acids is 84.0 per cent., with a, maximum of 84-6.I n the case of a butter of high quality, the addition of about 20 per cent. of margarine would lower the proportion of volatile acids from 8.5 to the minimum of 7 per cent., and would raise the non-volatile acids from 82.63 to 84-76. In the case of ordinary butter, the addition of 9 per cent. of margarine would reduce the volatile acids to 7 per cent. Optical Analyses of Butters. By C. VIOLRTTE (Compt. rend., 111, 348).-From his observations, the author concludes that butter and margarine have different indices of refraction, the deviations in the oleorefractometer being -35" to -27" for bucters, and - 15" to -so for margarines.The indications of the oleoref ractometer are suffi - ciently exact when the instrument is applied to mixtures of con- stituents giving known deviations. It is necessary to ascertain, by means of a large number of observations, the minimum deviation below which a butter may be regarded as adulterat4ed with margarine. The olcorefractomet,er may be used for the analysis of commerci81 butters, but its iudicidions will not be very exact, because these butters will give deviations below the minimum f o r good butters, and the proportion of margarine deduced from the results will be too low. Analysis of Lard, Cotton Oil, and Tallow. By J. MUTER and L. DE KONINGH (Analyst, 15, 48--50).--Employing the method described by themselves (Arkalyst, April, 1889) for estimating the 1).A. L. C. H. B. C. H. B.ANALYTICAL CHEMISTRY. 131 liquid fatty acids in fats, and for treating them with iodine without. exposure to air, the ttiithors have obtained the following results. They regard tallow as the best material for the preparation of olei'c acid, and for this acid they find the iodine absorption to be 90 per cent., and to vary at most 0.2 per cent. from theory. The olei'c acid from lard never gives so low a number, the average being about 93 per cent., whilst that from cotton oil is found to be 135, with very little variation. In consequence of this wide difference, the per- centzge of cotton oil in a sample of adulterated lard can be indirectly estimated with considerable accuracy.M. J. S. Beeswax. By A. BUISINE and P. BUISINE (Bull. SOC. Chim. [3], 3, 867-8731 --The authors confirm the results previously obtained by Hub1 and Hebner with respect to the free, total, and combined acids of beeswax ; further, they have det,ermined the iodine numbers for this substance, m d describe a process for estimating the alcohols present. This consists in the fusion of the wax with potaasium hydroxide and pot,a,sh lime a t 250°, which causes the evolution of Iijdrogen proportionally to the amount of alcohols acted on, and from the residue of this experiment the hydrocarbons existing in the wax are determined by extraction with a suitable solvent. Their results for pure, dry, washed beeswax are summarised :- M. p. 63-64'. Entirely soluble in hot chloroform.Wax Acids. Free acids correRponding with 19--21 m i l l i p m s KHO per gram. 7, 7, 97 13.5-15.5 per cent. cerotic acid. Total acids 9 ) 91-97 milligrams KHO per gram. Combined a c i h ,, 72-76 ,, 7, 7 9 9 , 9 , 9 7 32-85-34.67 per cent. palmitic acid Ratio of free io combined acid 3.5 to 3.8. Iodine Numbers. 100 parts of wa.x absorb 8-3-11 parts iodine ; which corresponds to 9-12 per ccnt. olejic wid. Wax Alcohols. Hydrogen liberated by fusion with KHO, 53.5-57.5 C.C. per gram. Wax Hydrocadbons. M. p. 49.5. Iodine fixed by 100 parts of Estimation of Resin in Soap. By R. WIT,T,TAMS (AnaZyst, 15, 81--82).-Gladding's method (Abstr., 1883, 603) yields vcry good remits. The author prefers to work on the soap itself rHther than on che acids separated from it.Estimation of Csmpkor. By F. FOERSTER ( B e y . , 23, 2981-- 2989).-A number of substances now occur in commerce, consisting Percentage 12-5-14. 11 y drocar-bon 22-03. T. G. N. M. J. S.232 ABSTRACTS OF OREMIOAL PAPERS of nitrocellulose and camphor, and up to the present no method is known for estimating the amount of camphor which they contain. The author proposes to carry out the estimation by distilling the substances with soda solution, when the camphor readily passes over. This may be then extracted with benzene, and the specific rotatory power of the benzene sol ution ascertained. Detailed instructions for carrying out the reaction, and tables of the rotation of camphor in benzene solution at different concentlrations and temperatures are given in the original.The results obtained are about 0.7-1.0 per cent. too low, probably owing to the difficulty of driving out the last portions of camphor. The autbor finds that sublimed camphor contains a small quantity of impurity, and that for the determination of its rotatory power, high temperatures must be avoided in its preparation, and the camphor finally twice recrystallised from 50 per cent. alcohol. It then melted at 174+3-173.3", and after six crystallisations a t 1 'i6*3-176-5", and after 10 crystallisations the solidifying point was found by Landolt's method (Abstr., 1890,l) to be 15'8.7" (con-.). The boiling point of the purified camphor was 209.1" under 739 mm. Estimation of Tannin in Tea. By P. MALTSCHEFFSKY (.I. P~CWWL. [ 5 ] , 22,270-271 ; from Pharm.Zed. f. RUSS., 29,12i).-The tanuiri is precipitated by meitus of normal copper acetate, and the excess of copper is titrated by the aid of potassium ferrocpnide solution, The copper solution contains 7.657 grams of copper oxide per litre (1 C.C. = 0.01 tannin), and its strength is controlled by evaporating a measured volume t o dryness, moistening with nitric acid, heating to redness, and weighing tbe oxide. The ferrocyanide solution is prepared by making up to 1 litre, 100 C.C. of a saiurated solution. To standardise this solution, it is added, 1 C.C. at R time, to 5 C.C. of the copper solu- tion diluted to 100 c.c., until a drop of the mixed liquids gives a blue colonr with a solution (1 : 100) of ferric chloride. A second assay, in which the additions of ferrocyanide solution are made by tenths of a C.C.towards the end, gives the exact strength of the solution. 2 grams of tea, dried at 100-107" is extracted four times with 100 C.C. of boiling water each t h e ; the filtrates are united, made up to 400 C.C. ; 100 C.C. of this solution is boiled and treated with 10 C.C. of copper solution. The precipitate is filtered oft', washed with hot water, and the filtrate and washiip are made up to 200 C.C. ; half of this is taken, and the excess of copper is determined approximately by means of the ferrocyenide solution ; the second half of tbe solution then serves for the exact determination of the copper. In 14 samples, the amount of tannin yaried from 6.10 to 11.08 per cent. The water varied from 5.59 to 12 48 per cent.; ash, 3.14 to 9.25 ; aqueous extract, 17.3 to 39.4; caffeine, 1.09 to 2.88 per cent. J. T. Estimation of Urea. By P. M~QUEL (Compt. rend., 111, 501- 502).-Many of the nrophagic microbes, and especially micrococci and earcinae, can develop in a neutral and even in tt slightly acid cnltivation fluid. Several grow solely a t the bottom of the vessels and produce more or leks granular deposits without rendering the H. G. C. .ANALYTICAL CHEYISTRP. 133 liquid turbid, whilst at the same time tbey produce a large quantity of the soluble ferment (this vol., p. 100 ). These clear liquids should be used for the estimation of urea. An aqueous solution of urea is simply mixed with the cultivation fluid containing the ferment; the alkalinity i s at once estimated by titration, and the liquid is heated at 50" for two hours in a well- closed vessel, which it nearly fills.The alkalinity is again deter- mined? and from the quantity of ammonium carbonate formed the amount of urea present is calculated. Urine and ohher organic liquids are previously heated with a sligbt excess of ammonium carbonate, filtered if necessary, and then mixed with the feiment, the object of this treatment being to prevent loss of ammonia from formation of double salts, neutralisation of any acid present, &c. A quantity of urea exceeding 10 per cent. interferes with the activity of the ferment, and in solutions o€ 30 per cent. the ferment is it mctive. Concentrated solutions must, therefore, be diluted. Am- monium carbonate, sodium chloride in small proportion, uric acid, arnmoniacal and alkaline salts, extractive matters, albumin, and sugar in large quantity do not interfere with the results.C. H. B, Simple Mode of Estimating Urea. By C. W. HEATON and S. A. VASEY (Analyst, 15, 106--107).-The method, which does not aim at great accuracy, is suggested for the use of medical men in cases where none of the special forms of apparatus is available. An &-ounce bottle is fitted with a thistle funnel and gas delivery tube which dips under water in a basin. In the bottle is placed 1 fluid drachm of bromine and 10 fluid drachms of a 40 per cent. solution of caustic soda. A bottle full of water is inverted over the delivery tube to receive the gas ; 2 fluid drachms of urine is then poured into the generator and rinsed in by 1 fluid dirtchm of water, and +,be bottle is shaken until gas ceases to be evolved. The receiver is then closed by the thumb, removed from the basin, placed in an upright position, and filled up with water, the volume required being noted. Deducting 200 minims for the volume of air dis- placed by tho urine and water introduced into the generator, the remainder is equal in volume to the nitrogen evolved, and each 100 minims corresponds with 0.25 per cent of urea.M. J. S. Rapid Method of Estimating Urea in Urine. By C. J. H. WARDEN (Analyst, 15, 201--203).-l'he apparatus iR a modified Crum's nitrometer, 630 mm. long and of about 75 C.C. capacity. Into its lower end is ground a stopper, on which 10 narrow grooves have been filed. The cup above the stopcock i s of 5 C.C.capacity, and is accurately marked a t 2.5 C.C. The tube is graduated to show percentages of urea a t once, asmmirig that 1 per cent. of urea in 2.5 C.C. of urine will yield 9.27 C.C. of gas. The hypo- brornite solution is stated to be made by dissolving 100 '' grains" (? grams) of caustic soda in 750 C.C. of water and adding 25 C.C. of bromine. The inverted tube is filled with this solution and the stopper inserted. Ifs cxterior and the cup are then rinsed and134 AUSTHACTS OF CHEhUCAL PAPERS. dried. It is stood in a vessel of brine and the stopper is removed. 2-5 C.C. of urine is then placed in the cup and there mixed with its own volume of saturated brine to increase its densify, and this mixture is allowed to enter the tube in small portions.The last traces are rinsed in by brine. The tube is then grasped by the right hand, the thumb being tightly pressed against tbe open end, aiid the contents thoroughly agitated. It is then transferred to a vessel of water, where the heavy sollitions flow away, and the volume of the nitrogen is read in the usufil manner. M-. J. S. Estimation of The'ine in Tea. By G. L. SPENCER (CZcex2, Centr., 1890, ii, 172 ; from J. Arner. Chern. Soc., 4, 158).-2 to 3 grams of the finely ground tea is extracted i n a small beaker seven times with boiling water, the extract being each time decanted off, and the residue finally transferred to a filter, and washed with a few C.C. of boiling water. Ha.sic lea*d acetate is added to the extract, about 8 C.C. usually being snfficient; the precipitate is filtervd, washed with hot water, and the lead sepayated as sulphide, after wbjch the filtrate is concentrated to about 50 c.c., with addition of about 5 grams of calcium hSdroxide or mngnesium oxide.The liquid is again filtered, the insoluble portion extracted with hot water, and the tiltrate is extracted with chloroform seyen times. 'I'he chloro- form extract is distilled from a tared flask, and the weight of the residual theine recorded after drying at 75". The method has been in use in the Department of Agriculture. J. W, L. Estimation of Quinine. By SEATON and H. D. RICHMOND (AnaZyst, 15, 42- 43) .-In soh tions containing quinine bisulphate dissolved in an acid, and free from salts whose base is pyecipitable by baryta, the quinine may be estimated by titration.Quinine bi- sulpbate is neutrai to methyl-o~ange, whilst the base itself has no action on phenolphthalein. To 25 C.C. of the solution there are added 2 drops of methyl-orange solution (0.25 gram iii a litre of water), and 2 drops of phenolphthalein solution (0.5 gram in a litre of 50 per cent. alcohol). Baryta solution (N/10) is then run in until the red colour changes to a brown, at which point all the free acid is neutralised. The addition of baryta is then continued until the pink colour of the phenolphthalein appears. As the pink colour develop8 slowly, care must be taken not to overstep this point. The number of cubic centimetres required for this second stage, multiplied by 0.0218, gives the weight of the hepta-hydrated quinine sulphate present.M. J. S. Reaction for Cocai'ne. By F. DA SILVA (Compt. rend., 111, 54$-349).-A small quantity of cocaine, or one of its salts, or of thc residue obtained by evaporating a solution, is mixed with a few drops of fuming nitric acid of sp. gr. 1.4, evaporated to dryness on the water-bath, and the residue mixed with 2 or 3 drops of concentrated alcoholic potasli. A distinct, and peculiar (;dour, recalling that of peppermint, iLi developed. In lhageudorfl's systematic scheme ofASALTTICAL CHEMISTRY. 135 analysis, cocaine is found among the alkaloidu extracted by benzene from an aqueous ammoniscal solution. Of the other alkaloids of the same group, atropine, hyoscyamine, strychnine, codeine, and eserine give colortttions wlien treated in the same way,and eseriiie also develops a disagreeable odour resembling that of phcn.ylcarbylamine.Del- phinine, brucine, and veratrine give only indistinct odours, which cannot be confonnded with that from cocaine. Sabadilline and narcotine can be recognised in the same way, but the other alkaloids give no sensitive reactions of this order. The reaction will detect 0.5 milligram of cocaine hydrochloride. C. H. B. Detection of Colchicine in Corpses. By N. OBOLONSEI (&it. a n d Chem., 29, 493).-The finely divided viscera are rubbed up with glass powder treated with oxalic acid, and digested for 2‘2 hours with alcohol. The liquid is squeezed out, and the dry residue twice mashed wit.h alcohol. The extract is concentrated at a temperature not exceeding SO”, and the cooled residue made up to the original volume with alcohol.The filtered liqriid is evaporated as before, nad this operation repeated until no clots separate on the addition of alcohol. The residue is then dissolved in water, the solution purified by shaking with light petroleum, and the colchicine finally extracted with chloroform as usual. Tbe alkaloid is best identified by means o€ the violet colour pro- duced by nitric acid ; by Erdmann’s reagent (nitrosnlphuric acid), which gives in succession green, dark-blue, violet, and yellow colourti, turning to raspberry-red on adding alkali ; also by Mandelin’s reagent (1 gram of ammonium vanadate in ‘200 grams of siilphuric acid) which gives a green colour. Colchicine is with difficulty destroyed by putrefaction of animal matter.The kidneys, bladder, and urine are best suited for forensic examination. M. J. S. Detection of Bile Constituents in Urine. By A. JOLLUS (Zeit. a n d Chenz., 29, 402 -406).--Of the various tests proposed for detecting bile pigments in mine (Grnelin’s, Huppert’s, Vitali’s, Rosenbach’s, Ultzmann’s, Hoppe-Seyler’s, Dragendorff ’s), those of Rosenbach and Huppert, with the following modifications, give the best results :- Rosenbach’s Test.-A large quantity of the urine is filtered through clean, white filter-paper, the interior of the filter is touched with a drop of strong nitric acid containing nitrous acid, and the funnel is gently warmed over a flame. After a few minutes a green ring is formed round the spot moistened by the nitric acid. Huppert’s Test.-About 10 C.C.of the urine is shaken with an equal volume of milk of lime containing 10 grams of calcium oxide in the litre. The success of the test depends on the proper concentratioti of the milk of lime. The precipitate is filtered off and washed into a test tube with alcohol and dilute hydrochloric acid, then filtered, and the filtrate boiled, With only traces of bile pigments, the liquid becomes green to blue. An estimate of the amount of bile con- stituents can be obtained from the iodine number oE the urine. If g136 ABSTRACTS OF CHEMICAL PAPERS. is the number of grams of iodine absorbed by 10 C.C. of the urine, and s the specific gravity, the iodine number is - The number s-1 for normal urine, filtered after cooling, is 6.3 to 8.1, though even in specimens rich in uric acid it rarely exceeds 7.8.The presence of even traces of bile pigments raises the uumber to 9.6, and values as high as 17.4 have been observed. New Test for Albumin. By A. JOLLES (Zeit. ai2aE. Chem., 29, 406--407).-About 8 or 10 C.C. of albuminous urine is mixed with an equal volume of concentrated hydrochloric acid, and then 2 or 3 drops of a saturated solution of bleaching powder deposited quietly on the surface. If a8 little as 0.01 gram of albumin per 100 C.C. is present, a white turbidity appears at the surface of contact. This test, being less sensitive than that with nitric acid, which latter will detect 0*0015 gram per 100 c.c., may be used to find approximately the proportion of albumin present, since by diluting the urine until the one test gives an iiidication but the other none, the percentage may be known to lie between the above minimum limits.M. J. S. M. J. S. Detection of Albumin in Bacterial Urines. By A. JOLLES (Zeit. anal. Chem., 29, 407--408).-The most sensitive test for albumin in urine is that with acetic acid and potassium ferrocyanide, the lower limit of which is 0.0008 gram in 100 C.C. It is, however, necessary to filter the urine to obtain a standard with which to com- pare the turbidity produced by the test. When bacteria are present, ti clear filtrate is best obtained by shaking with infnsorial earth before filtering. In the case of purulent., slimy urines, rich in leuco- cytes, traces of albumin may adhere to the precipitate ; but by wash- ing this with warm potash, and testing the filtrate, the smallest traces of albumin may be detected.M. J. S.ANALYTICAL CHEMISTRY. 107A n a l y t i c a l Chemistry.Estimation of Hydrogen Chloride in Solutions of Hydroxyl-amine Hydrochloride. By J. A. MULLEK. (Rzill. Xoc. Chim. [ 3 ] , 3,605).-Phenolphthalei'n is unaffected by solutions of hydroxylaminehydrochloride, and the amount of acid present may be estimated bymeans of a standard solution of sodium hydroxide, free from carbon-ate, using phenolphthalein as the indicator. Pyridine, picolines, andlutidines behave similarly. T. G. N.Estimation of Sulphur in Inorganic Sulphides. By L. BLUM(Zeit. anal. Gem., 29, 411412).--The method publiahed byJannasch (Abstr., 1889, 1244, and 1890, 1187) is not new, havingbeen already brought forward by Sauer, in 1873 (Abatr., 1873, 939).M.J. S.Estimation of Nitrogen by the Schultze-Tiemmaam(Schloesing's) Method. By F. COGHIUS and T. MOELLER (Chern.Zeit., 14, 3%).-Low results are obtained by this method, especially inthe examination of explosives. This is attributed by the authors tothe addition of too much water, and to the want of proper relation-ship between the size of the apparatus used and the quantity of mate-rial employed. In some test experiments they used a long-necked350 C.C. flask, a measuring tube of 150 C.C. capacity, ferrous chloridesolution containing 70 grams in 100 grams of water, hydrochloric acidof about 37 per cent., and employed 0-3-0.4 gram of potassium nitrate,5-15 C.C. of the ferrous chloride solution, and twice the quantity ofthe hydrochloric acid.The ordinary course of operation was followed,avoiding unuecessary boiling to drive out the air. When 25 to 50 C.C.of water was added, the analysis lasted 30 to 40 minutes, and theresults varied between 13.76 and 13.86, mean 13.81, whilst with 80to 150 C.C. of water the variation in the results was from 13.05 to1339, mean 13.21, and the analysis lasted 70 to 90 minutes.D. A. L.Estimation of Nitrogen in Sodium Nitrate. By 0. FOERSTER(Chem. Zeit., 14, 509-510 ; compare Ahstr., 1889, 547, 746).-Twoor three grams of the nitrate is dried at 150" or by heating to inci-pient fusion, weighed, and repeatedly evaporated to dryness on a water-bath in a tared crucible, with 25 C.C. of about 19 per cent.hydro-chloric acid. After about the third evaporation, the nitrate is com-pletely converted into chloride, which is dried at 150°, ignited slightly,and weighed, and the nitrogen calculated from the difference. Themethod yields satisfactory results, but only in the absence of othersubstances, which would be attacked by hydrochloric acid.D. A. L.Estimation of Nitric Nitrogen as Nitric Oxide. By F.SCHEIDING (Chem Zeit., 14, 635-637).-For estimating nitric nitrogenas nitric oxide, the author has devised and employs the apparatusshown in the drawing, which is provided with a measuring tub108 ABSTRAOTS OF CHEMIOAL PAPERS.having a globular expansion, a glass tap H with a small funnel at thetop, and a special arrangement intimately attached by india-rubbertubing or fusion to the bottom.In operation, tube L is connectedin a suithble manner with a, movable reservoir containing sodiumhydroxide, sp. gr. 1.25, with which the apparatus is charged to thelevel of 4 by raising the reservoir, and clip 4 is closed. The substanceis placed, along with a little water, in a 200-250 C.C. flask, to whichthe stopper and tubes are fitted, connections made, and to expel the airthrough tubes 2 and 3, the water in the flask is boiled until thewater into which tube 3 dips is caused to boil by the issuing steam,clip 5 is then closed, and the air still in tube 1 driven into the mea-suring tube by opening clip 4, which is again closed, and the flameremoved from below the flask. The measuring tube is filled to thetop with sodium hydroxide, and tap H is closed.20-25 C.C. of coldsaturated ferrous chloride, and then 8-10 C.C. of concentrated hydro-chloric acid are carefully drawn into the flask through tubes 2 and3, which are then washed with water in the same way; the flask,suspended a few cm. above the wire gauze, is now heated, and aANALYTIGA L OHEMISTRY. 109soon as a, pressure i R indicated in the india-rubber tube at 4, that clipis opened, t,be nitric oxide passes into the measuring tube, and by thetime the liquid has yolatilised in the flask, all the nitric oxide is con-chided to be in the measuring tube. The temperature in the jackettube surrounding the measuring tube is made to correspond with thati n the vicinity of the bulb, and the level in the reservoir beingadjusted to that in the measuring tube, the volume is read off, andafter the necessary corrections are made, the percentage of nitrogen is.calculated therefrom.The saucer under the measuring apparatus isfilled with water to keep the tubes immersed in it cool. For substanceswhich might be deromposed by boiling with water, a tap funnel isfitted to the flask, and is used for charging it. D. A. L.Estimation of Nitrogen in Organic Substances by means ofAlkaline Permangmate. By R. L. WAGNER (Chem. Zeit., 14. 269).-The autbor some years ago recognised the possibility of oxidisingnitrogenous organic substances by means of alkaline permanganate,without the formation of ammonia. In his experimcnts he mixed0.5 to 1 gram of substance with 25-30 times its weight of potassiumpermanganate, and 5 C.C.of 25 per cent. potassium hydroxide, placedthe mixture in a tube closed at one end, terminating at the other in acapillary for the escape of oxygen, warmed in a water-bath to aidadmixture, and theu heated at 150-170" in an air-bath for two totwo and a half hours. The conQents of tbe tube were turned into aporcelain basin, the excess of manganate reduced with manganesesulphate and sodium carbonate, and the nitric acid deteimined inthe clear liquid by a modification of Eder's method ; but irregularityof combustion and breaking of tubes rendered the method practicallyuseless, except, perhaps, for substances soluble in alkalis. Non-vola-tile nitro-derivatives and ethereal nitrates can be safely oxidised byalkaline permanganate in a porcelain dish, excess of permanganatebeing subsequently reduced with alcohol, and the diluted filtratetreated with ferrous sulphate, zinc-dust, and hydrochloric acid ; thenitrogen is then estimated as ammonia, by any of the usual distilla-tion methods.Carbon bisulphide and thiophen can be oxidised by similar treatment,and the sulphur estimated in them; they are enclosed in thin glassbulbs, and placed in tubes containing the alkaline permanganate ; thetube is sealed up, the bulb broken, and tbe digestion proceededwith. D.A. L.Detection of Foreign Raw Phosphates in Powdered BasicSlag. By L. BLUM (Zeit. anal. Chem., 29, 408--411).-The relativesuperiority of basic slag as a fertiliser over natural phosphaticminerals, owing to its ready absorbability, and the high price whichi t has in consequence atkained, have led to its falsification with otherraw phosphates.Only such are likely to be used as, from their lowpercentage of phosphoric acid, cannot profitably be worked a p assuperphosphate, and these in most cases contain much calcium carb-onate. Fresh basic slag is almost absolutely free from carbonates,and even ou long exposure to air, absorbs very little carbonic aci110 ABSTRAOTS OF OHEMIOAL PAPERS.(2.47 per cent. was found in an extreme case), so that the presence ofmuch carbonate i n a specimen would be enough to throw suspicionon it. A low percentage of iron and manganese might furnish anadditional indication, since tlhese metals are rarely present in naturalphosphates.In estimating the carbonic acid by decomposition withan acid, some chromic acid should be added, to prevent evolution ofhydrogen aulphide from the sulphides present, but a simple estima-tion of the loss on ignition would generally allow an opinion to beformed. M. J. S.Estimation of Water in Superphosphates. By J. STOKLASA (Zeit.anal. Chem., 29, 390--397).-Pure monocalcium tetrahydrogen phos-phate, CaH4(P04)2 + HzO, loses its water of crystallisation at loo",but only completely after 40 hours. It may be kept at 105" for20 hours with but little change, but on longer heating at the sametemperature begins to show decomposition. At higher temperatures,the amount of change is dependent not alone on the temperature,but also on the time of drying.The statement of Drewsen (Abstr.,1881, 465) that drying even at 300" does not diminish the proportionof soluble phosphate, but merely reduces it to a soluble pyroyhosphate,cannot be confirmed for pure or nearly pure monocalcium phosphate.I t might be true for a superphosphstc in which free phosphoric acidconstituted 80 per cent. of the total soluble phosphoric acid.On drying for one hour at ZOO", one-half of the monocalciumphosphate undergoes decomposition, thus :-4Cs€&( PO,), = Ca?,P207 + Ca(P03), + CaH2P207 + 2H3POa + 4H20. At lower tempera-tures for the same length of time, the proportion decomposed issmaller, but if the time is prolonged, a further decomposit'ion takesplace ecen at 150", and less free phosphoric acid is fouud in the solublepart.A temperature of 200" sufficiently prolonged results in thefollowing decomposition : 4 C a H 4 ( PO& = 3Ca(P03)2 + CaH2P207 + 7H20, whilst at 210", there remains nothing but insoluble, glassycalcium metaphosphate. I n presence of free phosphoric: acid, thecontrary action may on heating take place, thus: ChP,O, + 2H,PO,= 2CaH2P207 + H,O, and thus the soluble phosphoric acid actuallyundergo increase. M. J. S.By R. FRESENIUS(Zeit. anid. Chem., 2 9 , 4 1 3 4 3 0 ; see Abstr., l890,924).-A11 attemptsto Qbtain complete separation by niems of chvomic acid in a single pre-cipitation resulted in failures. The seemingly satisfactory separationobtained by Frerizhs and by Russmann (next abstract) resuited fromthe accidental compensation of opposite errors, since they washed thebarium chromate wibh acetic acid, in which it is distinctly soluble,and weighed it after drying a t 110", at, which temperature it stillretains some moisture.In a solution containing alkaline acetate anddichromate, barium chromate is, however, quite insoluble. It canalso be rendered anhydrous without decomposition by ignition at adull red heat, even the portion adhering to the filter reoxidising aftertemporary reduction. By double precipitation of the barium, a com-plete separation can be effected even when the proportion ofSeparation of Barium from StrontiumANALYTICAL CHEMISTRY. 111strontium is large. The solution of the chlorides is feebly acidifiedwith acetic acid, and diluted until it contains not more than 0.5 percent.of the bases, then precipitated hot with a n excess of ammoniumchromate, which has been carefully neutrahed with ammonia, Aftercooling €or an hour, the precipitate is washed by decantation withvery di1ut.e ammonium chromate until the washings no longer give aprecipitate with ammonium carbonate, and then further with warmwater until the washings are scarcely coloured by silver nitrate. Theprecipitate is then dissolved in the smallest possible quantity ofnitric acid, and the solution again diluted and heated. Ammoniummetate is added in sufficient quantit-v to displace the free nitric acidby acetic acid, and then ammonium chromate until the odour of aceticacid bas completely disappeared. After an hour, the liquid is pouredthrough a filter, the precipitate is digested with hot water, cooled,filtered, and washed thoroughly with cold water.It is then free fromstrontium, whilst the filtrates contain no barium. Double precipita-tion from neutral or alkaline solutions has not been successful.M. J. S.Separation of Barium, Strontium, and Calcium. By A.RUSSMANN (Zeit. anal. Chent., 29, 447-454; from Tnaug. Diss.Berlin, 1887).-Barium cannot be satisfactorily estimated by Frericbs’method (precipitation from an acetic acid solution by normalpotassium chromate), since the filtrate always contains traces ofbarium, and some potassium chromate is carried down by the preci-pitate. The precipitate will also contain strontium, if the proportionof the strontium in the solution exceeds 30 parts per 100 of barium.Calcium is not so precipitated.The simplest way to ascertain theweight of the barium chromate, is to dissolve it in dilute hydrochloricacid, add potassium iodide, and immediately tit rate with thiosulphate.Diehl’s method for separating barium and calcium by digesting thesulphates with sodium thiosulphate solution is complicated by somany sources of error that it cannot be recommended. Fresenius’method of separating barium and calcium by dilute sulphuric acid ina solution acidified with hydrochloric acid is thoroughly satisfactory.The method of Sidersky (Abstr., 1883, 509) for separating strontiumand calcium only yields approximate results.For separating bariumand calcium, it is, however, serviceable. Bloxam’s method (Abstr.,1886, 920) is not suitable for quantitative separations, as thestrontium sulphate carries down with it considerable quantities ofccLlcium, and the calcium ammonium arsenate cannot readily bebrought into a, form for weighing in which i t contains a constantproportion of calcium. Fleischer’s method for separating bariumand calcium by digestion with 3 parts of potassium sulphate and1 part of carbonate, followed by titration of the calcium carbonate inthe weighed precipitate gives good results. Lastly, Leison’s met.bodfor the estimation of the individual alkaline earths, by precipitationwith oxalic acid and alcohol, and titration of the oxalic acid in theprecipitate by permanganate, is accurate.The barium oxalate mustbe dissolved by hydrochloric acid, as it is not completely decomposed by.sulphuric acid. Strontium and calcium oxalates can be decomposedby sulphuric acid. The solutions must not be filtered throngh paper112 ABSTRACTS OF CHEMIOAL PAPERS.and must be highly dilute. Ignition of the oxalates is, however, asa rule, the quicker process.Estimation of Cadmium in the Products of Zinc Manu-facture and in Calamine. By W. MINOR (Chem. Zeit., 14, 4, 34,and 348-349) .-The material is dissolved in hydrochloric acid,treated with hydrogen sulphide, and the precipitate washed with hot,water, dissolved in hydrochloric acid, heated to boiling, and pouredinto dilute sodium hydroxide likewise heated to boiling.This preci-pitate, after washing with hot water, is ignited in a current of oxygen,and weighed as cadmium oxide. Material containing but little iron,such as “ pure cadmium,” is dissolved in hydrochloric acid, and preci-pitated directly with the sodium hydroxide. This method ofprecipitation may also be used to separate zinc and cadmium i n t,heordinary method of examining calamine ; the ammoniacal solutioncontaining the zinc and cadmium is rendered slightly acid andpoured hot into the hot hydroxide, &c.In the method described in the last of the three papers, the materialis dissolved in hydrochloric acid, filtered from undissolved lead,precipitated with hydrogen sulphide, the precipitate, containingzinc and an inconsiderable amount of arsenic, is washed, dried,weighed, dissolved in dilute hydrochloric acid, and treated withsodium hydroxide in excess.The cadmium hydroxide is filtered off,and the zinc titrated in the filtrate with sodium sulphide, calculated .to zinc sulphide, and deducted from the weight of the cadmiumsulphide precipitate. I n another method (requiring the absence ofother metah precipitated by sodium hydroxide) after removal ofiron with ammonia, the solution of zinc and cadmium is nearlyneutralised with hydrochloric acid, and then treated with sodiumhydroxide. The precipitate of cadmium hydroxide i R dissolved indilute hydrochloric acid, evaporated to dryness, dissolved in water,and titrated with standard sodium hydroxide, using litmus or sodiumsulphide papers as indicators.Good results have been obtained byboth methods, the first being the more suitable in the presence ofmuch zinc and vice versc2. D. A. L.M. J. S.Estimation of Cadmium as Sulphide by Precipitation withSodium Sulphide Solution. By W. MINOR (Chem. Zeit., 14,439-440) .-The material is dissolved in hydrochloric or nitric acid,and the lead separated by sulphuric acid ; the solution is then treatedwith soda, and the precipitate digested with ammonia. The ammoniacalsolution is free from lead, zinc, and iron, but contains all the cadmium,which can then be determined by means of sodium sulphide solution,either volumetrically by tit ration, nsing ferric hydroxide as indicator,or gravimetrically by precipitating, and weighing the precipitateafter drying for some hours at 140-145O.D. A. L.Volumetric Estimation of Zinc and Copper. By E. DONATRand G. HATTENSAUR (Chenz. Zeit., 14, 323--325).--Various experi-ments have been made by the authors. They find that for titratingzinc by Schaffner’s method, it is better to use sodium hydrosulphidANALYTICAL CHEMISTRY. 113(prepared by adding a known volume of dilute sodium hydroxide toan equal volume of the same solution previously saturated withhydrogen sulphide) than a solution of the crystalline sulphide ofcommerce ; howerer, in using this reagent in solutions containingtartaric acid and ammonia, the iron commences to precipitate beforeall the zinc is converted into sulphide. The estimation of zinc by usingexcess of ferrocyanide, after the removal of the iron, and titrating backwith permanganate does not answer, since in the cold a clear solutioncannot be obtained, whilst if warm, decompositions occur whichcause irregularities.It is noticed that ferrocyanide precipitates zincbu h not iron in the presence of tartaric acid and ammonia, and that theexcess of either of these substances does not seriously disturb therelative quantity of 1 mol. ferrocyanide to 2 atoms of zinc ; therefore1 C.C. of a solution containing 33.5 grams of potassium ferrocyanideper litre corresponds with 0.010 gram of zinc. As small an excess ofammonia as possible, and a hot solution, are favourable to the preci-pitation. The zinc precipitate is not decomposed by acetic acid;therefore, by placing drops of this acid and the solution under exami-nation in contact, in the presence of iron, a coloration indicatescomplete precipitation of' the zinc.The following method it; based onthese considerations :--3 t o 4 grams of material is dissolved in hydro-chloric acid with some nitric acid, diluted to a definite volume withwater, an aliquot part filtered, treated with 20-25 C.C. of concen-trated tartaric acid solution, a slight excess of ammonia added, andthe liquid warmed to about 80". The ferrocyanide is now run in untilthe precipitation of the zinc is complete, as indicated in the mannerdescribed above. The proportion of iron to zinc ili the solution underexamination should be the same as that present in the solution usedfor standardising the ferrocyanide.Under similar circumstances, copper is precipitated in a likemanner, but the precipitation is greatly influenced by ammonia ;fherefore the solutio~r for titration should be neutral or nearly so.The ferrocyanide is standardised from a solution of copper of knownstrength, and cannot, be approximated to by the weight of fcrrocyauideemployed, inasmuch as the composition of the copper precipitate isuncertain.Copper and zinc may be estimated in the same solutionby this method ; first both are titrated, then the copper is precipitatedout of another portion of solution, and the zinc alone titrated, &c.D. A. L.Estimation of Lead by Phosphomolybdic Acid. By H. BEUF(Bull.. Soc. Chinz. [3], 3, 852--855).-To the boiling neutral solutionof the metal, an aqueous solution of phosphomolybdic acid is addeduntil the supernatant liquid is coloured yellow by the excess ofreagent used.After washing, the precipitate is dried at 90-100°and weighed. It forms a dense, white powder which is insoluble inwater (1 in 500,000) and aqueous ammonia, but dissolves in nitricand in acetic acids ; it contaiiis 54.8 per cent. of lead, and correspondswith the formula Mo,Pb2,P2H,,0,,,; at a high temperature it loses7 mols. H20.By decomposition of the precipitate with dilute sulphuric acid andeinc at a gentle heat, a brown liquid is obtained, wbich may beYOL, LX. 114 ABSTRACTS OF CHEMIUAL PAPERS.titrated for lead by a solution of permanganate which has beenpreviously standardised against a solution resulting from tho similartreatment of a known weight of a lead salt.The phosphomolybdic acid is made by evaporating to dryness asolution of ammonium phosphomoly bdate in nitric acid.Iron iseliminated by a previous treatment with sodium hydroxide, copper,potassium, and ammonium by washing the mixed pbosphomolybdateswith ammonia-water, but the presence of zinc or arsenic vitiates theestimation. T. G. N.Separation of Copper from Arsenic by the Electric Current.By L. W. MCCAY (C‘laem. Zcib., 14, 509).-Under the influence ofthe current from four to six Meidinger elements, alkaline arsenatesremain in solution, whereas copper is completely and quantitativelyprecipitated, and has been estimated wikh good results.Moreover,t h e copper is quite free from arsenic, and the solution may be safelyemployed for the determination of the original amount of the lattermetal. D. A. L.Estimation of Aluminium in Commercial Aluminium. By0. KLEMP (Zeit. anal. Chsm., 29, 388--390).-The prccess employedfor zinc (Abst , 2890, 1190) cannot be applied to aluminium since,always evolved, but bv dissolving the aluminium in potash, and burn-ing the hydrogen in Fi=eserlins’ apparatus, a very accurate estimationcam be made. About 1 gram of the metal in filings is placed in a150 c c. flask with a little vaselin to prevent frothing, and the potashsolution (35 grams of KOH in ‘LOO c.c.) is added gradually, withwarming towards the close.Estimation of Alumina in Bread, &c.; Solubility of Alu-minium Phosphate in Acetic Acid.By W. C. YOUNG (dnalyst,15, 61-63 ; 83-S4).-1n Duprk’s process, the aluminium is precipi-tated as phosphate from an acid solution containing ammoniumchloride and acetate, and is collected after remaining all night in thecold. Test analyses, with weighed quantities of alum, show thatunder these conditions the resalts are much below the truth. Thebest result (from a mixture of alum, sodium phosphate, and aceticacid) was obtained by boiling the mixture both before and after theaddition of ammonium acetate, and filtering immediately. Theamount of ammonium acetate must not be too small, nor that ofacetic acid too large. For 0.1 gram of potash alum, there mas used1 gram of ammonium acetate and 5 C.C.of ordinary acetic acid. Thepresence of ammoriiuni chloride has little effect when the liquid isfiltered immediately after boiling, but lowers the result i E the pre-cipitation is performed iu the cold, or the mixture is allowed to coolbefore filtering. M. J. S.Estimation of Iron Oxide and Alumina in Phosphates. ByR. JONES ( C h e w Zeit., 14, 269--271).-The author criticises themethods employed until recently, and recommends as the bestthe following Combination of Glaser’s method, slightly modified, witheven with big ;i; ly dilute alkali and a large excess of iodate, hydrogen isThe operation takes about 45 minutes.M. J. SANALYTICAL CHEMISTRY. 115part of Stutzer's method. The phosphate is dissolved in hydrochloricand nitric acids, made up to a definite volume, an nliquot parttaken and treated with ft quarter of its volume of sulpluricacid of sp.gr. 1.84, and its om11 volume of 95 per cent. alcohol,making up to definite volume with the alcohol ; after 12 honrs,the gypsum is collected, and when weighed, gives good results forcalcium i n absence of much magnesium. The alcohol is driven offfrom the filtrate, which is rendered alkaline with ammonia andboiled to completely drive off the ammonia. The precipitate may beweighed, and half the weight taken as iron oxide and alumina, whichgives good results, or it may be treated with molybdic solution, thephosphoric acid 'separated in the usual way, the iron and aluminaprecipitated wlth dilute ammonia, redissolved in hydrochloric acid,reprecipitated, &c., and weighed.Titration of Chromates, Barium Salts, and Sulphates.ByP. SOLTPIEN (Clteni. Centr., 1890, ii, 217-218 ; from Pharm. Zeit.,35, 372) .-The titration of solutions of barium salts with potassium&chromate, and inversely the titration of chromates with bariumsalts, may be readily performed with either hzematoxylin or logwoodextract as indicator. A solution of barium chloride is prepared equalto one of potassium dichromate, and for the determination of bariumsalts, potassium dichromate is run in from the burette until a dropplaced on a warmed porcelain plate with a drop of haematoxylin justshows the formation of a blue-black coloration. The solution to betitrated must be neutral, and may not contain more than the meresttrace of either acetic acid or ammonia.Chlorides and nitrates do not in-terfere with the reaction, nor does rosolic acid, which latter may be useda s an indicatlor for the titration of soli~tions of salts of barium. If thesolution of a chromate contains sulphat,es, the titration with barhimchloride gives the total qnaritity of the two salts, from which mustbe deducted the amount of the latter as determined gravimetrically.For the determination of the combined snlphuric acid, an excess ofbarium chloride solution is added, and the excess determined bytitration with pot.assium dichromate.Salts of aluminium, copper, and iron must be removed from thesolutions. J. W. L.Estimation of Antimony by Marsh's Method.By A. VANBYLERT (Ber., 23, 2968-2971 ; compare Kuhn and Saeger, Abstr.,ISYO, 1187).-For the estimation of antimony in alloys of tin,silver, and antimony, the author recommends the following process :-A three-necked Woulffe's bottle is connected on the one hand with annpparatus for evolving carbonic anhydride, and on the other with thuusual calcium chloride tube and hard glass tube. The central neckof the Woulffe's bottle is fitted with a wide tube reaching to thebottom of the flask. About 0.5 gram of the alloy is dissolved in20 C.C. of mercury at 60", and poured, after cooling, into the fiask.100 C.C. of 10 per cent. sulphuric: acid is then added through one oLcthe side tubes, and the air expelled from the apparatus by carbonicanhydride.A freshly prepared sodium amalgam, obtained by dis-solving 5.5 grams of sodium in 25 c . ~ . of mcrcury, is then aclded dro]~D. A. IJ.i;116 ABSTRACTS OF CHEMICAL PAPERS.by drop through the wide tube. The sublimate of antimony quicklyappears in the heated tube ; the apparatus is then periodically shaken,care being taken that no liquid is allowed to pass into the centraltube. After the evolution of gas has ceased, carbonic anhydride isagain passed tbrough the apparatus t o expel all the hydrogen andhydrogen antimonide. The mercury solution is then poured off,dried with filter-paper, and divided into two equal portions, one ofwhich is returned t,o the cleaned and dried apparatus, and coveredwith 75 C.C. of a 10 per cent. sulphuric acid, whilst the other is mixedwith 3 grams of sodium, and added drop by drop through the centraltube as before.The results obtained are fairly accurate, but might possibly beimproved by employing lirdrogen in place of carbonic anhydride fordriving out the air. Another soiirce of error is the oxidation whichtakes place in the manufacture of the alloy, and during its solution inthe mercury.H. G. C.Estimation of Hardness of Natural Waters. By E. JJ. NEUGE-JMJER. (Zeit. anal. Chem., 29, 399-401 ).-The author proposes thefollowing modifications of Clark's test. The standard water is amixture of 8 vols. of calcium sulphate solution of 12" of hardness with2 vols. of a 12" magnesium sulphate solution. Of this mixture,100 C.C. is used. The soap solution is of such strength that 12 C.C. isrequired for the 100 C.C.of standard water. The following new tablehas been drawn up from titrations of the standard water diluted tothe required degrees :-Hardness.. .......... 0" lo 2" 3" 4" 5" 6"C.c of soap solution . . 0.6 1.7 2.8 3.9 4.9 5.9 6.9Hardness.. .......... I 8" 9" 10' 11" 12"C.c of soap solution ,. 7.8 8.7 9.6 10.4 11.2 1200F Oand a, special burette (titanometer) constructed, the readings of whichgive a t once the degrees of hardness.The Analysis of Sulphurous Waters. By D. VITALI (Chem.Cen.fr., 1890, ii, 166 ; from L'Orosi, 13, 73-778).-Thiosulphates maybe detected by the addition OE potassium nit,rite and a mineral acid oracetic acid. Nitric oxide is liberated, and the solution is therebycoloared yellow ; later, sulphur is precipitated, and the liquid becomesmilky.'Ibis reaction is extremely delicate, 0.0001 per cent. of thio-sulphate being detectable. I n testing for nitrites in presence of thio-sulphates with potassium iodide and starch, this reaction of the tbio-sulphate may prevent the formation of the blue iodide of starch, ayellow coloration being produced instead. In testing for iodine, inpresence of thiosulphates, with potassium nitrite and an acid, it isbetter to evaporate the water to dryness after neutralising withsodium carbonate, and then to extract the residne with absolutealcohol, which dissolves the iodide, leaving the thiosulphate undis-solved. In the case of waters containing large quantities of calciumsnlphnte, it is recommended to first precipitate the calcium as calciumcarbonate before determining the silicic anhydride. Xu order toprevent tho precipitation of sulphur during the evaporatior of waterM.J. SANALYTICAL UHEMISTRY. 117for determination of the total solid residue. the author recommendsthat a current of hydrogen should be passed through the water.J. W. L.Examination of Water for Contamination by Gas Works,By F. DICKMAEN (Zeit. miat. Cirem., 29, 398--399).-1n a specimen ofwater from a brook which had suffered contamination from a neigh-bouring gas works, and by which poultry had been poisoned, thoauthor detected traces of a substance giving the reactions of di-pbenylamine. Owing to the stability of this compound and thesensitiveness of its reaction with nitric acid, its presence might beused as a proof of contamination by tar-water, if i t should be foundto be a constant constituent of that liquid.Detection and Estimation of Organic and Inorganic Poisonsin Corpses.By A. SEYDA (Chem. Zeit., 14,31--32, 51-53,128 -129,181-184, and 198-200) .-The author describes his system ofexamining corpses. The chemical examination proper is preceded bya preliminary examination of the blood, urine, and contents of thestomach and accessories.The blood, when not too decomposed to show the absorption bands,is examined spectroscopically ; if dry, it is dissolved in water, and madevery slightly alkaline with sodium hydroxide ; the two oxyhaemoglobinbands amd the intermediate haemoglobin band merge into one con-tinuous band in partially decomposed blood; the faint band in thered is attributable to methaemoglobin in alkaline material or tohmmatin in acid blood.In the former case, fiwther examination isonly made under exceptional circumstances, such 8s the presence ofhydrogen sulphide not emanating from ordinary putrefactive pro-cesses ; but, in the latter case, the red band being due to hsematin, isregarded as indicating the presence of other reducing agents, or ofacids, potassium chlorate, ferricyanides, nitroglycerol, or nitro-benzene, which are tested for in the urine and in parts of the body.Other isolated lines in the red are carefully noted, and carbonic oxideis sought for ; the presence of hsmatin, already reduced or otherwise,indicates the absence of carbonic oxide poisoning ; carbonic oxide haemo-globia is recognised in presence of oxyhEmoglobin and hEmoglobinby the mere displacement of the absorption band towards the red partof the spectrum when ammonium sulphide is added ; chemical testswith sodium hydroxide with or without calcium chloride are con-sidered of little value.In the urine :-Notes are taken of the quantity, colour, odour, of re-actions as to the presence of blood, albumin, and sugar, of the action inalkaline copper solutions, of the behaviour toyvards barium chloridebefore and after treatment with hydrochloric acid, and of the occur-rence of balsams, alkaloids, soluble metallic poisons, and of such saltsas potassium chlorate, iodide, or bromide.The contents of tlie stomach are examined in the dark for phosphor-escence, which is only due to phosphorus in acid mixtures, otherwisefungoid growth may cause it.The, udour of the contents of thestomach may be acid, alkaline, like decayed cheese, or they may havea specific odour, or be putrid ; sometimes they are well preserved, andM. J. S118 ABSTRACTS OF OHEMICAL PAPERS.have a sweetish, repulsive odour, observed by the author in cases ofar.ienical poisoning. Food iizagmas and vomits are carefully sampled,treated with alcohol and then with ether, and examined macro- andmicro-scopically. The alcoholic extract is examined for oxalases andforeign bases and acids ; matters found in the folds are also examined.The arsenic test is applied, and an aqueous extract of the magma isexamined f o r soluble poisons.For the chemical examination proper, parts of organs, finely divided,arc heated with water in a boiling water-bath for several hours,acidified q-ith tartaric acid, and distilled with steam.Two fractionsare made: the first will contain the more volatile matters, such asalcohol, aldehyde, acetone, chloroform, nitrobenzene, ethereal oils,turpentine, camphor, amines, and their volatile corn binations ; theother, the remains of these more volatile products, and any lessvolatile substances, such as fatty acids, phenol, hydrocyanic acid, &c.A plain distillation of alkalilie material is required at times ; if, how-ever, the presence of chloral bydratc or hydrocyanic acid and ferro-cyanides is suspected, the finely divided orgaris are first moistenedwith potash or with hydrogen sodium carbonate respectively.Asteam distillation from alkaline solution, when necessary, is bestejfected, not directly, but with the liquid obtained by extraction withwater and tartaric acid. The residue from the acid distillat'ion isemployed in testing for alkaloids.The odour, colour, opdesceiice, quantity, &c., of the first fraction ofthe acid distillate are noted. I t is tested with silver nitrate, both innitric acid and in ammoniacal solution, with sodium nitroprusside,potash, and acetic acid ; with alkaline permanganate ; with iodine andpotash (iodoform reaction) ; with zinc-dust and hydrochloric acid fornitrobenzene ; with hydrochloric acid and alcoholic phloroglucinol forotheyeal oils (a reaction frequently takes place, but too much depend-ance is not to be placed on it; it is better to examine the urine for someof these substances, also for altered camphor).The reagents for tur-pentine oil, in tangible quantities, are a mixture of fresh guaiacumalcohol and fresh citronella oil. Resorcinol and potash are betterreagents for detecting chloroform than the isonitrile test. A quantita-tive examination for these substances is seldom possible, with theexception of alcohol, but this cannot be estimated by distillation in thepresence of amines ; therefore it is oxidised to acetic acid as follows.A portion of the distillate is redistilled, the first portions collectedare dried with potassium carbonate, distilled again, treated withsodium dichromate and sulphuric acid, rendered alkaline with potash,boiled t o eliminate amine bases, then acidified, steam distilled, andthe distillate, containing the acetic acid, titrated ; any sulphuric acid,if accidentally present, being estimabed and allowed for.The authorat,taches great importance to the estimation of alcohol, especially inthe case of children. Various parts of corpses of persons addicted t calcohol yield distillates containing alcohol, but not pure ethyl alcohol ;therefore such distillates reduce alkaline permanganate, &c., give theiodoform reaction, and yield an inflammable distillate on redistillationfrom potassium carbonate. Alcohols readily evaporate from corpses,the more volatile disappearing firstANALYTICAL CHEMISTRY.119Passing on to the second fraction from the acid distillation, phenol, asn normal product of the decomposition of nlbuminoids, is frequentlydetected by Millon's reagent, less readily by bromine-water. Largequantities of phenol are estimated by filtering the fraction containingit from the fatty acids, extracting with ether, drying the etherealresidue over sulphuric acid, and weighing, taking precautions againstthe phenol creeping over the edge of the evaporating dish. Asregards hydrocyanic acid, the distillate is tested with copper sulphateand guaiacum, and if the reaction is noticed, i t is confirmed by someother test, and the acid determined as silver cyanide.Phosphorus isgenerally recognised by the phosphorescence, but if this does notoccur phosphorous acid must be tested f o r and estimated in the residue.I n examining the distillate for phosphorus, it is redistilled, using anupright bulbed tube, the distillation being continued for an hourafter phosphorescence has ceased to appear; the new distillate istreated with silver nitrate, &c., and also is tested for phosphorus byoxidising with chlorine-water and adding ammonium molybdate.I n examining for alkaloids, special care must be taken not to mistakeptomaines for other alkalo'ids, and to allow for the impure form of thelatter. The material is treated with alcohol containing tartaric acid,the extract filtered, evaporated, dissolved in water, filtered, neutra-lised with potash, concentrated, treated with alcohol, separated fromthe potassium tartrate, and the neutral aqueous fiolution is testedwith alkaloid reagents (a preliminary test with tmtaric acid and iodicacid being made for morphine) and examined systematically ifrequired.A portion is rendered alkaline, and steam-distilled fornicotine, coniine, miline, &c. I n the absence of these volatile bases,another portion is extracted with ether successively when neutral,acid, and alkaline, ehen with chloroform while still alkaline, andfinally is made ammoniacal and extracted with aniyl alcohol. Thet8hird portion is reserved for the direct confirmatory examination ofany alkaloid icdicated in the other portions.The aqueous residue istested for narceine and curarine, whilst the various extracts areexamined separately. The residue from the dkaline-ether extract istested with phosphoric acid for aconitine. Vitali's atropine reactionis liable to be hidden by xaiithoprotcin colour reactions. For strych-nine, a double test is made: first., a drop of vanadic acid solution ismixed with the Gesidue, dissolved in sulphuric acid, which is subse-quently diluted with concentrated sulphuric acid, and then solidammonium vanadate is dusted over another portion of the samesolution. Attention is called to the fact that colocynthine givesreactions with both vanadic and chromic acids, which resemble thoseof strychnine with the same reagents. The atuyl alcohol extract,after purifying, serves for confirming the presence of morphine.Another portion of the original extract is examined for metallicpoisons soluble in alcohol.The examination for metallic poisonsgenerally is made with the residue from the first distillation or that,from the alcoholic extraction ; in the latter case the alcohol is expelledby warming. The residue is heated with hot water, potassium chlorate,and hydrochloric acid until the organic tissue is destroyed a r d allchlorine driven off, the magma is treated with tartaric .acid, the120 ABSTRAOTS OF OHEMIOAL PAPERS.largely diluted with water and, after 24 hours, filtered. Tho insolubleportion is treated (if required with more chlorate and hydrochloricacid, then) with alcohol, and with ether to extract fat, and is ignited,The ash is treated with very dilute hydrochloric acid, and the residuedried, ignited, weighed, and proved conclusively to be silica byfusion with sodium carbonate ; or is examined for silver, lead, barium,and strontium.The soluble portion is marde up to a definite volume,and must be free from chlorine and chloric acid.For mercury, a portion is nearly nentralised by means of potash,and is digested with brass wool €or 15 minutes a t 70" ; if the brass isvisibly amnlgnmatecl, the presence of mercury is confirmed by heatingin a test-tube, &c. ; but when the presence of niercury is not so evident,the brass wool is burnt with copper oxide in a current of air in a tabe25 cm. long, drawn out to a doubly bent capillary, in which anymercury is accumulated, and identified with iodine. To estimatemercury, the hot hydrochloric solution is treated with hydrogensulphide, the precipitate collected on an asbestos filter (or if arsenic ispresent, i t is first digested with yellow ammonium sulphide) washedwith hydrochloric acid, dissolved in nitric acid, filtered through someasbestos, and the washings and filtrate diluted and treated with phos-phorous acid.After 24 hours, the calomel is filtered off, washed with,water, alcohol, and ether, and weighed on a tared filter. Tbi*oughoutthe estimation, high temperatures and contact with organic matterare to be avoided.To detect antimony, some of t,he liquid partly neutralised withammonia is placed in a bright platinum dish with a piece of zinc forsix hours ; the brownish-black antimony flakes obtained in this mannerbeing more trustworthy than Marsh'R test.This test does not answei-in the presence of tin ; but by fusing the mixed oxides wit11 sodiumhydroxide, most of the tin can be separated. To estimate antimony,hydrogen sulphide is passed through the slightly acid, and at firstboiling, solution until it has cooled down ; after three days, most ofthe hydrogen sulphide is driven off by carbonic anhydride, the preci-pitate washed with an acetic acid solution of ammonium acetate,treated and washed with a solution of sodium sulphide, containinghydrogen sulphide, the solution treated carefully with hydrochloricacid, warmed, and then boiled. After 24 hours, the precipitate is col-lected, treated with an acetic acid solution of ammonium acetate, thencarefully with nitric acid, evaporated, the residue moistened withsodium hydroxide, intimately mixed with dry sodium carbonate, dried,introduced by small quantities at a time into fused sodium nitrate in a,silver crucible, and the mass, when cold, treated with water.After24 hours, the precipitate is washed with 45 per cent. alcohol, contain-i n g soda, digested with il hot solution of tartaric and hydrochloricacids for half an hour, filtered, and washed with a dilute solution oftartaric a d hydrochloric acids. The filtrate and wasbings combinedare concentrated in a water-bath, the excess of acid reduced withammonia, and the antimony precipitated by hydrogen sulphide as a pureorange-coloured sulphide which is converted into oxide by Bunsen'smethod.The purity of the antimony is ultimately confirmed by itsvolatilityANALYTICAL CHEMISTRY. 121To detect arsenic, mercury and antimony being absent, variousobvious precautions are observed in applying the Marsh test to someof the liquid, and when a mirror is obtained, the tube containing i tis divided by a diamond into four parts, of which one is used for theodour test, another for solubility in freshly-prepared sodium hypo-chlorite, a third for dissolving in nitric acid arid testing with silvernitrate, whilst the fourth is dissolved in nitric acid, and convertedinto arsenic sulphide by colourless ammoniuin sulphide. To estimatearsenic, hydrogen sulphide is passed through the warm hydrochloricsolution for 12 hours, and after remaining three to five days in aclosed flask, most of the hydrogen sulphide is driven off by a currentof carbonic anhydride ; the procedure then resembles that described inthe antimony estimation, but various points are to be observed :-1.Ammonia or ammonium carbonate are the only solvents used forarsenic sulphide on the filter. 2. The fusion is conducted in a porcelaincrucible with fusion mixture and potassium nitrate. 3. The arsenic isalways weighed as magnesium pyroarsenate. 4. The alkaline solutionis not precipitated directly with magnesia mixture, but is first Rub-mitted to the following treatment :-Neutralisation with nitric acid,expulsion of carbonic anhydride and nitrous acid, precipitation withhydrogen sulphide, and conversion into arsenic acid. 5.The ammo-nium magnesium arsenate is redissolved in hydrochloric acid and re-precipitated by ammonia. 6. Small quantities of magnesium arsenateare converted into pyrosrsenate by dissolving in very dilute nitric acid,evaporating in a porcelain crucible over a water-bath, and carefullyand gradually igniting the residue ; the method is susceptible of greataccuracy ; as little as 0.0093 to 0.0077 gram of arsenic in a portion ofa dead body has been estimated. 7. Large quantities of pyroarsenateare preserved as such for reference ; small quantities aro convertedinto metallic arsenic in a Marsh’s apparatus, and are preserved in ELsealed tube.In the absence of mercury, antimony, and arsenic, the hydro-chloric acid solution is made alkaline with soda, acidified with aceticacid, hydrogen sulphide passed in at the boiling point of the liquid anduntil cold, sodium carbonate added to distinct alkalinity, and the wholeallowed to remain corked up until clear.The solution serves for de-tecting and estimating tin. The precipitate is washed with sodiumsulphide containing hydrogen sulphide, oxidised with nitric acid, evapo-rated, moistened with sodium hydroxide, mixed with fusion mixture,dropped into molten nitre in a silver crucible, extracted with water,supersaturated with hydrochloric acid, filtered, and the hydrochloricacid solutions submitted to the ordinary methods of analysis, weighingany metal isolated in a definite form. The separation of iron, alumina,and zinc in the presence of calcium and magnesium phosphates iseffected in the following manner :-The hydrochloric acid filtrate fromthe hydrogen sulphide precipitate is concentrated on the water-bath,treated with chlorine-water, evaporated, the residue dissolved in verydilute hydrochloric acid, filtered, the solution supersaturated with am-monia, excess of the latter nearly expelled on the water-bath, the pre-cipitate removed, the solution acidified with acetic acid, and hydrogensulphide passed into the boiling hot liquid until it gets cold.The zin122 ABSTRACTS OF CHEMICAL PAPERS.sulphide is weighed. The ammonia precipitate is dissolved in nitricacid, treated in a platinum dish with tin, which by repeated and carefultreatment with nitric acid is converted into stannic oxide, and with i tthe phosphoric acid into insoluble stannic phosphate, from which thealumina is washed out by yery dilute nitric acid, and estimated inthe solution by precipitating with ammonia, igniting the precipitate,fusing the ignition residue with sodium carbonate, extracting withwater, filtering, &c.The alkaline filtrate from the hydrogensulphide precipitate is examined for tin :-It is acidified with hydro-chloric acid, boiled, hydrogen sulphide passed through until it is cold ;after remaining for 24 hours in a warm place the precipitate is collected,washed with an acetic acid solution of ammcinium acetate, and ignitedwith the filter.The residue is moistened with nitric acid, evapo-raked, ignited, and to get rid of the iron present it is washed into asilver crucible, dried, and treated for I.~df-nn.hour with moltensodium hydroxide, extracted with water, filtered, the filtrate acidifiedwith hydrochloric acid, and the tin obtained in the usual manner.I n concliision, it is pointed out that not only are potassium, sodium,calcium, magnesinm, iron, and niaiiganese noimally present in thehuman body, but that aluminium, copper, and zinc are always met with,and less frequently tin and lead. These extraneous metals are derivedfrom food, cooking utensils, medicine, &c. ; aluminium comes fromvarious sources, and even after death may be introduced iii the dust,when the post-mortem takes place i n the countr-y.The authoi* in advo-cating his employment of a solution prepayed directly froin the corpseinaterial for the detection of arsenic, points out that consideriiig thesensitiveness of the arsenic reaction a concentrrttion of the solutionis not necessary, that the “brown speck” on the porcelain lidreferred to by Otto cannot interfepe in his method, which, more-over, obviates any chance of vitiation through arsenical hydrogensulphide. It is also shown that the presenceof chlorides and nitratesdoes not stop the formation of gaseous hydrogen arsenide, providedthat the zinc and hydrochloric acid are in excess and the evolutionof hydrogen is allowed to proceed snfficiently long ; but the presenceof free nitric acid stops the evolution temporarily.It is still doubtfulwhether solid hydrogen areenide is converted into the gaseous modi-fication by zinc and hydrochloric acid.Ordinarily only one poison is found in a corpse, but nevertheless i tshould he borne in mind that there is the possibility of more thanone being present.Detection of Paraffin in Beeswax. By H. HAGEI~ (Zeit. anat.Cliem., 29, 480481 ; from Pharrn. Centi-allmlle, 30, 565).-A fewgrams of the substancs in fine, air-dried shavings is gradually heatedin a small, porcelain capsule, until fumes begin to rise. A half-litrewide-mouthed bottle is then inverted upon the capsule, and whenfilled with white vapours is closed and set aside until the fumes bavecondensed upon its walls. The sublimate is then dissolved in 3 C.C.of chloroform, the chloroform evaporated in a test-tube, and theresidue boiled with 4 C.C.of soda solution. If paraffin was present, it,will after cooling be found floating on the clear solution. A drop ofD. A. LANALYTICAL CHEMISTRY. 123the chlorofoi*m solution niay also be evaporated on a slip of glass andexamined microscopically.The fumes from pure beeswax are not so whiteas from paraffin, andare only obtained at a higher teinpe~ature (300-320"). The sub-limate gives a coloured solution with chloroform, and a coloured andturbid solution with soda. The residue from the chloroEorm solutionis a dnll film ; paraffin on the contrary gives separate grains in aclear field. M. J. S.Condition of the Sulphuric Acid in Plastered Wines, and aMethod of Distinguishing between Plastered Wines and Winesmixed with Sulphuric Acid.By L. Roos and E. THOMAS (Compt.reitd., 111, 573--577).-Wines which have been mixed with calciumsulphate do not contain potassium hydrogen sulphate. The liberatedtartaric acid interacts with the organic potassium compounds in thewine, and forms a new quantity of potassium hydrogen tartrate.Direct experiment shows that when calcium sulphate is added to asolution of potassium hydrogen tartrate, and an acetate, malate,citrate, or succiaate, the liquid contains no free sulphuric or tartaricacid, but acetic, citric, malic, or succinic acid is liberated. No potas-sium hydrogen sulphate could be detected i n plastered wines by thefollowing method, which will detect the addition of 0-25 gram ofsulphuric acid per litre.'l'he proportion of chlorine and the total sulphuric acid in the wineare estimated. 50 C.C.of the wine is mixed with a small quantity ofammonium acetate, and exactly procipitated with a standaiad solutionof barium chloride. The filtrate is evaporated to dryness, heatedgently, and the chlorine in the residue is estimated. If only normalpotassiuni sulphate is present, the reaction is &SO, + BaC'I, =BaSOl + 2KC1, and the chlorine in the residue should be equal tothe chlorine of the barium chloride, plus the chlorine originallypresent in the wine ; i f the acid sulphate i s present, the reaction iaKHSO, + BaCl, = BaSOp + HC1 t KC1, and the free hydrogenchloride is cxpelled i n the process of evaporation, the loss increasingwith the quantity of hydrogen-sulphate present.Estimation of Dissolved Solids in Wine.By E. L ~ S Z L ~ (Chem.Zeit., 14, 438, 455).--Results are quoted, showing t,he unsatisf'nctsrycharacter of estimations of " extractives " made by drying residuesfor 2$ hours. The author suggests determining the alcohol both bydistillation and by an alcoholometerat 15" ; the difference between t.hetwo observations being due to the "extractives" present may beutilised as a measure for them, and he finds that miiltiplying thisdifference by 0.32 gives numbers for the quantity of dissolved solidmatter in 100 C.C. of wine concordant with actual determinations.'l'he alcoholometer should not have a greater range than lo", or at theoutside 12", and f o r wines of sp.gr. greater than 1.000, a saccharo-ueter showing volume percentages is emplcyed.Detection of Methylated Nitrous Ether. By J. MUTER(Analyst, 15, 48).-Much of the sweet spirits of nitre in commerce isprepared from- methylated spirit instead of from pure ethyl alcoholC . H. B.D. A. L124 AliSTRAOTS OF CHEMICAL PAPERS.as prescribed in the pharmacopceia. The two may be discriminatedby dissolving a fragment of solid potash in a sample. Themethylated ether darkens, the colour varying from deep-yellow toorange-red, while the odour of methylated spirit becomes verydistinct. The ether from pure spirit loses its odour of ethyl nitrite,and retains only that of ethyl alcohol, and it does not dnrkeu beyondthe faintest straw colour.On treating with Hubl’s reagent the dis-tillate obtained after digestion with potash, tho methylated sample willabsorb 0.4 to 0.7 per cent. of iodine, but that from pure spirit none.Analysis of Carbolic and Sulphurous Disinfecting Powders,By J. MUTER (AnaZyst, 15, 63--68).-The author calls attention totbe ambiguities in the usual forms of specification for disinfectingpowders. Whilst the contracts are nominally for “ carbolic acid,” i tis commonly understood that the powder may contain chiefly cresoland other high-boiling tar phenols. There have, however, been caseswhere the supply of the more costlyabsolute phenol has been insisted on.The omiesion of the word “ available ” before “ sulphurous acid” some-times renders a literal compliance with a specification impossible.For the estimation of the phenols, the author still employs his ownprocess (Abstr., 1888, 92), with the single modification that 150 C.C.of a 10 per cent.solution of sodium hydroxide is now used instead of200 C.C. of a 5 per cent. solution. The cresol, measured in contactwith brine, retains about 5 per cent. of water. Since anhydi-ouscresol increases in volume by about 5 per cent. when shaken with3 volumes of brine, whilst that containing water does not increase o rmay even diminish, this furnishes a rough but ready test for t h epresence of water. For more accurate work the water must be dis-tilled out. Naphthalene, which is usually present in commercialcresol, may be estimated as follows :-50 C.C. is shaken with 200 C.C.of a 10 per cent.solution of sodium hydroxide. The phenols dissolve,leaving the naphthalene floating. The solution is removed, thenaphthalene washed with a 5 per cent. soda, solution, then rapidlyfiltered off. It is rinsed from the filter with water and again collectedon a pair of filters. After drying as far as possible by pressingbetween blotting paper, the filters are separated and the inner onewith its contents is weighed, using the outer one as a tare.For estimating the available sulphurous acid, 2 grams of the powderis washed 011 a filter with dry ether until the phenols and tarrymatters are removed. As soon as the ether has evaporated, thecontents of the filter are thrown into a bottle containing 50 C.C.ofN/10 iodine solution, and after half an hour the residual iodirie istitrated by thiosulphate. This method is unsatisfactory when thebasis of the powder is lime.I n sulphurous powders which have undergone osidation, the amountof original sulphurous acid cannot be ascertained if the mixture hadconsisted of gypsum and calcium sulphite, but where the basis issilica, the sulphates present may be regarded as oxidised sulphites,and where sodium hydrogen sulphite has been mixed with gypsum, theestimatiou of calcium, sulphuric, and sulphurous acids in an aqueousextract will give the necessary data.M. J. S.M. J. SANALYTIOAL OHEMISTRY. 125Arabinose.Milligrams.17 -018 *620 '321 -923.525 -126 *728.329.931 *533.1---Detection of Diresorcinol as an Impurity in SyntheticallyPrepared Phloroglucinol.By J. HERZIG and S. ZEISEL ( J h a t s h . , 11,421-423) .-The presence of diresorcinol, as an impurity in phloro-glucinol, scarcely affects its melting point, or the nnmbere obtainedon estimating carbon and hydrogen. It may be best detected bydissolving a few milligrams of the sample in about 1 C.C. of concen-trated snlphuric acid, adding 1-2 C.C. of acetic anhydride, andwarming the mixture for a few minutes i n a water-bath. If diresor-cinol-or its tetrethyl ether or tetracetyl derivative-be present, abluish-violet colour, which disappears on the addition of much wateror of an excess of alkali, will be produced. By this means, the presenceof 0.4 per cent.of diresorcinol may be clearly shown, and the delicacyof the test is probably much greater. G. T. M.Estimation of Sugars by means of Copper PotassiumCarbonate Solution. By H. OST (Bey., 23, 3003-3011 ; compareAbstr., 1890, 103l>.-A solution cmtaining 23.5 grams of crystallisedcopper sulphate, 250 grams of potassium carbonate, and 100 grams ofhydrogen potassium carbonate per litre has the following advantagesover Fehling's solution for the gravimetric determination of sugars :-(1) It is unchanged by keeping. (2) Its action on cane-sugar isrelativcly slight. (3) After 10 minutes boiling, the precipitation ofcuprous oxide is practically complete, and thus more concordantresults are obtained. (4) The monosaccharoses precipitate almosttwice asmuch cuprous oxide from this solution as from Pehling'ssolution.( 5 ) The quantity of precipitate obtained from differentkinds of sugars varies considerably, thus rendering it possible todetermine the composition of mixtures. The solution may also beemployed for Folumetric estimations, as the end reaction is sharp ; thetime required for boiling, is, however, longer than with Fehling'Hsolution. For gravimetric determinations, 30 C.C. of the copper solu-tion is mixed with 25 C.C. of the sugar solution, water is added andthe liquid boiled for 10 minutes, filtered through an asbestos filter,and the cuprous oxide reduced in a stream of hydrogen. The follow-ing table shows the quantity of copper precipitated by differentsugars :-Copper.Xilligmins.50556065707580859095100----Invert-sugar.Milligrams.15 *216 *618'019 *420.822-323-785 *226 *628 *129 ' 5--Dextrose.Milligrams.15 *617 *O18 '519 '921 '422 *924 -425.827 -328 6830 -3---Levulose.Milligrams.14 *716 '117 * 518 *920 '321 -723.024 -325 -727 -128 -5&lac tose .Milligrams.17 '419 *120 *822'524 *225'927 -629 -381 '132 -834 -5-ABSTRACTS OF CHEMICAL PAPERS.Copper.Milligrams.1051101151201251301351401151501551601651701751801861901952002c5210215220225230235240245250255260265270275280285290295298 -7CI-vInvert-sugar.Milligrams.31 '032 *433 -935.336 -838 *239 *741 '142 *644-045 -547.048 -550 '051 -553 -054.556 -057 -559-160 *762 '4184 *165 -867 *569 *371 -17s -974 -876.778 *680 -582 -584.787 *I89.792 -395 -198 '0103 '0--Dextrose.Milligrains.31'833 -334 *836 '337'839 '340 *s42.343-s45 -346.848.34g9 * 851 -452 *954'556.057 *c;a9 -260 *862 *464 '165.867.869 *270-972'774 *576 *478 -480 -582.885.187'589.992.494 -997.6100 '4102 *8--Levulose.Milligrams.29 -831 -232.634.035.436 *838 *23'3.641 -042.543 .945-346.748'149.561 -052 -554 -055 *557 -058 fi60.261 .S63.565.26G 968 -770 *G72 -574 -476 -578 *881 '183 -585 -988 691 '394 '297 -299 '0~Galactose.I'Jilligrams.36 '238 -039 -741 '443 -144 *846 548 -350.051 *853.655 *457.259 *o60.862 *764 -566 '468 -370 *372 '374 *376 *378 -380 *382 -484 -586 -688.991.293.595 -998.31GO * 7103 -3106 *l109 -0112 -0115'1117 *O-- Arabinose.Milligrains.34 -736.337 *939 *541 142 -844.346 '047'649 '350 '952 *G54 '355 .957 *559 -260 962 -761 '466 *268.069.871.673 -575 477 -379 *381 -383.485 -587 -689 -892 -294 -697 *I99 '6102 -3105 *1107 -9109 -5--In the case of lactose, the factor copper/l~ctose = 1.31 to 1.57 forsolutions containing from 125 to 198 milligrams of sugar.Forvolumetric work, a n indicator must be employed; after 20 minutesboiling, 198 milligrams of lactose precipitate 190 milligrams of copper,Ra5ose, C,H,Ola + 5H20, does not affect the copper solutionANALYTICAL CHEMISTRY. 127but after hydrolysis, it has the highest reducing power, 50 milligramsprecipitating 150 milligrams of copper.Estimation of Sugar in Milk. By M. KUHN (Bied. Centr., 19,628 ; from 3IiZc*hzeit., 18, 926) .-Results obtained by Tollens’method agree better with those obtained by Soxhlet’s method, whenonly so much serum solution is employed that the colour is bluishafter boiling. If so much sugar solution is used that the liquid isgreenish after reduction, results will be obtained which are 0.1 to0-15 per cent.too low. The phosphotungstic acid method is notrccornmended. If Soxhlet’s method is not used, the lead acetatemethod should be employed.Estimation of Ash in Raw Sugar. By W. MINOR (Chenz. Zeit.,14,51O).-Stammer objects to the use of oxygen, and recommends airfor the incineration of raw sugay in estiniations of ash. The authorhas investigated the point, and sees no reason for disqualifyingoxygen nor any special virtue in the atmospheric nitrogen, and asburning the charred sugar in oxygen takes 25 minutes, whilst corn-biistion in air, with the aid of mechanical agitation, requires from6 to 15 hours, he considers the oxygen method is distinctly to berecommended.11. A. L.J. B. T.N. H. J. M.Estimation of Starch. By 0. REINKE (Zeit. anal. Cl2etn., 29.472-475 ; froin Zed. XpiritiiLdusf.) .-The author divides the processeshitherto proposed into those with and without high pressuw, andrecommends the following as the best of the respective methods :-With high pressure : 3 gi-arns of the finely ground substance is stirredwith 25 C.C. of a 1 per cent. solution of lactic acid and 30 C.C. ofwater in a metallic beaker, then covered and heated for 24 hours ina digester (Soxhlet’s or Lintiier’s) a t 3-& atmospheres pressure, thenmixed with 50 C.C. of hot water and, after cooling, made up to 250 C.C.and filtered. 200 C.C. is then inverted by cohobating with 15 C.C. ofhydrochloric acid (1.125 ~ p . gr.) for Z& hours, then neutralised withsoda, made np to 500 c.c., and 25 C.C.of it titrated with Febling’ssolution. Without high pressure : 3 grams of the substance is boiledwith 50 C.C. of water, and then digested for au hour a t 62.3” with0.05 gram of Lintnep’s diastase. It is then cooled, mads up to 250 c.c.,and 200 C.C. inverted with acid 8s above. For the preparation ofLintner’s wade diastase, I part of green malt is extracted for24 hours with 2 to 4 parts of 20 per cent. alcohol. The extract,filtered by suction, is precipitated with twice, or at most 2$ times, itsvolume of absolute alcohol. The upper liquor is poured off and theprecipitate thrown upon a pressure filter, then rubbed down withabsolute alcohol in a mortar, again filtered and washed with absolutealcohol and then with ether, and finally dried in a vacuum oversulphuric acid.For the purification of this raw product, the precipi-tation and digestion with alcohol, washing with ether, and dryingare repeated. By this means, fclbuminoiid impurities are renderedinsoluble and dextrino’id ex tractive matters removed. The driedproduct is a loose, yellowish-white powder, which has no action o128 ABSTRACTS OF CmMICAL PAPERS.Fehling’s solution either before or after boiling with hydrochloricacid, and which does not turn brown when its solution is evaporatedon the water-bath.M. J. S. .A New Application of Molisch’s Reactions. By G, COLASANTI(Gazzetta, 20, 2C39--%05) .-Molisch (Abstr., 1886, 923) found that,the merest traces of sugar or glucosides (O*OOOOl per cent.) couldbe detected by the addition of one or two drops of an alkaline solu-tion of a-naphthol or thymol (15 to 20 per cent.), together with anexcess of coiicentrated sulphuric acid.Molisch further derived fromthis reaction a confirmation of the alleged presence of sugar in normalurine.The author finds that extremely dilute solutions of potassium orsodium thiocyanate, treated ih the same manner, show first a greenband and, on agitation, an iiiiense violet coloration resembling in allrespects that obtained from solutions of sugar. On cooling the liquid,a, compound containing the naphthalene nucleus and the sulphonicgroup separates in a mass of long, slender needles. The solution ofthiocyanate or thiocynnic acid must be very dilute, or on addition ofsulphuric acid a brown coloration is produced, and hydrogen sulphideis evolved.Urine must similarly be diluted before treatment witha-naphthol, and altogether fails to give the thymol reaction.As urine has been found to contain thiocyanic acid, Molisch’sreaction affords no confirmation of the presence of sugar in khat fluid.Reaction of Thiocyanic Acid. By G. COLASANTI (Gazzetta, 20,306--308).-1f a few drops of a solution of auric chloride (&th percent.) made alkaline with a saturated solution of sodium carbonateor a 5 per cent.. solution of potash are added to a few C.C. of a dilutesolution of a thiocyanate (0.01 per cent.), a deep violet coloration isobtained, and a precipitate of metallic gold gradually separates.Thethiocyanic acid in urine does not give the reaction, the liquid merelyacquiring a reddish coloration.Schneider’s Method €or the Estimation of Malic Acid inWine. Uy IS. NIEDERHAIJSER (C’hem. Centr., 1890, ii, 172; fromPharm. CentraZhaZZe, 31, 378-379) .-lo0 C.C. of t3he wine is neutral-ised with decinormal alkali, evaporated, incinerated, and the carbonicanhydride in the ash determined. From t,his amount, the quantity ofcarbonic anhydride equivalent to the total tartaric acid present isdeducted, the difference being then calculated into malic acid.Since, however, wines usually coiitain other substances (tannic,succinic, acetic acids), all of which rieutralise alkalis, and wouldwhen incinerated produce carbonates, the author considers the methodvalueless.J. W. L.It exhibits great hydrolytic activity.S. B. A. A .S. B. A. A.comparison between Methods for Estimating Tartaric Acid.By J. T ~ T H (Chem. Beit., 14, 63-64).---To compare the three rivalmethods for the estimation of tartaric acid, the “ original Goldenberg ’ 9method, the “ Ilorenz-Goldenberg” method, and the ‘( modifiedGoldenberg ” method, the author made simultaneous and duplicatANALYTICAL CEEMISTttY. 129estimations in crystalline calcium tartrate, in wine lees, in argol, andin tartaric acid, following rigidly the directions laid down in eachmethod ; the numbers obtained are tabulated, and from the results i tis concluded thstt the Lorenz modification of the Goldenberg methodis the best method, and is applicable in all cases, a specially valuablefactor about it being the introduction of one-third normal soda forthe titration.With regwd to Roessneck's suggested method, theauthor shows that the amount oE antimonious oxide taken up by thecalcium tartrate is not + a mol. for 1 mol., but is a variable quantity,which seems to depend on the amount of free tartrate in solution.D. A. L.Estimation of Tartaric Acid. By J. WOLFMANN (Ohem. Zeit.,14, 320 ; compare T6th, preceding abstract).-The author considerathe use of litmus tincture unsatisfactory in deeply colonred tartaricsolutions ; he has noticed neutralisation of alkali by humus in suchsolutions, and does not regard the question of the estimation oEtartaric acid as solved bay the Lorenz method, in fact, looks withgreater favour on the Goldenberg-Geromont results.He himselfendeavoured unsuccessfully to determine tartaric acid by titrationwith permangnnate. 1). A. L.Estimation of Tartaric Acid in the Crude Products ofTartaric Acid Factories. By J. TELRISZ (Crhem. Zeit., 14, :347).-In consideration of results recently published by T6th (see above),the author has made several estimations of tartaric acid in varioussamples of calcium tartrate and dried wine lees, applying, with muchprecision, both the " original '' and " modi6ed " Goldenberg-Geromont,and also the Lorenz method; the results are tabulated, and in hishands the latter method yielded undoubtedly higher results than thefirst two methods, and he agrees with Wolfmann (preceding abstract)in considering tbe modified Goldenberg-Geromont method the mosttrustworthy, up to the present time.Variations as great as 7-10per cent., noted by Tdth, in different estimations of the same sampleby this method, have not been obaerved in the preseut experiments.D. A. L.Estimation of Citric Acid in Parts of Plants. By E. Cr,AAssEN( Z e i t . anal. Chern., 29, 468--469).-The plant is extracted with verydilute ammonia and ammonium csrbonate, the liquid somewhat con-centrated, precipitated with lead acetate, and filtered. The driedprecipitate is boiled out with strong alcohol, then suspended in water,and decomposed by hydrogen sulphide. The filtrate is evaporated tozt thin ~yrup, mixed with ammonium chloride, excess of ammonia,and calcium chloride, and 3 volumes of alcohol added.The precipi-tate is filtered, washed with 75 per cent. alcohol, dried, and dissolvedin hot dilute hydrochloric acid. After cooling, it is filtered, treatedwith excess of ammonia, and again filtered, and evaporated on thewater-bath to dryness. The residue is %taken up with boilingammoniacal water, and the insolkble calcium citrate collected on aweighed filter. Traces of citrate in the filtrate may be recovered byrepeating the evaporation. M. J. S.VOL. r,x. 130 ABSTRACTS OF CHEMICAL PAPERS.Amount of Volatile Fatty Acids in Rancid Butter. By P.C o m E w A (Chern. Zed., 14, 406).--8amplen of fresh butter were takenand examiried on the 16th of Febriiary for volatile fatty acids ; theywere then exposed in vessels covered with psper, and again examinedon April 3rd, when, in all cases, a reduction in tbe quantity ofvolatile fatty acids was observed ; in a subsequent examination onApril 30th, no further change was noted, but a final test, on AuguHtgth, indicated a still further falling off in these acids.The disappear-ance of T-olatilc fatty acids in the rancid buttJer, although progressivein these experiments, was in no instance very considerable, and in nocase could volatile fatty acids be washed from the rancid butter eitherby water or sodium hydrogen carbonate.Butter and Margarine. By C. VIOLETTE (Compt. rend., 111,345-347).--'l'he acids resulting from the saponification of 50 gramsof pure, dry butter by aqueons potash are distilled in a current ofateam, and the successive portions of the aqueous distiliste (the totalvolume of which should not be less than 10 litzes) are titrated withnormal sodium hydroxide, using phenolphthalein as an indicator.The volatile acids, which solidify, and tho non-volatile acids also, areweighed, after being dried in a vacuum and melted.A table i s givenshowing the results obtained with various butters and with margarine.It is assumed, on t,he evidence of Duclaux's results, that the ratiobetween butyric and caproic acids in genuine butter remains constant,and equal to 1.645.In ordinary butters the mean proportion of volatile acids is 7.6 percent., wit,h a minimum of 7.0, and the proportion of non-volatileacids is 84.0 per cent., with a, maximum of 84-6.I n the case of abutter of high quality, the addition of about 20 per cent. of margarinewould lower the proportion of volatile acids from 8.5 to the minimumof 7 per cent., and would raise the non-volatile acids from 82.63 to84-76. In the case of ordinary butter, the addition of 9 per cent. ofmargarine would reduce the volatile acids to 7 per cent.Optical Analyses of Butters. By C. VIOLRTTE (Compt. rend., 111,348).-From his observations, the author concludes that butter andmargarine have different indices of refraction, the deviations in theoleorefractometer being -35" to -27" for bucters, and - 15" to -sofor margarines. The indications of the oleoref ractometer are suffi -ciently exact when the instrument is applied to mixtures of con-stituents giving known deviations.It is necessary to ascertain, bymeans of a large number of observations, the minimum deviationbelow which a butter may be regarded as adulterat4ed with margarine.The olcorefractomet,er may be used for the analysis of commerci81butters, but its iudicidions will not be very exact, because thesebutters will give deviations below the minimum f o r good butters, andthe proportion of margarine deduced from the results will be too low.Analysis of Lard, Cotton Oil, and Tallow. By J. MUTER andL. DE KONINGH (Analyst, 15, 48--50).--Employing the methoddescribed by themselves (Arkalyst, April, 1889) for estimating the1). A. L.C. H. B.C. H. BANALYTICAL CHEMISTRY.131liquid fatty acids in fats, and for treating them with iodine without.exposure to air, the ttiithors have obtained the following results.They regard tallow as the best material for the preparation of olei'cacid, and for this acid they find the iodine absorption to be 90 percent., and to vary at most 0.2 per cent. from theory. The olei'c acidfrom lard never gives so low a number, the average being about 93per cent., whilst that from cotton oil is found to be 135, with verylittle variation. In consequence of this wide difference, the per-centzge of cotton oil in a sample of adulterated lard can be indirectlyestimated with considerable accuracy. M. J. S.Beeswax. By A. BUISINE and P. BUISINE (Bull. SOC. Chim. [3],3, 867-8731 --The authors confirm the results previously obtainedby Hub1 and Hebner with respect to the free, total, and combinedacids of beeswax ; further, they have det,ermined the iodine numbersfor this substance, m d describe a process for estimating the alcoholspresent.This consists in the fusion of the wax with potaasiumhydroxide and pot,a,sh lime a t 250°, which causes the evolution ofIijdrogen proportionally to the amount of alcohols acted on, andfrom the residue of this experiment the hydrocarbons existing in thewax are determined by extraction with a suitable solvent. Theirresults for pure, dry, washed beeswax are summarised :-M. p. 63-64'. Entirely soluble in hot chloroform.Wax Acids.Free acids correRponding with 19--21 m i l l i p m s KHO per gram.7, 7, 97 13.5-15.5 per cent.cerotic acid.Total acids 9 ) 91-97 milligrams KHO per gram.Combined a c i h ,, 72-76 ,, 7, 7 99 , 9 , 9 7 32-85-34.67 per cent. palmitic acidRatio of free io combined acid 3.5 to 3.8.Iodine Numbers.100 parts of wa.x absorb 8-3-11 parts iodine ; which correspondsto 9-12 per ccnt. olejic wid.Wax Alcohols.Hydrogen liberated by fusion with KHO, 53.5-57.5 C.C. per gram.Wax Hydrocadbons.M. p. 49.5. Iodine fixed by 100 parts ofEstimation of Resin in Soap. By R. WIT,T,TAMS (AnaZyst, 15,81--82).-Gladding's method (Abstr., 1883, 603) yields vcry goodremits. The author prefers to work on the soap itself rHther thanon che acids separated from it.Estimation of Csmpkor. By F. FOERSTER ( B e y . , 23, 2981--2989).-A number of substances now occur in commerce, consistingPercentage 12-5-14.11 y drocar-bon 22-03.T. G. N.M. J. S232 ABSTRACTS OF OREMIOAL PAPERSof nitrocellulose and camphor, and up to the present no method isknown for estimating the amount of camphor which they contain.The author proposes to carry out the estimation by distilling thesubstances with soda solution, when the camphor readily passes over.This may be then extracted with benzene, and the specific rotatorypower of the benzene sol ution ascertained. Detailed instructionsfor carrying out the reaction, and tables of the rotation of camphorin benzene solution at different concentlrations and temperatures aregiven in the original. The results obtained are about 0.7-1.0 percent. too low, probably owing to the difficulty of driving out the lastportions of camphor.The autbor finds that sublimed camphor contains a small quantityof impurity, and that for the determination of its rotatory power, hightemperatures must be avoided in its preparation, and the camphorfinally twice recrystallised from 50 per cent.alcohol. It then meltedat 174+3-173.3", and after six crystallisations a t 1 'i6*3-176-5", andafter 10 crystallisations the solidifying point was found by Landolt'smethod (Abstr., 1890,l) to be 15'8.7" (con-.). The boiling point of thepurified camphor was 209.1" under 739 mm.Estimation of Tannin in Tea. By P. MALTSCHEFFSKY (.I. P~CWWL.[ 5 ] , 22,270-271 ; from Pharm. Zed. f. RUSS., 29,12i).-The tanuiriis precipitated by meitus of normal copper acetate, and the excess ofcopper is titrated by the aid of potassium ferrocpnide solution, Thecopper solution contains 7.657 grams of copper oxide per litre (1 C.C.=0.01 tannin), and its strength is controlled by evaporating a measuredvolume t o dryness, moistening with nitric acid, heating to redness,and weighing tbe oxide. The ferrocyanide solution is prepared bymaking up to 1 litre, 100 C.C. of a saiurated solution. To standardisethis solution, it is added, 1 C.C. at R time, to 5 C.C. of the copper solu-tion diluted to 100 c.c., until a drop of the mixed liquids gives a bluecolonr with a solution (1 : 100) of ferric chloride. A second assay,in which the additions of ferrocyanide solution are made by tenthsof a C.C.towards the end, gives the exact strength of the solution.2 grams of tea, dried at 100-107" is extracted four times with 100 C.C.of boiling water each t h e ; the filtrates are united, made up to400 C.C. ; 100 C.C. of this solution is boiled and treated with 10 C.C.of copper solution. The precipitate is filtered oft', washed with hotwater, and the filtrate and washiip are made up to 200 C.C. ; half ofthis is taken, and the excess of copper is determined approximately bymeans of the ferrocyenide solution ; the second half of tbe solutionthen serves for the exact determination of the copper. In 14 samples,the amount of tannin yaried from 6.10 to 11.08 per cent. The watervaried from 5.59 to 12 48 per cent. ; ash, 3.14 to 9.25 ; aqueous extract,17.3 to 39.4; caffeine, 1.09 to 2.88 per cent.J. T.Estimation of Urea. By P. M~QUEL (Compt. rend., 111, 501-502).-Many of the nrophagic microbes, and especially micrococciand earcinae, can develop in a neutral and even in tt slightly acidcnltivation fluid. Several grow solely a t the bottom of the vesselsand produce more or leks granular deposits without rendering theH. G. C.ANALYTICAL CHEYISTRP. 133liquid turbid, whilst at the same time tbey produce a large quantityof the soluble ferment (this vol., p. 100 ). These clear liquidsshould be used for the estimation of urea.An aqueous solution of urea is simply mixed with the cultivationfluid containing the ferment; the alkalinity i s at once estimated bytitration, and the liquid is heated at 50" for two hours in a well-closed vessel, which it nearly fills.The alkalinity is again deter-mined? and from the quantity of ammonium carbonate formed theamount of urea present is calculated.Urine and ohher organic liquids are previously heated with a sligbtexcess of ammonium carbonate, filtered if necessary, and then mixedwith the feiment, the object of this treatment being to prevent loss ofammonia from formation of double salts, neutralisation of any acidpresent, &c.A quantity of urea exceeding 10 per cent. interferes with theactivity of the ferment, and in solutions o€ 30 per cent. the ferment isit mctive. Concentrated solutions must, therefore, be diluted. Am-monium carbonate, sodium chloride in small proportion, uric acid,arnmoniacal and alkaline salts, extractive matters, albumin, and sugarin large quantity do not interfere with the results. C.H. B,Simple Mode of Estimating Urea. By C. W. HEATON andS. A. VASEY (Analyst, 15, 106--107).-The method, which does notaim at great accuracy, is suggested for the use of medical menin cases where none of the special forms of apparatus is available.An &-ounce bottle is fitted with a thistle funnel and gas delivery tubewhich dips under water in a basin. In the bottle is placed 1 fluiddrachm of bromine and 10 fluid drachms of a 40 per cent. solution ofcaustic soda. A bottle full of water is inverted over the deliverytube to receive the gas ; 2 fluid drachms of urine is then poured intothe generator and rinsed in by 1 fluid dirtchm of water, and +,bebottle is shaken until gas ceases to be evolved.The receiver isthen closed by the thumb, removed from the basin, placed in anupright position, and filled up with water, the volume requiredbeing noted. Deducting 200 minims for the volume of air dis-placed by tho urine and water introduced into the generator, theremainder is equal in volume to the nitrogen evolved, and each100 minims corresponds with 0.25 per cent of urea. M. J. S.Rapid Method of Estimating Urea in Urine. By C. J. H.WARDEN (Analyst, 15, 201--203).-l'he apparatus iR a modifiedCrum's nitrometer, 630 mm. long and of about 75 C.C. capacity. Intoits lower end is ground a stopper, on which 10 narrow grooveshave been filed. The cup above the stopcock i s of 5 C.C.capacity,and is accurately marked a t 2.5 C.C. The tube is graduated toshow percentages of urea a t once, asmmirig that 1 per cent. ofurea in 2.5 C.C. of urine will yield 9.27 C.C. of gas. The hypo-brornite solution is stated to be made by dissolving 100 '' grains"(? grams) of caustic soda in 750 C.C. of water and adding 25 C.C.of bromine. The inverted tube is filled with this solution and thestopper inserted. Ifs cxterior and the cup are then rinsed an134 AUSTHACTS OF CHEhUCAL PAPERS.dried. It is stood in a vessel of brine and the stopper is removed.2-5 C.C. of urine is then placed in the cup and there mixed with itsown volume of saturated brine to increase its densify, and thismixture is allowed to enter the tube in small portions.The lasttraces are rinsed in by brine. The tube is then grasped by theright hand, the thumb being tightly pressed against tbe open end,aiid the contents thoroughly agitated. It is then transferred to avessel of water, where the heavy sollitions flow away, and thevolume of the nitrogen is read in the usufil manner. M-. J. S.Estimation of The'ine in Tea. By G. L. SPENCER (CZcex2,Centr., 1890, ii, 172 ; from J. Arner. Chern. Soc., 4, 158).-2 to 3 gramsof the finely ground tea is extracted i n a small beaker seven timeswith boiling water, the extract being each time decanted off, andthe residue finally transferred to a filter, and washed with a fewC.C. of boiling water. Ha.sic lea*d acetate is added to the extract,about 8 C.C. usually being snfficient; the precipitate is filtervd,washed with hot water, and the lead sepayated as sulphide, afterwbjch the filtrate is concentrated to about 50 c.c., with addition ofabout 5 grams of calcium hSdroxide or mngnesium oxide. The liquidis again filtered, the insoluble portion extracted with hot water, andthe tiltrate is extracted with chloroform seyen times. 'I'he chloro-form extract is distilled from a tared flask, and the weight of theresidual theine recorded after drying at 75". The method has beenin use in the Department of Agriculture. J. W, L.Estimation of Quinine. By SEATON and H. D. RICHMOND(AnaZyst, 15, 42- 43) .-In soh tions containing quinine bisulphatedissolved in an acid, and free from salts whose base is pyecipitable bybaryta, the quinine may be estimated by titration. Quinine bi-sulpbate is neutrai to methyl-o~ange, whilst the base itself has noaction on phenolphthalein. To 25 C.C. of the solution there areadded 2 drops of methyl-orange solution (0.25 gram iii a litre ofwater), and 2 drops of phenolphthalein solution (0.5 gram in a litreof 50 per cent. alcohol). Baryta solution (N/10) is then run in untilthe red colour changes to a brown, at which point all the free acid isneutralised. The addition of baryta is then continued until the pinkcolour of the phenolphthalein appears. As the pink colour develop8slowly, care must be taken not to overstep this point. The numberof cubic centimetres required for this second stage, multiplied by0.0218, gives the weight of the hepta-hydrated quinine sulphatepresent. M. J. S.Reaction for Cocai'ne. By F. DA SILVA (Compt. rend., 111,54$-349).-A small quantity of cocaine, or one of its salts, or of thcresidue obtained by evaporating a solution, is mixed with a few dropsof fuming nitric acid of sp. gr. 1.4, evaporated to dryness on thewater-bath, and the residue mixed with 2 or 3 drops of concentratedalcoholic potasli. A distinct, and peculiar (;dour, recalling that ofpeppermint, iLi developed. In lhageudorfl's systematic scheme oASALTTICAL CHEMISTRY. 135analysis, cocaine is found among the alkaloidu extracted by benzenefrom an aqueous ammoniscal solution. Of the other alkaloids of thesame group, atropine, hyoscyamine, strychnine, codeine, and eserinegive colortttions wlien treated in the same way,and eseriiie also developsa disagreeable odour resembling that of phcn.ylcarbylamine. Del-phinine, brucine, and veratrine give only indistinct odours, whichcannot be confonnded with that from cocaine. Sabadilline andnarcotine can be recognised in the same way, but the other alkaloidsgive no sensitive reactions of this order.The reaction will detect 0.5 milligram of cocaine hydrochloride.C. H. B.Detection of Colchicine in Corpses. By N. OBOLONSEI (&it.a n d Chem., 29, 493).-The finely divided viscera are rubbed upwith glass powder treated with oxalic acid, and digested for 2‘2 hourswith alcohol. The liquid is squeezed out, and the dry residue twicemashed wit.h alcohol. The extract is concentrated at a temperaturenot exceeding SO”, and the cooled residue made up to the originalvolume with alcohol. The filtered liqriid is evaporated as before, nadthis operation repeated until no clots separate on the addition ofalcohol. The residue is then dissolved in water, the solution purifiedby shaking with light petroleum, and the colchicine finally extractedwith chloroform as usual.Tbe alkaloid is best identified by means o€ the violet colour pro-duced by nitric acid ; by Erdmann’s reagent (nitrosnlphuric acid),which gives in succession green, dark-blue, violet, and yellow colourti,turning to raspberry-red on adding alkali ; also by Mandelin’sreagent (1 gram of ammonium vanadate in ‘200 grams of siilphuricacid) which gives a green colour. Colchicine is with difficultydestroyed by putrefaction of animal matter. The kidneys, bladder,and urine are best suited for forensic examination. M. J. S.Detection of Bile Constituents in Urine. By A. JOLLUS(Zeit. a n d Chenz., 29, 402 -406).--Of the various tests proposedfor detecting bile pigments in mine (Grnelin’s, Huppert’s, Vitali’s,Rosenbach’s, Ultzmann’s, Hoppe-Seyler’s, Dragendorff ’s), those ofRosenbach and Huppert, with the following modifications, give thebest results :-Rosenbach’s Test.-A large quantity of the urine is filtered throughclean, white filter-paper, the interior of the filter is touched with adrop of strong nitric acid containing nitrous acid, and the funnel isgently warmed over a flame. After a few minutes a green ring isformed round the spot moistened by the nitric acid.Huppert’s Test.-About 10 C.C. of the urine is shaken with an equalvolume of milk of lime containing 10 grams of calcium oxide in thelitre. The success of the test depends on the proper concentratiotiof the milk of lime. The precipitate is filtered off and washed into atest tube with alcohol and dilute hydrochloric acid, then filtered, andthe filtrate boiled, With only traces of bile pigments, the liquidbecomes green to blue. An estimate of the amount of bile con-stituents can be obtained from the iodine number oE the urine. If 136 ABSTRACTS OF CHEMICAL PAPERS.is the number of grams of iodine absorbed by 10 C.C. of the urine,and s the specific gravity, the iodine number is - The numbers-1for normal urine, filtered after cooling, is 6.3 to 8.1, though even inspecimens rich in uric acid it rarely exceeds 7.8. The presence ofeven traces of bile pigments raises the uumber to 9.6, and values ashigh as 17.4 have been observed.New Test for Albumin. By A. JOLLES (Zeit. ai2aE. Chem., 29,406--407).-About 8 or 10 C.C. of albuminous urine is mixed with anequal volume of concentrated hydrochloric acid, and then 2 or3 drops of a saturated solution of bleaching powder deposited quietlyon the surface. If a8 little as 0.01 gram of albumin per 100 C.C. ispresent, a white turbidity appears at the surface of contact. Thistest, being less sensitive than that with nitric acid, which latter willdetect 0*0015 gram per 100 c.c., may be used to find approximatelythe proportion of albumin present, since by diluting the urine untilthe one test gives an iiidication but the other none, the percentagemay be known to lie between the above minimum limits.M. J. S.M. J. S.Detection of Albumin in Bacterial Urines. By A. JOLLES(Zeit. anal. Chem., 29, 407--408).-The most sensitive test foralbumin in urine is that with acetic acid and potassium ferrocyanide,the lower limit of which is 0.0008 gram in 100 C.C. It is, however,necessary to filter the urine to obtain a standard with which to com-pare the turbidity produced by the test. When bacteria are present,ti clear filtrate is best obtained by shaking with infnsorial earthbefore filtering. In the case of purulent., slimy urines, rich in leuco-cytes, traces of albumin may adhere to the precipitate ; but by wash-ing this with warm potash, and testing the filtrate, the smallesttraces of albumin may be detected. M. J. S

ISSN:0368-1769    

DOI:10.1039/CA8916000107

出版商:RSC    

年代:1891

数据来源: RSC

摘要:

137 Li.. ...... No ....... I(.. ...... Rb ....... Ga ....... General and Physical Chemistry. 28586 109625 24476 110122 21991 114450 20939 121193 19743 I 122869 I Spectra of the Alkali Metals. By H. KAYSER and C . RUNGE (Ann. Phys. C'hem. [a], 42, 302--320).-The alkali metals or their salts were volatilised in the electric arc, and their spectra, obtained by means of a Rowlnnd grating, were examined. It was found that lines belonging to any one series could be expressed in terms of X-', the reci- procal of their wave-lengths, by the formula X-' = A + Bn-2 + Crt-l, which is a modification of Balmer's formula, and in which n is a whole number, which may vary from 3 to 16. All the alkali metals have a number of reversible lines, which occur in pairs (except in the case of lithium), and are divided over the whole length of the spectram ; these form the chief series.The formulae for the first lines in each series of pairs are as follows:- Lithium,. .. At. wt. 7.01 A - ' = 4358493 - 1331369n-~ - 1100084n-'. Sodium.. ... ,, 22.995 A - ' = 4153631 - 1299851t-: - 803301n-'. Potassium .. ,, 39.09 h" = 35086'53 - 126983n-2 - 625318n-4. Rubidium . . ,, 85.2 A-' = 33762.11 - 125521n-2 - 5622551t-4. Cesium .... ,, 132.7 h-' = 33501.56 - J25077n-' - 489885n-4. The wave-lengths are given in &stroni units. It will be seen that all three constants in the formula decrease as the atomic weight rises. The wave-lengths, therefore, increase with rising atomic weight, as Boisbaudran has already pointed out. The difference between the values of X-' for lines in each pair is inversely pro- portional to the fourth power of ?L, the lowest value of n being always 3.In addition to the above, there are also two series of lines for lithium, rubidium, and cEsium, which (again with the exception of lithium) form one series of pairs ; and there are four series of lines for sodium and potassium, forming two series of pairs. The first lines in each pair me given by the above formula, the value of the constants being Second Series. I First Series. I 1 A. I B. 3267 111241 133207 311224 28666 122391 231700 24549 120726 197913 22021 1 119393 1 63243 - 1 - 1 - I - 1 - l - The difference between the values of X-' for lines in the same pair It is equal to that of the first VOL. LX. 1 is alw%ys the same for each element.138 ABSTRAOlS OF OHEMIOAL PAPERS.series when n = 3, and appears, therefore, to be characteristic for each element. The mean values of this difference are Na, 172, K, 568, Rb, 234.2, Cs, 5450, in wave-numbers. These numbers are very nearly in the proportion of the squares of the atomic weights, for if their equnre roots be multiplied by 1.706 w e get Na, 23.0 K, 40.6 Rb, 82.6 Cs, 126.0, instead of 22.995 39.99 85.2 132.7. For lithium, assuming the above law to be general, the calculated difference between the pairs is one which would quite fall within the liniits of ohservcttion, but as the lithium lines do not foym pairs, this metal seems to be an exception to the rule. A comparison has been made between the lines here measured and the Fraiinhofer lines in Rowland’s solar atlas. Only two pairs in the Ghief series of sodium lines could be detected, the lines of all the other elements being apparently absent.H. C. Dispersive Power of Organic Compounds. By R. NASIXI (Guzzetta, 20, 356-361) .-A claim for priority as against Barbier and Roux (Abstr., 1890, 1:353). Relation between the Refractive and Rotatory Powers of Chemical Compounds. By I. I. KANOKNTROFF ( J . Russ. Chem. Soc., 22, 85--96).-1n two previous papers (Abstr., 1888, 326, 453), the author has shown that on expressing the relation of the refractive and rotatory powers of a substance by the equation a = A$ - B, the relnt,ion A/B = C, a constant peculiar for the solvent, and independent Qf the optically active substance. The author has investigated solu- tions of camphor and turpentine in over 70 different organic solvents, and gives his results in tabnlar form. It is found that in homologous compounds, such as aliphatic alcohols, ethercd salts of fatty acids and their halogen derivatives, the free acids, the aldehydes, chlorides, bromides, &c., the constant C (as a mean = about 26) increases with every increase of CH2, the differences diminishing from the lower to the higher members.and rarying between 1.35 and 0.46, or, as a mean = 0.85. The difference for an increase of H, = 1.4 in gonetically connected compounds, and -2.5 for compounds of dis- similar constitution. Similar values are found for other changes in composition and constitution (double linkage, isomerism, polymerism. substitution), but it would occupy too much spane t o give the results in detail.For aroniatic compounds, the equation a = A$-- B of the fatty series is converted irito a = A$ + B. But where in aliphatic compounds increasing complexity in composition is regularly nccom- panied by an increase of the value of C, in the case of aromatic com- 1)ounds a decrease is ohserved. The author proposes to investigate the influence of inorganic solvents on the value C. B. B. New Photographic Method. By A. G. GREEN, C. F. CROSS, and E. J. BEVAN (Ber., 23, 3131-3133).-The diazo-compounds of de- hpdrot hiotoluidine and its condensed derivatins, which form theGENERAL AND PHYSICAL CEEMISTRY. 139 dyes of the primuline group, can be employed for photographic pnr- poses ; as the sensitiveness of these compounds is increased by com- bination with the complex colloids which constitute animal or vegekable textile fabrics.The sensitive surface is prepared by colonr- ing a cotton or silk fabric with primuline ( 1 to 2 per cent.), and then diazotising. Such a surface will give a complete positive picture after 40 to 180 seconds exposure, that is t o say, in the bright lights the diazo-compound is completely, in the half lights only partially, decomposed, so that a perfect reproduction of the original is obtained in the form of diazo-primuline. The picture can be developed with any of the various amines or phenols which form a dye with the diazo- compound. The authors' experiments have already brought to light the follow- i n g facts :-(1,) The action of light consists in the decomposition of the diazo-group, with evolution of nitrogen, probably with formation of the corresponding primuline phenol. (2.) The rapidity of the action of light varies, cceferis paribus, with !he nature of the substance with which the diazo-compound is combined.(3.) Photographic reproductions of the spectrum show that, as regards intensity of action, the various rays of light are not in the same order as that in wliich they stand with reference to halogen salts of silver. F. S. K. Action of Borax in Developers for Photographic Plates. By P. MERCIER (Compt. rend., 111, 644--645).-Borax, a.lthough an alkaline salt, acts as a retarder of development when mixed with pyrogallol or catechol. The author points out that this is doubtless due to the formation of the conjugated acids described by Lambert, (Abstr., 1889, 864).Quinol, resorcinol, sodium amidonaphthol-P- sulphonate (eikonogen) , and hydroxylamine hydrochloride do not form similar conjugated acids, and with these compounds borax acts as a very good accelerator of development. By E. WIEDEMANN (Ann. Phys. C'hern. [2], 41, 299-301). The violet colour of iodine dissolved in carbon bisulphide changes to brown when the solution is cooled by means of ethcr and solid carbonic anhydride (Abstr., 1888, 543). The author now finds, in accordance with a statement by Liebreich, that. when the brown solutions of iodine in ethereal salts of the fatty acids are heated to about SO" they become violet, provided the solutions be not too concentrated. Solutions of eosin or Magdala-red in alcohol, heated in capillary tubes, are found to exhibit a very marked fluorescence at temperatures above the critical.Experiments with saffranine failed owing to its Contact Difference of Potential of Metals. By F. PASCREN (An.ia. Phys. Chem. [2j, 41, 186-209).-The author shows that an amalgam prepared by the electrolytic deposition of zinc on mercury changes in the electromotive properties which it a t first exhibits, on merely being allowed to stand for some time. I n order to restore its original properties, it must be submitted to a new and longer electro- C. H. B. Optical Notes. decomposition. H. c.140 ABSTRAOTS OF CHENIOAL PAPERS. Iysis. Thus 705.8 grams of mercury were placed in a solution of zinc sulphate of sp. gr. 1.288, and zinc deposited by a current from two Daniel1 cells for 30 seconds.The amalgam thus produced would contain 0.0000656 gram of zinc to 100 grams of mercury. The E.M.F. of freshly-prepared amalgam I ZnSOa I , amalgamated zinc, was then measured and found to be 0.14 volt. After remaining for three hours, the E.JY1.F had risen to 1.1291 volts, and a further electrolysis for 26 seconds was necessary to restore it to its original value. Tho above change is, however, only exhibited by an amalgam which con- tains very small quantities of zinc, and by increasing the quantity of zinc to a sufficient degree the property of the amalgam becomes practically constant. The suggestion is made that dropping electrodes, similar to those described by the author (Ann. Phys. Chem. [2], 41, 62), might, be used in determining the contact difference of potential of metals, if filled with the molten metals, and these be then allowed to flow into some suitable liquid electrolyte.If, as in the case of mercury, there is no potential difference a t the place where the metal enters the electrolyte, the potential difference between two such electrodes will be that of the metals which they contain. Great practical difficulties lie in the way of such experiments as those here suggested, but it may in some cases be possible to use in place of the metals themselves the amalgams which they form with mercury. The author describes a number of experiments made in this manner with zinc amalgam, and shows that the E.M.F. amalgam I mercury, varies with the amount of zinc contained in the amalgam, tbe variation in these experiments being from 0.021 to 0.156 volt.Electrical Conductivity of Precipitated Membranes. By G. TAMMANN (Zeit. physikal. Chem., 6 , 237--240).-A solution of cuprlc sulphate superposed on a solution of potassium ferrocyanide precipitates at the dividing surface an exceedingly fine membrane of cupric ferro- cyanide, which permits the transfusion of water, but not of any of the salts present in the solutions. Notwithstanding this, the author finds that, the presence of such membrane in an electric circuit does not increase the resistance. His mode of experiment was as follows. He prepared solutions of the above-mentioned salts, having equal electrical conductivity, and snperposed them in an electrolytic cell, so that one horizontal electrode was in one solution, the other electrode in the other.The current had thus to traverse the precipitated semi- permeable membrane, and it WRS found that the resistance remained exactly as before. A membrane of zinc ferrocyanide behaves similarly at first, but after some time it increases in thickness, becomes opaque and permeable for the salt^, its resistance meanwhile growing greater, and attaining a maximum i n about 1 5 minutes. Precipitated membranes of zinc and cupric hydroxides thicken rapidly and diminish the con- ductivity by from 5 to 8 per cent. Membranes of insulating material, mch as pyroxylin, increase the resistance enormously, the only con- duction being probably t'hat through the pores. (Compare Ostwald, Abstr., 1890, 1354.) J.W. H. C.GENERAL AND PHYSICAL OHEMISTRY. 141 Influence of Water of Crystallisation on the Electrical Conductivity of Salt Solutions. By J. TROTSCH ( A m . Phys. Chem. [ZJ, 41,259-287).--The conductivities of solutions of a large number of different salts have been determined for temperatures ranging from 10" to 80". The Kohlrausch telephone method was employed, and in order to obviate the difficulty arising from evaporation of the solutions at the higher temperatures the top of each solution was covered with a layer of molten paraffin. The conductivities were measured at every lo", and the difference d between consecutive readings is taken as a mean temperature coefficient for the 10" rise of temperature. Solutions of salts which are ordinarily anhydrous in the solid state, such as KCI, NaCI, KN03, have temperature coefficients which rise continually with the temperature, or which attain a maximum and then remain constant.On the other hand, the temperature coefficient of solutions of hydrated salts at 6rst increases, reaches a maximum, and t,hen decreases, the author attributing this last behaviour to the loss by the salt of its water of crystallisation. Calcium chloride forms ;t:i exception to this rule, tbe three solutions examined, which con- tained 4.5, 19.2, and 32 per cent. CaC12, behaving throughonit as solutions of anhydrous salts. The temperature coefficient in the case oC the second solution, however, only' undergoes a slight increase with rising temperature, and i3 far smaller than that of the first or third solutions.Five solutions of cupric chloride were examined, having the percentages 1.35, 9, 18.2, '28.7, 35.2. The t w o concentrated solu- tions are green, the two dilute solutions blue, and the colour of the third solution is intermediate between the two. All these solutions behave as solutions of hydrated saits, the temperature coeflicient in each case reaching a maximum at between 40" and 50". At the same temperatures, a change in colour is also observed, the green solutions becoming yellow and the blue solutions becoming green. I n each cas9 these changes seem, therefore, to be conditioned by a dehydration of the salt taking place as the temperature rises. Cobalt chloride shows a somewhat similar behaviour, the colour of the solutions changing from red to blue on heating, and at the same time the tem- perature coefficient reaching a maximum.The temperature of the change is, however, higher in this case, and therefore it is not so readily observed. The author concludes that salts are contained in solution partly as hydrates and partly i n the anhydrous state. At high temperatures, the hydrates part with their water, this taking $lace the more readily in the more concentrated solutions. The water of hydration exercises a specific influence 011 the electrical conductivity of solutions. H. C. Electrical Conductivity of Saline Solutions. By P. CHROU- SHTCHOFF and W. PASHKOFF (J. Russ. Chem. Soc., 22, 110-115), and by CHROVSHTOHOVF (ibid., 115--116).-The two papers contain tt large number of experimental data as regards the conductivity of aqueous solutions of salts and mixtures of salts and acids, but the conclu- sions arrived at are the same as those contained in Chroushtchoff's previous papers (Abstr,, 1P89, 808-809).B. B.14 2 ABSTRACTS OF CHEMICAL PAPERS. Solubility of Mixtures of Electrolytically Dissociated Substances. By A. A. NOYES (Zeit. physikal. Chem., 6,84i -267) .- It has been shown by Nernst (this vol., p. 3 ) that the principles regu- lating the influence of two salts on each other's solubility are those deduced from the general law of mass action as interpreted in the light of the electrolytic dissociation theoiy. The author, in the present paper, contributes an account of his experimental work on the subject. He investigated 11 pairs of salts, and fintls the results of his experiments in very good agreement with the theoretical values.Most of the work was done with binary electrolytes, for example, AgBrO, : AgNO?, TlSCN : T1N03, but a few ternary electro- lytes were shown to give results equallp in harmony with the theory. Experiments were made not only with pairs of salts con- taining one ion in common, but also with pairs whose ions were all diff wen t . Reckoning back from the solubilities, i t is possible to calculate the dissociation constants of strong electroljtes. This is a fact of COD- siderable importance, for the ordinary method of calculation from the electrical conductivity fails in such cases to give a constaat number at all. J. W. Method of Determining Thermal Expansion for Equal Quantities of Heat.By E. J. DRAGOCMIS (Zeit. physikal. Chem., 6, 281--284).-Let V be the volume of a substance; g its weight ; a its coefficient of cubical expansion ; c its specific heat ; g its specific gravity ; At the rise of temperature, and A the expansion caused by the communication of 1 cal.; then A = Vaht. But At = l/cg and V/g = 11s; therefore A = ales. In the case of gases, A is evidently inversely proportional to the molecular heat, for a is constant for all gases, and s varies inversely as the molecular weight. The author determines A in the following manner : A dilatometer packed in cotton wool contains the substance whose expansion is to be measured, and also a platinum spiral, the ends of which are fused through the walls. By means of this spiral the substance is heated, a current of about 0.2 ampere being passed. From the current, the heat communicated is easily calculat'ed, and the expansion for this amount is obserred.Comparative experiments with various liquids were executed, and the results found to be satisfactory. J. W. Estimation of the Specific Gravity of Frothy Syrups. By A. GENIESER (Zeit. ang. C'hern., 1890, 44-45).-A tared pyknometer is about two-thirds filled with the syrup, in which air-bubbles are entangled, and the weight is noted. It is then carefully heated in a salt bath, and maintained in ebullition for a few moments. The whole of the air rises to the surface, where it forms an extremely thin layer of froth. After cooling, water is added, so as to float on the surface without mixing. The froth readily dissolves, and the air escapes.The pyknometer is then filled to the mark with water, and weighed. On deducting the excess of weight, above that of the syrup taken, from the total amount of water which the pyknometer willGENERAL AND PHYSICAL CHEMISTRY. 143 contain, the remainder gives the weight of water equal in volume to the syrup taken, and thence the specific gravitty. By A. W. v. H o F b r m N (Ber., 23, 3303-3319).-Dissociation of Cadonic Anhydride.--In 1860, the author published a paper in conjunction with H. Buff, in which i t wits stated that carbonic anhydride is gradually decomposed by the passage of a series of electric sparks through the gas, and that after a time the carbonic oxide and oxygen recombine with explosive violence. A repetition of these experiments has shown that the explosion only occuis under certain special conditions.6-10 C.C. of dry carbonic anhydride under a pressure of 650-700 mm. are brought into a stout glass tube standing over mercury; a short piece of platinum wire is fused into the shorter limb of a, thin U-shaped tube, the tube is filled with mei-cury, and a second piece of wire wound spirally round the outside of the shorter limb, which is then passed up into the vessel containing the gas; in this way the length of the spark may be readily regulated; in general it should be 2.5-3 mm. Connection is made b7 two wires dipping into the mercury contained in the U -tube and trough respectively. The electric current is obtained from two Bunsen’s elements of medium size, which are connected with a Rnhmkorff’s coil and a small Leyden jar, the coil being 30 cm.long and 10 cm. in diameter. The first explosion usually occurs after 15-20 minutes, aud the subsequent ones at shorter intervals, since the regeneration of the carbonic anhydride is not complete. The dissociation of carbonic anhydride may be shown by passing the gas tbrough a glass tube, in the middle of which two plat<inum terminals are fused ; a series of sparks is allowed to paw, and the issuing gas collected over potash ; part of the gas remains undissolved, and is found to be explosive. Carb- onic anhydride does not appear to be at all affected by a glowing spiral of wire ; it was not found pomible to prepare the gas free from air. Dissociation of Steam-The accompanying illustration (next page) shows a form of apparatus which niay be employed for the purpose of showing the dissociation of steam at varying pressures.The wide glass tube is 2.5 cm. in diameter and 20 cm. in length, the lower tube is 1 cm. in diameter and 40 cm. in length ; the apparatus is filled with moist mercury and heated with steam; instead of fixed terminals, the U-tnbe and wires described above may be employed ; in one experi- ment 2.9 C.C. of gas were obtained after ten minutes ; no regeneration of water occurred, as in the case of carbotiic anhydride. The experi- ment may be varied by allowing the apparatus to cool whilst the electric current is continued ; the dissociated gases gradually combine, and the whole tube becomes refilled with mercury.The current employed is obtained from three Bunsen cells, with the coil and Leyden jar as before. Steam may also be dissociated by means of a glowing white hot spiral of platinum wire; the two ends are con- nected with accumulators, stearn is passed over the coil, and the mixed gases are collected over cold water, which serves to condense the excess of steam. Dissociation of Gases and Vapours by the Silent Discharge.-Experi- M. J. S. Dissociation Phenomena.144 ABSTRAOTS OF OHEMIOAL PAPERS. ments in this direction show that ozone is produced by the decompo- sition of carbonic anhydride, the results of Andrews and Tait, Brodic, and others being thus confirmed. Steam may also be decomposed by passing it through 8 Siemens ozone tube, or by the use of the modi- fied apparatus devised by Berthelot ; various experiments were made to prove that the explosive gas obtained was really derived from the steam, and was not due to electrolysis.Berthelot’s results on the decomposition of ammonia by means of the silent discharge are con- firmed. The vapours of methyl alcohol, ethyl alcohol, and ethyl ether may also be dissociated by mems of the silent discharge. Influence of Mineral Acids on the Velocity of the Reaction between Brornic and Hydriodic Acids. By G. MAGNANINI (Gazzeffa, 20,377-393).-The reaction between bromic and hydriodic acids was shown by Ostmald (Abstr., 1885, 1024) to form an excep- tion to the ordinary rule of mass action, and neither Meyerhoffer’s (Abstr., 1889, 9) nor Burchard’s (Abstr., 1889, 208) expressions are found to satisfy the experimental data respecting the vmiation of the speed of the reaction.These discrepancies are evidently occasioned by secondary reactions, which alter the velocity of thc changes at every instant. Ostwald found that mineral acids increase the speed of the reaction, and that the increments are sensibly proportional to the affinity coefficients of the respective acids, or to the quantity of hydrogen electrolytically dissociated from them. The author has continued Ostwald’s investigations on the accelerating or retarding J. B. T.GENERAL AND PHYSICAL CHEMISTRY. 145 effecto. of mineral acids on this reaction, esperimenting with hydro- chloric, nitric, sulphuric, and bromic acids, with mixtures of some of these acids, and with potassiuni bromate ; from the tabulated results, he draws the following conclusions.During tohe course of the different changes, the reaction is influenced in the same way by the secondary actions. The reciprocal values of the times required for the separation of a determinate quantity of iodine vary as the velocity of the respective reactions. The velocity of the reaction is accelerated by hydrochloric acid, but the acceleration is not propor- tional to the quantity of acid present. The quantity of iodine deposited after equal times in presence of equivalent quantities of hydrochloric and nitric acids is the same. Mixtures of hydrochloric and nitric acids, in any proportions, are equivalent to either of the acids, so that, independently of the nature of the electro-negative radicle, it may be said that the velocity of the reaction depends entirely on the quantity of hydrogen electrolytically dissociated, without, however, being proportional t o it.The action of sulphuric acid is more complicated, on account o€ t.he incomplete dissociation of that acid. The :tccelerating effect of bromic acid is almost six times that of hydrochloric or nitric acid. S. B. A. A. Velocity of the Halogenisation of Fatty Hydrocarbons. By If. WILDERMAN" (BAT., 23, 317&3175).--The following two laws are deduced from a study of the action of bromine or chlorine in sunlight on amyl bromide, amylene bromide, liquid and solid tri- bromopentane, tetrabromopentane, and amylene chloride :-( 1) Sub- stitution proceeds more slowly as the quantity of positrive hydrocarbon becomes smaller.(2) The larger the quantity of hydrocarbon present, the quicker the substitution. Cryoscopic Investigation of Colloidal Substances. By A. SABAN~EFF ( J . Russ. Chew. SOC., 22, 102--107),-The author has shown that Raoult's method may be conveniently employed for the determination of tbe molecular weight of colloidal substances (Abstr., 1890, 1215). Similar results were obtained by Morris and Brown, by Ekstraud and Mauzelius. 0 1 1 the other hand, Paternb, in his research on gallic and tannic acide, has arrived a t the conclusion that their molecular. weights cannot be determined by Rao ult's method. The values obtained by Paternb give 10 mols. of the first, and 109 ruols. of the second, as the molecular weights in solution. The author shows that Paternb's paper includes an error in calculation, and that the values greatly depend on the purity of the material.First the molecular weight of gallic acid was determined. It mas dried at 120°, iosing 9.65 per cent. water, corresponding with the formula C,H6OS + H20. In aqueous solution, containing 0.5238 per cent., the depres- sion was 0*06", and the rnolecular weight 166 ; i n acetic acid, con- taining 0.4107 part, the depression was 0*095", molecular weight = 168, whereas the value for C7H606 is 170; gallic acid exists, there- fore, as a. airigle molecule in solutions. Commercial tannin was found to contain some gallic acid, the quantity of which, as calculated from the depression of the impure J. B. T.146 ABSTRACTS OF CHEMICAL PAPERS.preparation, compared with that of the pure preparation, was found to be 2-39 per cent. It was dried for 20 hours at 120', and the loss was 10.66 per cent. Aqueous solutions with a concentration of 0-822-3.773 shorn a depression of 0*015--0~060, giving a molecular weight of 1044-1195 (mean, 1104). More concentrated solutions, contain- ing 5.5 to 9.5 per cent., gave higher molecular weights, 1497 to 2436, but the values are useless, as solutions of more than 4 per cent. of tannin in water become turbid a t O", tannin separating out. I n Paternb's solutions, containing 11.5-23 per cent. of tannin, $--3 Of the tannin must have separated tit 0" in the insoluble state, and h i s (corrected) molecular weights, = 2643-3700, are of no value. The author finds in acetic solution, molecular weights = 1105-1114 (mean 1113).Pure tannin was pwpared by Lowe's method, but it was impossible to work with aqueous solutions, as not more than 0-5 per cent. is dissolved in water at O", and even such weak solutions became turbid. I n acetic acid solution, as a mean, M = 1322 was found, whereas, M calculated for (C14Hlo09)4 = 1288, so that tannin exists in solutions as a quadruple molecule. The author thinks that Paternb's tannin was not quite dry, and shows by experiment that such a preparation causes a much larger depression, owing to the contamination of the glacial acetic acid by the water of crystallisation of the compound. The author says that the empirical formula of tannin requires confirmation by further research. Apparatus for Distillation under Reduced Pressure.By H. W ISLICENUS (Ber., 23,3292-3295).--The author describes two forms of apparatus for use with the the Bunsen pump, to prevent backward diffusion. The first consists of a tube, with one round and one pear- shaped bulb; in the depression between these a rubber ring is placed, one end of the tube is sealed, 5 small opening is made in the side and is covered with a piece of rubber tube, or an ordinary Bunsen valve may be attached; the other end of the tube is connected with the vessel to be exhausted, the pear-shaped bulb fits into a wide tube, the rubber ring serving to make the connection air-tight ; the second tube is joined to the pumpin the usual manner. The second form of valve consists of two tubes, one closely resembling a thistle funnel, the narrow end of which is attached to the pump; a bulb with a small aperture is blown a t the end of the second tube, and i t is covered with a rubber cap, through which an opening is pierced st a litt.le distance from the one in the glass; the rubber cap serves to make an air-tight connection between the bulb and the wide end of the first tube.An apparatus for fractional distillation under reduced pressure is also descrihed ; it consists of a combination of several of the first of these joints, and provision is made for changing the receiver without interrupting the distillation. Isomorphism. Part 111. By J. W. RETGERS (Zeit. physikaE. Chem., 6,193-236).-1n this communication (for previocs papers see Abstr., 1890,328,1208), the author first discusses the relations of morphotropy.He would limit the term morphotropic to such substances as show a B. B. J. B. T.GENERAL AND PHYSICAL CHEMISTRY. 147 total analogy of form, and not, for instance, merely analogy of angles in one zone. Isomorphons substances have not only this total form- analogy, but also analogy of chemical constitution. Morphotropic substances are not necessarily cheniically analogous, but must be chemically connected with each other. Substances which show a total form-analogy, but have no chemical rcsemblance, are termed isogonic. In the regular system, for instance, potassium chloride and rubidium chloride are isomorphous ; potassium chloride and sodium chloride, morphotropic ; and sodium chloride and sodium chlorate, isogonic. lsomorphous mixtures are proved by the continuous linear change of physical properties with the composition of thc mixture.No intimate crystalliue mixture can be obtained with merely morphotropic Substances, and in this case identity of system, and of degree of hemi- hedry, are not essential. The author rejects Marignttc and Klein’s conception of mas3 isomorphism, according to which an element, o r group, largely preponderating in a compound, determines the crystal - line form, no matter what the other components may be. It is the volume and not the weight of the group that is decisive. An investigation follows of the supposed isomorphism between potassium and sodium sulphates. The author proves that a definite double salt, 3K2S04,Na$04, crystallisev from a solution of the mixed snlphates.It usually crystallises in hexagonal prisms or pyramids, but when the mother liquor contains sodium chloride, i t separates in tables-the “ plate-sulphate ” obtained in the manufacture of iodine from kelp. Potassium chloride does not effect this change of form. The three simple forms are then- K2S04. Rhornbic, pseudo-hexagonal. Forms pyramids and prisms of hexagonal section. Optically biaxial. Weak birefringence. Sp. gr. = 2.666. 3KZSO4,Na,SO4. Hexagonal. Forms pyramids and prisms. Optic- ally uniaxial. Marked birefringence. Sp. gr. = 2.695. Easily fukible. NhSO,. Rhombic, but not pseudo-hexagonal. Forms only pyramids with rhombic section. Optically biaxial. Strong birefrin- gence. Sp. gr. 2.673. Fusible with great difficulty. The double salt is not an isomorphons mixture, as is shown by a consideration of its properties in relation to those of the simple salts.Each simple salt can take up a minute quantity of the other, which points to a very limited isodimorphism. Not easily fusible. The general results are- (1) K&Oa and Na2S04 are not isomorphous. (2) They only form one double salt, 3KzSOa,Na2S04. (3) From mixed solution the pure double salt separates out along- (4) K,SO, and the double salt are morphotropic. (5) NazS04 is not, morphotropic either with K2S04 or with thO double salt, but is crystallographically completely independent. The dolomite series is next discussed. In this series we have calcspnrs containing a little magnesium carbonate, magnesites con- taining a little calcium carbonate, and dolomites which have the two salts in nearly equal molecular proportions.Calculated from the side one or other of the simple salts.148 ABSTRACTS OF OHFJIICAL PAPERS. specific gravities of the component salts, that of dolomite shonld be 2.843 ; it is actually 2.872. The author considers the series not iso- morphoua, but merely morphotropic. J. W.137Li.. ......No .......I(.. ......Rb .......Ga .......General and Physical Chemistry.28586 10962524476 11012221991 11445020939 12119319743 I 122869 ISpectra of the Alkali Metals. By H. KAYSER and C . RUNGE(Ann. Phys. C'hem. [a], 42, 302--320).-The alkali metals or theirsalts were volatilised in the electric arc, and their spectra, obtained bymeans of a Rowlnnd grating, were examined.It was found that linesbelonging to any one series could be expressed in terms of X-', the reci-procal of their wave-lengths, by the formula X-' = A + Bn-2 + Crt-l,which is a modification of Balmer's formula, and in which n is awhole number, which may vary from 3 to 16.All the alkali metals have a number of reversible lines, whichoccur in pairs (except in the case of lithium), and are divided overthe whole length of the spectram ; these form the chief series. Theformulae for the first lines in each series of pairs are as follows:-Lithium,. .. At. wt. 7.01 A - ' = 4358493 - 1331369n-~ - 1100084n-'.Sodium.. ... ,, 22.995 A - ' = 4153631 - 1299851t-: - 803301n-'.Potassium .. ,, 39.09 h" = 35086'53 - 126983n-2 - 625318n-4.Rubidium .. ,, 85.2 A-' = 33762.11 - 125521n-2 - 5622551t-4.Cesium .... ,, 132.7 h-' = 33501.56 - J25077n-' - 489885n-4.The wave-lengths are given in &stroni units. It will be seenthat all three constants in the formula decrease as the atomic weightrises. The wave-lengths, therefore, increase with rising atomicweight, as Boisbaudran has already pointed out. The differencebetween the values of X-' for lines in each pair is inversely pro-portional to the fourth power of ?L, the lowest value of n beingalways 3.In addition to the above, there are also two series of lines forlithium, rubidium, and cEsium, which (again with the exception oflithium) form one series of pairs ; and there are four series of linesfor sodium and potassium, forming two series of pairs.The firstlines in each pair me given by the above formula, the value of theconstants beingSecond Series. I First Series. I1 A. I B.326711124113320731122428666 122391 23170024549 120726 19791322021 1 119393 1 63243- 1 - 1 -I - 1 - l -The difference between the values of X-' for lines in the same pairIt is equal to that of the firstVOL. LX. 1is alw%ys the same for each element138 ABSTRAOlS OF OHEMIOAL PAPERS.series when n = 3, and appears, therefore, to be characteristic for eachelement. The mean values of this difference are Na, 172, K, 568,Rb, 234.2, Cs, 5450, in wave-numbers. These numbers are verynearly in the proportion of the squares of the atomic weights, for iftheir equnre roots be multiplied by 1.706 w e getNa, 23.0 K, 40.6 Rb, 82.6 Cs, 126.0,instead of 22.995 39.99 85.2 132.7.For lithium, assuming the above law to be general, the calculateddifference between the pairs is one which would quite fall within theliniits of ohservcttion, but as the lithium lines do not foym pairs, thismetal seems to be an exception to the rule.A comparison has been made between the lines here measured andthe Fraiinhofer lines in Rowland’s solar atlas.Only two pairs in theGhief series of sodium lines could be detected, the lines of all theother elements being apparently absent. H. C.Dispersive Power of Organic Compounds. By R. NASIXI(Guzzetta, 20, 356-361) .-A claim for priority as against Barbierand Roux (Abstr., 1890, 1:353).Relation between the Refractive and Rotatory Powers ofChemical Compounds.By I. I. KANOKNTROFF ( J . Russ. Chem.Soc., 22, 85--96).-1n two previous papers (Abstr., 1888, 326, 453),the author has shown that on expressing the relation of the refractiveand rotatory powers of a substance by the equation a = A$ - B, therelnt,ion A/B = C, a constant peculiar for the solvent, and independentQf the optically active substance. The author has investigated solu-tions of camphor and turpentine in over 70 different organic solvents,and gives his results in tabnlar form. It is found that in homologouscompounds, such as aliphatic alcohols, ethercd salts of fatty acidsand their halogen derivatives, the free acids, the aldehydes, chlorides,bromides, &c., the constant C (as a mean = about 26) increaseswith every increase of CH2, the differences diminishing from thelower to the higher members.and rarying between 1.35 and 0.46, or,as a mean = 0.85. The difference for an increase of H, = 1.4 ingonetically connected compounds, and -2.5 for compounds of dis-similar constitution. Similar values are found for other changes incomposition and constitution (double linkage, isomerism, polymerism.substitution), but it would occupy too much spane t o give the resultsin detail. For aroniatic compounds, the equation a = A$-- B of thefatty series is converted irito a = A$ + B. But where in aliphaticcompounds increasing complexity in composition is regularly nccom-panied by an increase of the value of C, in the case of aromatic com-1)ounds a decrease is ohserved.The author proposes to investigatethe influence of inorganic solvents on the value C. B. B.New Photographic Method. By A. G. GREEN, C. F. CROSS, andE. J. BEVAN (Ber., 23, 3131-3133).-The diazo-compounds of de-hpdrot hiotoluidine and its condensed derivatins, which form thGENERAL AND PHYSICAL CEEMISTRY. 139dyes of the primuline group, can be employed for photographic pnr-poses ; as the sensitiveness of these compounds is increased by com-bination with the complex colloids which constitute animal orvegekable textile fabrics. The sensitive surface is prepared by colonr-ing a cotton or silk fabric with primuline ( 1 to 2 per cent.), andthen diazotising. Such a surface will give a complete positive pictureafter 40 to 180 seconds exposure, that is t o say, in the bright lightsthe diazo-compound is completely, in the half lights only partially,decomposed, so that a perfect reproduction of the original is obtainedin the form of diazo-primuline.The picture can be developed withany of the various amines or phenols which form a dye with the diazo-compound.The authors' experiments have already brought to light the follow-i n g facts :-(1,) The action of light consists in the decomposition ofthe diazo-group, with evolution of nitrogen, probably with formationof the corresponding primuline phenol. (2.) The rapidity of theaction of light varies, cceferis paribus, with !he nature of the substancewith which the diazo-compound is combined. (3.) Photographicreproductions of the spectrum show that, as regards intensity ofaction, the various rays of light are not in the same order as that inwliich they stand with reference to halogen salts of silver.F.S. K.Action of Borax in Developers for Photographic Plates.By P. MERCIER (Compt. rend., 111, 644--645).-Borax, a.lthough analkaline salt, acts as a retarder of development when mixed withpyrogallol or catechol. The author points out that this is doubtlessdue to the formation of the conjugated acids described by Lambert,(Abstr., 1889, 864). Quinol, resorcinol, sodium amidonaphthol-P-sulphonate (eikonogen) , and hydroxylamine hydrochloride do not formsimilar conjugated acids, and with these compounds borax acts as avery good accelerator of development.By E.WIEDEMANN (Ann. Phys. C'hern. [2], 41,299-301). The violet colour of iodine dissolved in carbon bisulphidechanges to brown when the solution is cooled by means of ethcr andsolid carbonic anhydride (Abstr., 1888, 543). The author now finds,in accordance with a statement by Liebreich, that. when the brownsolutions of iodine in ethereal salts of the fatty acids are heated toabout SO" they become violet, provided the solutions be not tooconcentrated.Solutions of eosin or Magdala-red in alcohol, heated in capillarytubes, are found to exhibit a very marked fluorescence at temperaturesabove the critical. Experiments with saffranine failed owing to itsContact Difference of Potential of Metals. By F. PASCREN(An.ia. Phys. Chem. [2j, 41, 186-209).-The author shows that anamalgam prepared by the electrolytic deposition of zinc on mercurychanges in the electromotive properties which it a t first exhibits, onmerely being allowed to stand for some time.I n order to restore itsoriginal properties, it must be submitted to a new and longer electro-C. H. B.Optical Notes.decomposition. H. c140 ABSTRAOTS OF CHENIOAL PAPERS.Iysis. Thus 705.8 grams of mercury were placed in a solution ofzinc sulphate of sp. gr. 1.288, and zinc deposited by a current fromtwo Daniel1 cells for 30 seconds. The amalgam thus produced wouldcontain 0.0000656 gram of zinc to 100 grams of mercury. TheE.M.F. of freshly-prepared amalgam I ZnSOa I , amalgamated zinc, wasthen measured and found to be 0.14 volt.After remaining for threehours, the E.JY1.F had risen to 1.1291 volts, and a further electrolysisfor 26 seconds was necessary to restore it to its original value. Thoabove change is, however, only exhibited by an amalgam which con-tains very small quantities of zinc, and by increasing the quantity ofzinc to a sufficient degree the property of the amalgam becomespractically constant.The suggestion is made that dropping electrodes, similar to thosedescribed by the author (Ann. Phys. Chem. [2], 41, 62), might, beused in determining the contact difference of potential of metals, iffilled with the molten metals, and these be then allowed to flow intosome suitable liquid electrolyte. If, as in the case of mercury, thereis no potential difference a t the place where the metal enters theelectrolyte, the potential difference between two such electrodes will bethat of the metals which they contain.Great practical difficulties liein the way of such experiments as those here suggested, but it mayin some cases be possible to use in place of the metals themselves theamalgams which they form with mercury. The author describes anumber of experiments made in this manner with zinc amalgam, andshows that the E.M.F. amalgam I mercury, varies with the amountof zinc contained in the amalgam, tbe variation in these experimentsbeing from 0.021 to 0.156 volt.Electrical Conductivity of Precipitated Membranes. By G.TAMMANN (Zeit. physikal. Chem., 6 , 237--240).-A solution of cuprlcsulphate superposed on a solution of potassium ferrocyanide precipitatesat the dividing surface an exceedingly fine membrane of cupric ferro-cyanide, which permits the transfusion of water, but not of any of thesalts present in the solutions.Notwithstanding this, the authorfinds that, the presence of such membrane in an electric circuit doesnot increase the resistance. His mode of experiment was as follows.He prepared solutions of the above-mentioned salts, having equalelectrical conductivity, and snperposed them in an electrolytic cell, sothat one horizontal electrode was in one solution, the other electrodein the other. The current had thus to traverse the precipitated semi-permeable membrane, and it WRS found that the resistance remainedexactly as before.A membrane of zinc ferrocyanide behaves similarly atfirst, but after some time it increases in thickness, becomes opaque andpermeable for the salt^, its resistance meanwhile growing greater, andattaining a maximum i n about 1 5 minutes. Precipitated membranesof zinc and cupric hydroxides thicken rapidly and diminish the con-ductivity by from 5 to 8 per cent. Membranes of insulating material,mch as pyroxylin, increase the resistance enormously, the only con-duction being probably t'hat through the pores. (Compare Ostwald,Abstr., 1890, 1354.) J. W.H. CGENERAL AND PHYSICAL OHEMISTRY. 141Influence of Water of Crystallisation on the ElectricalConductivity of Salt Solutions. By J. TROTSCH ( A m . Phys. Chem.[ZJ, 41,259-287).--The conductivities of solutions of a large numberof different salts have been determined for temperatures ranging from10" to 80".The Kohlrausch telephone method was employed, and inorder to obviate the difficulty arising from evaporation of the solutionsat the higher temperatures the top of each solution was covered with alayer of molten paraffin. The conductivities were measured at every lo", and the difference d between consecutive readings is taken as amean temperature coefficient for the 10" rise of temperature.Solutions of salts which are ordinarily anhydrous in the solid state,such as KCI, NaCI, KN03, have temperature coefficients which risecontinually with the temperature, or which attain a maximum andthen remain constant. On the other hand, the temperature coefficientof solutions of hydrated salts at 6rst increases, reaches a maximum,and t,hen decreases, the author attributing this last behaviour to theloss by the salt of its water of crystallisation.Calcium chloride forms;t:i exception to this rule, tbe three solutions examined, which con-tained 4.5, 19.2, and 32 per cent. CaC12, behaving throughonit assolutions of anhydrous salts. The temperature coefficient in the caseoC the second solution, however, only' undergoes a slight increase withrising temperature, and i3 far smaller than that of the first or thirdsolutions. Five solutions of cupric chloride were examined, havingthe percentages 1.35, 9, 18.2, '28.7, 35.2. The t w o concentrated solu-tions are green, the two dilute solutions blue, and the colour of thethird solution is intermediate between the two.All these solutionsbehave as solutions of hydrated saits, the temperature coeflicient ineach case reaching a maximum at between 40" and 50". At the sametemperatures, a change in colour is also observed, the green solutionsbecoming yellow and the blue solutions becoming green. I n eachcas9 these changes seem, therefore, to be conditioned by a dehydrationof the salt taking place as the temperature rises. Cobalt chlorideshows a somewhat similar behaviour, the colour of the solutionschanging from red to blue on heating, and at the same time the tem-perature coefficient reaching a maximum. The temperature of thechange is, however, higher in this case, and therefore it is not soreadily observed.The author concludes that salts are contained in solution partly ashydrates and partly i n the anhydrous state.At high temperatures,the hydrates part with their water, this taking $lace the more readilyin the more concentrated solutions. The water of hydration exercisesa specific influence 011 the electrical conductivity of solutions.H. C.Electrical Conductivity of Saline Solutions. By P. CHROU-SHTCHOFF and W. PASHKOFF (J. Russ. Chem. Soc., 22, 110-115), andby CHROVSHTOHOVF (ibid., 115--116).-The two papers contain tt largenumber of experimental data as regards the conductivity of aqueoussolutions of salts and mixtures of salts and acids, but the conclu-sions arrived at are the same as those contained in Chroushtchoff'sprevious papers (Abstr,, 1P89, 808-809).B. B14 2 ABSTRACTS OF CHEMICAL PAPERS.Solubility of Mixtures of Electrolytically DissociatedSubstances. By A. A. NOYES (Zeit. physikal. Chem., 6,84i -267) .-It has been shown by Nernst (this vol., p. 3 ) that the principles regu-lating the influence of two salts on each other's solubility are thosededuced from the general law of mass action as interpreted in thelight of the electrolytic dissociation theoiy. The author, in thepresent paper, contributes an account of his experimental work onthe subject. He investigated 11 pairs of salts, and fintls the resultsof his experiments in very good agreement with the theoreticalvalues. Most of the work was done with binary electrolytes, forexample, AgBrO, : AgNO?, TlSCN : T1N03, but a few ternary electro-lytes were shown to give results equallp in harmony with the theory.Experiments were made not only with pairs of salts con-taining one ion in common, but also with pairs whose ions were alldiff wen t .Reckoning back from the solubilities, i t is possible to calculate thedissociation constants of strong electroljtes.This is a fact of COD-siderable importance, for the ordinary method of calculation from theelectrical conductivity fails in such cases to give a constaat numberat all. J. W.Method of Determining Thermal Expansion for EqualQuantities of Heat. By E. J. DRAGOCMIS (Zeit. physikal. Chem., 6,281--284).-Let V be the volume of a substance; g its weight ; aits coefficient of cubical expansion ; c its specific heat ; g its specificgravity ; At the rise of temperature, and A the expansion caused bythe communication of 1 cal.; then A = Vaht.But At = l/cg andV/g = 11s; therefore A = ales. In the case of gases, A is evidentlyinversely proportional to the molecular heat, for a is constant for allgases, and s varies inversely as the molecular weight.The author determines A in the following manner : A dilatometerpacked in cotton wool contains the substance whose expansion is tobe measured, and also a platinum spiral, the ends of which are fusedthrough the walls. By means of this spiral the substance is heated,a current of about 0.2 ampere being passed. From the current, theheat communicated is easily calculat'ed, and the expansion for thisamount is obserred.Comparative experiments with various liquidswere executed, and the results found to be satisfactory. J. W.Estimation of the Specific Gravity of Frothy Syrups. ByA. GENIESER (Zeit. ang. C'hern., 1890, 44-45).-A tared pyknometeris about two-thirds filled with the syrup, in which air-bubbles areentangled, and the weight is noted. It is then carefully heated in asalt bath, and maintained in ebullition for a few moments. Thewhole of the air rises to the surface, where it forms an extremely thinlayer of froth. After cooling, water is added, so as to float on thesurface without mixing. The froth readily dissolves, and the airescapes. The pyknometer is then filled to the mark with water, andweighed. On deducting the excess of weight, above that of the syruptaken, from the total amount of water which the pyknometer wilGENERAL AND PHYSICAL CHEMISTRY.143contain, the remainder gives the weight of water equal in volume tothe syrup taken, and thence the specific gravitty.By A. W. v. H o F b r m N (Ber., 23,3303-3319).-Dissociation of Cadonic Anhydride.--In 1860, theauthor published a paper in conjunction with H. Buff, in which i twits stated that carbonic anhydride is gradually decomposed by thepassage of a series of electric sparks through the gas, and that aftera time the carbonic oxide and oxygen recombine with explosiveviolence. A repetition of these experiments has shown that theexplosion only occuis under certain special conditions. 6-10 C.C.ofdry carbonic anhydride under a pressure of 650-700 mm. arebrought into a stout glass tube standing over mercury; a shortpiece of platinum wire is fused into the shorter limb of a, thinU-shaped tube, the tube is filled with mei-cury, and a second pieceof wire wound spirally round the outside of the shorter limb, whichis then passed up into the vessel containing the gas; in this waythe length of the spark may be readily regulated; in general itshould be 2.5-3 mm. Connection is made b7 two wires dipping intothe mercury contained in the U -tube and trough respectively. Theelectric current is obtained from two Bunsen’s elements of mediumsize, which are connected with a Rnhmkorff’s coil and a smallLeyden jar, the coil being 30 cm. long and 10 cm.in diameter.The first explosion usually occurs after 15-20 minutes, aud thesubsequent ones at shorter intervals, since the regeneration of thecarbonic anhydride is not complete. The dissociation of carbonicanhydride may be shown by passing the gas tbrough a glass tube, inthe middle of which two plat<inum terminals are fused ; a series ofsparks is allowed to paw, and the issuing gas collected over potash ;part of the gas remains undissolved, and is found to be explosive. Carb-onic anhydride does not appear to be at all affected by a glowing spiralof wire ; it was not found pomible to prepare the gas free from air.Dissociation of Steam-The accompanying illustration (next page)shows a form of apparatus which niay be employed for the purpose ofshowing the dissociation of steam at varying pressures.The wide glasstube is 2.5 cm. in diameter and 20 cm. in length, the lower tube is 1 cm.in diameter and 40 cm. in length ; the apparatus is filled with moistmercury and heated with steam; instead of fixed terminals, theU-tnbe and wires described above may be employed ; in one experi-ment 2.9 C.C. of gas were obtained after ten minutes ; no regenerationof water occurred, as in the case of carbotiic anhydride. The experi-ment may be varied by allowing the apparatus to cool whilst theelectric current is continued ; the dissociated gases gradually combine,and the whole tube becomes refilled with mercury. The currentemployed is obtained from three Bunsen cells, with the coil andLeyden jar as before.Steam may also be dissociated by means of aglowing white hot spiral of platinum wire; the two ends are con-nected with accumulators, stearn is passed over the coil, and themixed gases are collected over cold water, which serves to condensethe excess of steam.Dissociation of Gases and Vapours by the Silent Discharge.-Experi-M. J. S.Dissociation Phenomena144 ABSTRAOTS OF OHEMIOAL PAPERS.ments in this direction show that ozone is produced by the decompo-sition of carbonic anhydride, the results of Andrews and Tait, Brodic,and others being thus confirmed. Steam may also be decomposed bypassing it through 8 Siemens ozone tube, or by the use of the modi-fied apparatus devised by Berthelot ; various experiments were madeto prove that the explosive gas obtained was really derived from thesteam, and was not due to electrolysis.Berthelot’s results on thedecomposition of ammonia by means of the silent discharge are con-firmed. The vapours of methyl alcohol, ethyl alcohol, and ethylether may also be dissociated by mems of the silent discharge.Influence of Mineral Acids on the Velocity of the Reactionbetween Brornic and Hydriodic Acids. By G. MAGNANINI(Gazzeffa, 20,377-393).-The reaction between bromic and hydriodicacids was shown by Ostmald (Abstr., 1885, 1024) to form an excep-tion to the ordinary rule of mass action, and neither Meyerhoffer’s(Abstr., 1889, 9) nor Burchard’s (Abstr., 1889, 208) expressions arefound to satisfy the experimental data respecting the vmiation of thespeed of the reaction.These discrepancies are evidently occasionedby secondary reactions, which alter the velocity of thc changes atevery instant. Ostwald found that mineral acids increase the speedof the reaction, and that the increments are sensibly proportional tothe affinity coefficients of the respective acids, or to the quantity ofhydrogen electrolytically dissociated from them. The author hascontinued Ostwald’s investigations on the accelerating or retardingJ. B. TGENERAL AND PHYSICAL CHEMISTRY. 145effecto. of mineral acids on this reaction, esperimenting with hydro-chloric, nitric, sulphuric, and bromic acids, with mixtures of some ofthese acids, and with potassiuni bromate ; from the tabulated results,he draws the following conclusions. During tohe course of thedifferent changes, the reaction is influenced in the same way by thesecondary actions.The reciprocal values of the times required forthe separation of a determinate quantity of iodine vary as thevelocity of the respective reactions. The velocity of the reaction isaccelerated by hydrochloric acid, but the acceleration is not propor-tional to the quantity of acid present. The quantity of iodinedeposited after equal times in presence of equivalent quantities ofhydrochloric and nitric acids is the same. Mixtures of hydrochloricand nitric acids, in any proportions, are equivalent to either of theacids, so that, independently of the nature of the electro-negativeradicle, it may be said that the velocity of the reaction dependsentirely on the quantity of hydrogen electrolytically dissociated,without, however, being proportional t o it.The action of sulphuricacid is more complicated, on account o€ t.he incomplete dissociation ofthat acid. The :tccelerating effect of bromic acid is almost six timesthat of hydrochloric or nitric acid. S. B. A. A.Velocity of the Halogenisation of Fatty Hydrocarbons. ByIf. WILDERMAN" (BAT., 23, 317&3175).--The following two lawsare deduced from a study of the action of bromine or chlorine insunlight on amyl bromide, amylene bromide, liquid and solid tri-bromopentane, tetrabromopentane, and amylene chloride :-( 1) Sub-stitution proceeds more slowly as the quantity of positrive hydrocarbonbecomes smaller.(2) The larger the quantity of hydrocarbon present,the quicker the substitution.Cryoscopic Investigation of Colloidal Substances. By A.SABAN~EFF ( J . Russ. Chew. SOC., 22, 102--107),-The author hasshown that Raoult's method may be conveniently employed for thedetermination of tbe molecular weight of colloidal substances (Abstr.,1890, 1215). Similar results were obtained by Morris and Brown,by Ekstraud and Mauzelius. 0 1 1 the other hand, Paternb, in hisresearch on gallic and tannic acide, has arrived a t the conclusion thattheir molecular. weights cannot be determined by Rao ult's method.The values obtained by Paternb give 10 mols. of the first, and 109ruols. of the second, as the molecular weights in solution. The authorshows that Paternb's paper includes an error in calculation, and thatthe values greatly depend on the purity of the material.First themolecular weight of gallic acid was determined. It mas dried at 120°,iosing 9.65 per cent. water, corresponding with the formula C,H6OS +H20. In aqueous solution, containing 0.5238 per cent., the depres-sion was 0*06", and the rnolecular weight 166 ; i n acetic acid, con-taining 0.4107 part, the depression was 0*095", molecular weight =168, whereas the value for C7H606 is 170; gallic acid exists, there-fore, as a. airigle molecule in solutions.Commercial tannin was found to contain some gallic acid, thequantity of which, as calculated from the depression of the impureJ. B. T146 ABSTRACTS OF CHEMICAL PAPERS.preparation, compared with that of the pure preparation, was found tobe 2-39 per cent.It was dried for 20 hours at 120', and the loss was10.66 per cent. Aqueous solutions with a concentration of 0-822-3.773shorn a depression of 0*015--0~060, giving a molecular weightof 1044-1195 (mean, 1104). More concentrated solutions, contain-ing 5.5 to 9.5 per cent., gave higher molecular weights, 1497 to 2436,but the values are useless, as solutions of more than 4 per cent. oftannin in water become turbid a t O", tannin separating out. I nPaternb's solutions, containing 11.5-23 per cent. of tannin, $--3 Ofthe tannin must have separated tit 0" in the insoluble state, and h i s(corrected) molecular weights, = 2643-3700, are of no value. Theauthor finds in acetic solution, molecular weights = 1105-1114(mean 1113).Pure tannin was pwpared by Lowe's method, but itwas impossible to work with aqueous solutions, as not more than0-5 per cent. is dissolved in water at O", and even such weak solutionsbecame turbid. I n acetic acid solution, as a mean, M = 1322 wasfound, whereas, M calculated for (C14Hlo09)4 = 1288, so that tanninexists in solutions as a quadruple molecule. The author thinks thatPaternb's tannin was not quite dry, and shows by experiment thatsuch a preparation causes a much larger depression, owing to thecontamination of the glacial acetic acid by the water of crystallisationof the compound. The author says that the empirical formula oftannin requires confirmation by further research.Apparatus for Distillation under Reduced Pressure.By H.W ISLICENUS (Ber., 23,3292-3295).--The author describes two formsof apparatus for use with the the Bunsen pump, to prevent backwarddiffusion. The first consists of a tube, with one round and one pear-shaped bulb; in the depression between these a rubber ring is placed,one end of the tube is sealed, 5 small opening is made in the side andis covered with a piece of rubber tube, or an ordinary Bunsen valvemay be attached; the other end of the tube is connected with thevessel to be exhausted, the pear-shaped bulb fits into a wide tube, therubber ring serving to make the connection air-tight ; the second tubeis joined to the pumpin the usual manner. The second form of valveconsists of two tubes, one closely resembling a thistle funnel, thenarrow end of which is attached to the pump; a bulb with asmall aperture is blown a t the end of the second tube, and i t iscovered with a rubber cap, through which an opening is pierced st alitt.le distance from the one in the glass; the rubber cap serves tomake an air-tight connection between the bulb and the wide end ofthe first tube.An apparatus for fractional distillation under reduced pressure isalso descrihed ; it consists of a combination of several of the first ofthese joints, and provision is made for changing the receiver withoutinterrupting the distillation.Isomorphism.Part 111. By J. W. RETGERS (Zeit. physikaE. Chem.,6,193-236).-1n this communication (for previocs papers see Abstr.,1890,328,1208), the author first discusses the relations of morphotropy.He would limit the term morphotropic to such substances as show aB.B.J. B. TGENERAL AND PHYSICAL CHEMISTRY. 147total analogy of form, and not, for instance, merely analogy of anglesin one zone. Isomorphons substances have not only this total form-analogy, but also analogy of chemical constitution. Morphotropicsubstances are not necessarily cheniically analogous, but must bechemically connected with each other. Substances which show atotal form-analogy, but have no chemical rcsemblance, are termedisogonic. In the regular system, for instance, potassium chloride andrubidium chloride are isomorphous ; potassium chloride and sodiumchloride, morphotropic ; and sodium chloride and sodium chlorate,isogonic.lsomorphous mixtures are proved by the continuous linear changeof physical properties with the composition of thc mixture. Nointimate crystalliue mixture can be obtained with merely morphotropicSubstances, and in this case identity of system, and of degree of hemi-hedry, are not essential. The author rejects Marignttc and Klein’sconception of mas3 isomorphism, according to which an element, o rgroup, largely preponderating in a compound, determines the crystal -line form, no matter what the other components may be. It is thevolume and not the weight of the group that is decisive.An investigation follows of the supposed isomorphism betweenpotassium and sodium sulphates. The author proves that a definitedouble salt, 3K2S04,Na$04, crystallisev from a solution of the mixedsnlphates. It usually crystallises in hexagonal prisms or pyramids,but when the mother liquor contains sodium chloride, i t separates intables-the “ plate-sulphate ” obtained in the manufacture of iodinefrom kelp. Potassium chloride does not effect this change of form.The three simple forms are then-K2S04. Rhornbic, pseudo-hexagonal. Forms pyramids and prismsof hexagonal section. Optically biaxial. Weak birefringence. Sp.gr. = 2.666.3KZSO4,Na,SO4. Hexagonal. Forms pyramids and prisms. Optic-ally uniaxial. Marked birefringence. Sp. gr. = 2.695. Easilyfukible.NhSO,. Rhombic, but not pseudo-hexagonal. Forms onlypyramids with rhombic section. Optically biaxial. Strong birefrin-gence. Sp. gr. 2.673. Fusible with great difficulty.The double salt is not an isomorphons mixture, as is shown by aconsideration of its properties in relation to those of the simple salts.Each simple salt can take up a minute quantity of the other, whichpoints to a very limited isodimorphism.Not easily fusible.The general results are-(1) K&Oa and Na2S04 are not isomorphous.(2) They only form one double salt, 3KzSOa,Na2S04.(3) From mixed solution the pure double salt separates out along-(4) K,SO, and the double salt are morphotropic.(5) NazS04 is not, morphotropic either with K2S04 or with thOdouble salt, but is crystallographically completely independent.The dolomite series is next discussed. In this series we havecalcspnrs containing a little magnesium carbonate, magnesites con-taining a little calcium carbonate, and dolomites which have the twosalts in nearly equal molecular proportions. Calculated from theside one or other of the simple salts148 ABSTRACTS OF OHFJIICAL PAPERS.specific gravities of the component salts, that of dolomite shonld be2.843 ; it is actually 2.872. The author considers the series not iso-morphoua, but merely morphotropic. J. W

ISSN:0368-1769    

DOI:10.1039/CA8916000137

出版商:RSC    

年代:1891

数据来源: RSC

摘要:

148 ABSTRACTS OF OHFJIICAL PAPERS. I n o r g a n i c Chemistry. Afinities of Iodine in Solution. By H. GAUTIER and G. CHARPY (Compt. rend., 111, 645--647).-1f mercnry is agitated with any solution of iodine, a green precipitate of mercurous iodide is formed, but if the mercury coutains another metal, the iodine combines with the latter in proportions depending on the nature of the solvent. In the case of an amalgam of lead, the difference in colour between lead and mercurous iodides enables the change t o be followed. Brown solutions of iodine (in alcohol, ether, acetone) yield with lead amalgam ft yellow precipitate of lead iodide, even when the pro- portion of lead is aery small, and no mercurous iodide is formed nnt.il .all the lead has been converted into iodide. On the other hand, violet solutions of iodine (in chloroform, carbon bisulphide) give green mercurous iodide, eveti in presence of con- siderable quantities of lead and when the iodine is in excess.Solutions of intermediate tint give precipitates intermediate in colou- between lead iodide and mercurous iodide, and it is found that it’ the solutions of iodine in various solvents are arranged in order according to their colour, and a h according to the colour of the pre- cipitate which they yield when agitated with lead amalgam, the two orders are the same. The colour of the precipitate is indepen- dent of the composition of the amalgam and the concentration of the iodine solution. Careful examination of the reaction shows that brown solutions of iodine and pure mercury at first yield mercuric iodide, which passes into solution, whilst violet solutions of iodine at once form mercurous iodide, even whilst some free iodine remains. I n presence of lead amalgam, brown solutions of iodine first form mercuric iodide, which attacks the lead, forming lead iodide and mercurous iodide, and the latter is again converted into mercuric iodide by the free iodine.No permanent precipitate of mercurous iodide is formed with brown solutions until all the lead has been converted into iodide. It follows from these results that violet solutions of iodine contain the element in a more simple molecular condition, with a tendency to at once form mercurous iodide, this tendency beiug more marked, the simpler the condition of the iodine. The phenomena seem $0 belong t o the same order as those to which Berthelot has given ihe name “ tendency to conservation of type.” By H.BECQUEKEL and H. MOISSAN (Compt. rend., 111, 669--672).--It is well known that certain C. H. B. Fluorapar from Quinci6.INORBANIO OHEMISTRY. 149 specimens of fluorspar, when powdered, emit a peculiar odour, which has been attributed by different observers to free fluorine, hypo- chlorous acid, ozone, hydrocarbons, &c. Thc fluorspar examined by the authors was deep violet in colour, and came from QuinciB, near Villefranche. I t had the composition Ca, 36.14 (= CaF,, 70.47); Fez03 + A1,03, 3-93 ; SO4, 25.00 ; loss at a red heat 2-10 per cent ; sp. gr. 3.117. When powdered, it emitted an odour recalling that of ozone and likewise that of fluorine.Moissan has shown that fluorine decom- poses water with liberation of ozone. The odour from the fluorspar is very similar to that emitted from the electrolytic cell in the isola- tion of flumine, and even if the odour is due to ozone, the latter may be a product of the action of free fluorine on the moisture of the air. Fluorspar from Quincik, when powdered in contact with moist air, evolves a gas which at once acts on ozone paper. If moistened with starch paste and potassium iodide solution, and powdered under a microscope, bubbles of gas are seen to escape, and an intense blue coloration is produced. When the fluorspar is powdered with sodium chloride or potassium bromide or iodide, free chlorine, bromine, or iodine is liberated. When heated above a red heat, the fluorspar decrepitates, loses its colour, and becomes ochreous, and after wards gives no trace of ozone when powdered.If heated at 250" for an hour, which is quite sufficient to destroy all ozone, it still gives, when powdered, a strong reaction with ozone paper. Small fragments of the mineral, when heated in a small glass tube, corrode its surface ; when powdered with silicon, a pungent odour is emitted, and if the mixture is heated, silicon fluoride IS evolved. If small fragments of the mineral are left in contact with water, the water becomes acid, and if the liquid is then evaporated in watch glasses, the latter are corroded. No similar results were obtsined with a white fluorspar from the Pyrenees, and although i t is possible that the fluorine results from the dissociation of a perfluoride, the authors regard it as more probable that the free fluorine is occluded in the mineral.The Molecular Weight and Refractive Energy of Sulphur Dichloride. By T. COSTA (Gazzetta, 20,367-372).--The existence of definite compound of the composition SC1, has been repeatedly called in question (see this Journal, 2870,455 ; 1871,1163 ; Abstr., 1878,553 ; 1886, 977) ; and the substance held by some to be sulphur dichloride has been variously regarded as a solution of chlorine in the mono- chloride, or as rt compound in a state of partial dissociation. The author has determined cryoscopically the molecular weight of the reddish-brown liquid obtained by saturating the monochloride with chlorine below O", and then removing any excess of chlorine by passing in a current of carbonic anhydride, and the results of the determinations, both in benzene and acetic acid solution, agree with the molecnlar formula SCI,. This substance can, therefore, no longel*- be said to exist in a state of partial dissociation.Its density at 15.4" is 1.64819 and its molecalar refractive energy PHa = 1.57169, pNa = 1.57806. S. B. A. A. C. H. B.150 ABSTRACTS OF UHEMICAL PAPERS. Specific Gravity of Sulphuric Acid of Different Degrees of Concentration. By G. LUNGE and M. ISLER (Zeit. ang. Chem,., 1890,129-1 36) .-In consequence of tohe discovery of errors in Kolb'F table, the authors have made fresh determinations with great care. The curve plotted from the results, whilst agreeing in many places closely with that of Kolb, is much smoother, and at the extremes, differs somewhat considerably.The table, of which the following is an abstract, was obtained by graphic interpolation ; iu the original, i t is given for intervals of 0.005 (lo Twaddell) in the specific gravity :- Sp. gr. at 15" in vacuo. 4 O 1,000 1 -020 1 -044) 1 -060 1 -060 1 -100 1.120 1 -144) 1'160 1.180 1.200 1 -220 1 *240 1 -860 1 -280 1 -300 1 *320 1 '34.0 1 -860 1 *380 ~~~ Percentage of H2S0,. 0 *09 3 *03 5 *96 8 -77 11 *60 14 -35 17 -01 19 61 22.19 24 *76 27 -32 29 '84 32 '28 34.57 36 -87 39.19 41 *50 43 '74 45 *88 48 -00 8p. gr. st 15" in vacuo. e0 -- 1 -400 1 '420 1 *440 1.460 1 -480 1 '500 1 0520 1.540 1-560 1 *580 1 *600 I *620 1 -640 1 * 660 1 -680 1 -700 1 -720 1 *740 1 -760 1.780 Percentage of H2S04.50-11 52 -15 54 -07 55 *97 55' -83 59 -70 61 *59 63 -43 65 *C8 66 -71 68 *51 70 -38 71 *99 73 -64 75 '4.2 77 -17 78 '92 80 -68 82 -44 M -50 Sp. gr. at in vacuo. -- 1 -800 1 *820 1 -824 1 *826 1 *828 1.830 1 -832 1 -834 1 -836 1,838 1 *840 1 -8405 1 *8410 1 -8415 1 *8410 1 % a 5 1 93400 1 -8395 1 * 8390 1 -8385 Percentage of HSSOI. -- 86 '90 90 '05 90 *80 91 -25 91 -70 92 -10 92 -52 93 -05 93 -80 94 *60 95 *60 95 -95 97 -00 97 -70 98 -20 98 *70 99 *20 99.45 99 *70 99 *95 M. J. S. Reduction of Oxygen Compounds with Sodium. By. M. ROSENFELD (Ber., 23, 3147-3149).-Sodiiim may be obtained in a finely-powdered condition by triturat ion with some other solid sub- stance. Such a niixtnre ot' sodium and zinc oxide ignites spon- taneously, and leaves a residue of metallic zinc.Ferric oxide and lead oxide react in a similar manner, whilst gypsum is reduced to calcium sulphide. Certain orgauic compounds, sach as pyrogallol, wheat starch, or salicylic acid, inflame immediately on admixture with sodium, carbon being separated ; other substances, such as milk sugar and cane sugar, after admixture with sodium, require to be ex- posed t o moist air before reaction takes place. In the cme of com- pounds which only contain carboxylic oxygen, the sodium salt of the acid is formed. Sodium benzoate and sodium oxulaie are obtained from benzoic and oxalic acids respectively. The carbonaceous residue from rosaniline, toluidine, albumin, and other amido-compounds contains sodium cyanide ; brucine, morphine, and strychnine yield aIKOROANIC CHEMISTRY.151 porous mass of charcoal free from cyanogen. Both sodium cyanide iLnd sodium cyanate were obtained from uric acid. “ Saccharin ” vields a residae containing sodium thiosulphate and sodium cyanide. J. B. T. By A. FOCK and K. KLUSS (Ber., 23, 3149-3151).-Ammoniu1n pyrosulphite, ( NH,),S205. is prepared by passing sulphurous anhydride into cold, concentrated, aqueous ammonia until the liquid becomes yellow; i t is then allowed to evaporate spontaneously in a vacuum. The salt crystallises in large, thick, deliquescent plates, which belong to the rhombic system. M.arignac has shown that the corresponding potassium salt crystal- lises in the monoclinic system. Ammonium Pyrosulphite. J. B. T. Properties of some Beryllium Salts and of the correspond- ing Aluminium Compounds.By F. SESTINI {Guzzetta, 20, 313-319).-( 1.) Phosphates. The phosphates mere prepared in the gelatinous state by precipitating ber.yllium sulphate and potassium alum respectively with disodium phosphate, and washing the pre- cipitate for 4 to 6 days ; they are both sparingly soluble in distilled water, the beryllium salt being considerably t-he more soluble of the two. On igniting the moist beryllium phosphate, it left 6 per cent. of its weight of white anhydrous phosphate. A litre of a saturated solution of beryllium phosphate in 2 per cent. acetic acid contains 0.550 gram of t h e anhjdrous salt (containing, however, 74.9 per cent. P,& instead of 74.2 per cent.). A similar solution of the aluminium salt, however, contains 0.373 gram of phosphate dissolved, containing 87.1 per cent.P205 (instead of 54.8 per cent.) ; this excess of acid is probably due to the formation of a little beryllium pyrophosphate and to the conversion of f~ portion of tho aluminium phosphate by the acetic acid int.0 a more soluble acid phosphate. A litre of a saturated solution of the beryllium salt in 10 per cent. acetic acid conlains 1.725 grams, and the corresponding niu miniuin solution Q.30 gram of the respective anhydrous Phosphates. On gently heating the acetic acid solution of beryllium phosphate, it becomes turbid, and near the boiling point a white precipitate of a basic phosphate, of the formula 3Be0,P20,,3H20 + Aq, is deposited; a solution of the aluminium salt at most becomes opalescent. (2.) Cai-bonates.-lOO C.C.of water saturated with carbonic an- hydride at the ordinary pressure dissolves 0.185 gram of anhydrous beryllium oxide, and the solution becomes turbid on agitation or on !ioiling. Under the same conditions, only 0.001 gram of aluminium oxide passes into solution. The solubility of the beryllium oxide is due, according to the author, to the formation of an acid carbonate. ;5. B. A. A. Magnesium Lead Chloride. By R. OTTO and D. DREWES ( A w . ~ . Pha~n.t., 228, 495-498) .-A hot concentrated magnesium chloride solution dissolves a considerable amount of lead chloride and deposits, on cooling, a double chloride, PbC12,2MgC12 + 13H20, in small, white, lustrous, indistinct crystais. The salt is exceedingly hypo- scopic ; moisture quickly converts it into a solution of magnesium152 ABSTRACTS OF CHEMIOAL PAPERS.chloride, holding lead chloride in suspension. chlorides appear to give a similar compound. Electrolysis of Fused Aluminium Fluoride. By A. MINET (Uontpt. reud., 111, 603-606). The composition of the bath which gives the best results corresponds with the formula 12NaCl + AI,F,,GNaF ; melting point 675" ; temperature at which vapours are evolved, 1035"; sp. gr. at 820" = 1.76; coefficient of expansion 5 x 10-4; electrical conductivity at 870" = 3.1. The relation o€ the conductivity to the temperature is expressed by the equation Ct = 3*1[1 + 0*0022(t - 870")J. For a current of 1200 amphres, the mass of the bath is 20 kilos., the intensity of the current a t the positive pole is 1 ampere, and the difference of potential between the electrodes is 5.5 volts.The composition of the bath is kept constant bg the gradual addition of a mixture of aluminium hydroxide, &41,02( OH),, 416.4 parts, cryolite, 210.4 parts, and aluminiuni oxy- fluoride, A12F,,3A1,0,, 238.4 parts. The difference of potential, e, between the electrodes when the electromotive force is considerably below that required to produce decomposition is expressed by the equation E = KI, I being the in- tensity of the current, and the temperature being constant. S s t'he point is approached at which the electromotive force of polarisation is equal to the electromotive force of decomposition of the electrolyte, the diEerence of potential cannot be calcutated by means of any simple expression.At 870°, the maximum density of the current a t the electrodes, corresponding with the first, period of electrolysis of the bath specified, varies between 0.02 and 0.03 amp8re. During the second period of electrolysis, when the electromotive force is sufficient to produce decomposit'ion, up to a density of 1 ampere at the positive electrode, the difference of potential is expressed by the equation a = e + p l , where e is the electromotive force of decomposition, and p is the resistance of the electrolyte. At 852', e = 2.15 and p = 0 31 ; at 890", e = 2.40 and p = 0.0044 ; at 980°, e = 0.34 and p = 0.0033. For densities of current higher than 1 ampBre, the difference of potential cannot be calculated as a function of the intensity of the current by any simple expression ; it rapidly attains a value simiiar to that existing in the electric arc.In presence of salts of iron or silicon, within certain limits of density of current at the positive electrode, the salts decompose according to Sprague's law. At 810°, with salta of iron, e = 0.75 and p = 0.0093 ; at 840°, with silicou compounds, e = 1.37 and p = 0.0089 ; at 870°, with aluminium salts, e = 2.15 and p = 0.0085. Prepamtion of Chromium from Potassium Chromium Chloride and Magnesium. By E. GLATZEL (Rer., 23, 3127- S130).-Chromium can be quickly prepared in an almost chemically pure condition in the following mancer :-Potassium dichromate (100 grams) is dissolved in the least possible quantity of water, the solution mixed with hydrochloric acid of sp. gr. 1.124 (400 c.c.), and then 80 per cent.alcohol (100 c.c.) gradually added. The solu- tion of potassium chromium chloride obtained in this way is treated Calcium and lead J. T. C. H. BMINERALOGICAL CHEMISTRY. 153 with potassium chloride (160 grams), the filtered solution evaporated to dryness, the residue heated until anhydrous, freed from the green portions, which are produced by the decomposition of the double salt, then powdered, and mixed with magnesium filings (50 grams). This mixture is heated, for about half an hour, to a bright-red heat, in a closed Hessian crucible in a wind-furnace, care being taken that the potassium chloride does not volatilise completely, otherwise the chrom- ium is partially oxidised. The melt is separated from the super- ficial layer of chromium oxide, treated with water, and the finely divided metal freed from salts and unchanged magnesium by washing it with water, then boiling it with dilute nitric acid, and again wash- ing with water, all the washing being done by decantation.The yield of the metaI, dried at iOO", is about 27 grams. Chromium, prepared in this way, is a light-grey, crystalline, non- magnetic powder of sp. gr. 6.7284 at 16"; it can be melted in a Deville's furnace, but only with great difficulty, and after being melted it shows a silvery fracture. Two analyses of the powder showed that it contained 99.33 to 99.37 per cent. of chromium, and that it was free from silver and magnesium. F. S. K.148 ABSTRACTS OF OHFJIICAL PAPERS.I n o r g a n i c Chemistry.Afinities of Iodine in Solution.By H. GAUTIER and G. CHARPY(Compt. rend., 111, 645--647).-1f mercnry is agitated with anysolution of iodine, a green precipitate of mercurous iodide is formed,but if the mercury coutains another metal, the iodine combines withthe latter in proportions depending on the nature of the solvent.In the case of an amalgam of lead, the difference in colour betweenlead and mercurous iodides enables the change t o be followed.Brown solutions of iodine (in alcohol, ether, acetone) yield withlead amalgam ft yellow precipitate of lead iodide, even when the pro-portion of lead is aery small, and no mercurous iodide is formed nnt.il.all the lead has been converted into iodide.On the other hand, violet solutions of iodine (in chloroform, carbonbisulphide) give green mercurous iodide, eveti in presence of con-siderable quantities of lead and when the iodine is in excess.Solutions of intermediate tint give precipitates intermediate incolou- between lead iodide and mercurous iodide, and it is found thatit’ the solutions of iodine in various solvents are arranged in orderaccording to their colour, and a h according to the colour of the pre-cipitate which they yield when agitated with lead amalgam, thetwo orders are the same.The colour of the precipitate is indepen-dent of the composition of the amalgam and the concentration of theiodine solution.Careful examination of the reaction shows that brown solutions ofiodine and pure mercury at first yield mercuric iodide, which passesinto solution, whilst violet solutions of iodine at once form mercurousiodide, even whilst some free iodine remains.I n presence of leadamalgam, brown solutions of iodine first form mercuric iodide, whichattacks the lead, forming lead iodide and mercurous iodide, and thelatter is again converted into mercuric iodide by the free iodine. Nopermanent precipitate of mercurous iodide is formed with brownsolutions until all the lead has been converted into iodide.It follows from these results that violet solutions of iodine containthe element in a more simple molecular condition, with a tendency toat once form mercurous iodide, this tendency beiug more marked, thesimpler the condition of the iodine. The phenomena seem $0 belongt o the same order as those to which Berthelot has given ihe name“ tendency to conservation of type.”By H.BECQUEKEL and H. MOISSAN(Compt. rend., 111, 669--672).--It is well known that certainC. H. B.Fluorapar from Quinci6INORBANIO OHEMISTRY. 149specimens of fluorspar, when powdered, emit a peculiar odour, whichhas been attributed by different observers to free fluorine, hypo-chlorous acid, ozone, hydrocarbons, &c. Thc fluorspar examined bythe authors was deep violet in colour, and came from QuinciB, nearVillefranche. I t had the composition Ca, 36.14 (= CaF,, 70.47);Fez03 + A1,03, 3-93 ; SO4, 25.00 ; loss at a red heat 2-10 per cent ;sp. gr. 3.117.When powdered, it emitted an odour recalling that of ozone andlikewise that of fluorine. Moissan has shown that fluorine decom-poses water with liberation of ozone.The odour from the fluorsparis very similar to that emitted from the electrolytic cell in the isola-tion of flumine, and even if the odour is due to ozone, the latter maybe a product of the action of free fluorine on the moisture of the air.Fluorspar from Quincik, when powdered in contact with moist air,evolves a gas which at once acts on ozone paper. If moistened withstarch paste and potassium iodide solution, and powdered under amicroscope, bubbles of gas are seen to escape, and an intense bluecoloration is produced. When the fluorspar is powdered with sodiumchloride or potassium bromide or iodide, free chlorine, bromine, oriodine is liberated. When heated above a red heat, the fluorspardecrepitates, loses its colour, and becomes ochreous, and after wardsgives no trace of ozone when powdered.If heated at 250" for anhour, which is quite sufficient to destroy all ozone, it still gives,when powdered, a strong reaction with ozone paper.Small fragments of the mineral, when heated in a small glasstube, corrode its surface ; when powdered with silicon, a pungentodour is emitted, and if the mixture is heated, silicon fluoride ISevolved. If small fragments of the mineral are left in contact withwater, the water becomes acid, and if the liquid is then evaporated inwatch glasses, the latter are corroded.No similar results were obtsined with a white fluorspar from thePyrenees, and although i t is possible that the fluorine results fromthe dissociation of a perfluoride, the authors regard it as moreprobable that the free fluorine is occluded in the mineral.The Molecular Weight and Refractive Energy of SulphurDichloride.By T. COSTA (Gazzetta, 20,367-372).--The existence ofdefinite compound of the composition SC1, has been repeatedly calledin question (see this Journal, 2870,455 ; 1871,1163 ; Abstr., 1878,553 ;1886, 977) ; and the substance held by some to be sulphur dichloridehas been variously regarded as a solution of chlorine in the mono-chloride, or as rt compound in a state of partial dissociation. Theauthor has determined cryoscopically the molecular weight of thereddish-brown liquid obtained by saturating the monochloride withchlorine below O", and then removing any excess of chlorine bypassing in a current of carbonic anhydride, and the results of thedeterminations, both in benzene and acetic acid solution, agree withthe molecnlar formula SCI,.This substance can, therefore, no longel*-be said to exist in a state of partial dissociation. Its density at 15.4"is 1.64819 and its molecalar refractive energy PHa = 1.57169, pNa =1.57806. S. B. A. A.C. H. B150 ABSTRACTS OF UHEMICAL PAPERS.Specific Gravity of Sulphuric Acid of Different Degrees ofConcentration. By G. LUNGE and M. ISLER (Zeit. ang. Chem,.,1890,129-1 36) .-In consequence of tohe discovery of errors in Kolb'Ftable, the authors have made fresh determinations with great care.The curve plotted from the results, whilst agreeing in many placesclosely with that of Kolb, is much smoother, and at the extremes,differs somewhat considerably. The table, of which the following isan abstract, was obtained by graphic interpolation ; iu the original, i tis given for intervals of 0.005 (lo Twaddell) in the specific gravity :-Sp.gr. at15" in vacuo.4 O1,0001 -0201 -044)1 -0601 -0601 -1001.1201 -144)1'1601.1801.2001 -2201 *2401 -8601 -2801 -3001 *3201 '34.01 -8601 *380~~~Percentageof H2S0,.0 *093 *035 *968 -7711 *6014 -3517 -0119 6122.1924 *7627 -3229 '8432 '2834.5736 -8739.1941 *5043 '7445 *8848 -008p. gr. st15" in vacuo. e0--1 -4001 '4201 *4401.4601 -4801 '5001 05201.5401-5601 *5801 *600I *6201 -6401 * 6601 -6801 -7001 -7201 *7401 -7601.780Percentageof H2S04.50-1152 -1554 -0755 *9755' -8359 -7061 *5963 -4365 *C866 -7168 *5170 -3871 *9973 -6475 '4.277 -1778 '9280 -6882 -44M -50Sp. gr.atin vacuo.--1 -8001 *8201 -8241 *8261 *8281.8301 -8321 -8341 -8361,8381 *8401 -84051 *84101 -84151 *84101 % a 51 934001 -83951 * 83901 -8385Percentageof HSSOI.--86 '9090 '0590 *8091 -2591 -7092 -1092 -5293 -0593 -8094 *6095 *6095 -9597 -0097 -7098 -2098 *7099 *2099.4599 *7099 *95M. J. S.Reduction of Oxygen Compounds with Sodium. By. M.ROSENFELD (Ber., 23, 3147-3149).-Sodiiim may be obtained in afinely-powdered condition by triturat ion with some other solid sub-stance.Such a niixtnre ot' sodium and zinc oxide ignites spon-taneously, and leaves a residue of metallic zinc. Ferric oxide andlead oxide react in a similar manner, whilst gypsum is reduced tocalcium sulphide. Certain orgauic compounds, sach as pyrogallol,wheat starch, or salicylic acid, inflame immediately on admixturewith sodium, carbon being separated ; other substances, such as milksugar and cane sugar, after admixture with sodium, require to be ex-posed t o moist air before reaction takes place. In the cme of com-pounds which only contain carboxylic oxygen, the sodium salt of theacid is formed. Sodium benzoate and sodium oxulaie are obtainedfrom benzoic and oxalic acids respectively.The carbonaceous residuefrom rosaniline, toluidine, albumin, and other amido-compoundscontains sodium cyanide ; brucine, morphine, and strychnine yield IKOROANIC CHEMISTRY. 151porous mass of charcoal free from cyanogen. Both sodium cyanideiLnd sodium cyanate were obtained from uric acid. “ Saccharin ”vields a residae containing sodium thiosulphate and sodium cyanide.J. B. T.By A. FOCK and K. KLUSS (Ber., 23,3149-3151).-Ammoniu1n pyrosulphite, ( NH,),S205. is prepared bypassing sulphurous anhydride into cold, concentrated, aqueousammonia until the liquid becomes yellow; i t is then allowed toevaporate spontaneously in a vacuum. The salt crystallises in large,thick, deliquescent plates, which belong to the rhombic system.M.arignac has shown that the corresponding potassium salt crystal-lises in the monoclinic system.Ammonium Pyrosulphite.J.B. T.Properties of some Beryllium Salts and of the correspond-ing Aluminium Compounds. By F. SESTINI {Guzzetta, 20,313-319).-( 1.) Phosphates. The phosphates mere prepared in thegelatinous state by precipitating ber.yllium sulphate and potassiumalum respectively with disodium phosphate, and washing the pre-cipitate for 4 to 6 days ; they are both sparingly soluble in distilledwater, the beryllium salt being considerably t-he more soluble of thetwo. On igniting the moist beryllium phosphate, it left 6 per cent. ofits weight of white anhydrous phosphate. A litre of a saturatedsolution of beryllium phosphate in 2 per cent.acetic acid contains0.550 gram of t h e anhjdrous salt (containing, however, 74.9 per cent.P,& instead of 74.2 per cent.). A similar solution of the aluminiumsalt, however, contains 0.373 gram of phosphate dissolved, containing87.1 per cent. P205 (instead of 54.8 per cent.) ; this excess of acid isprobably due to the formation of a little beryllium pyrophosphate andto the conversion of f~ portion of tho aluminium phosphate by the aceticacid int.0 a more soluble acid phosphate.A litre of a saturated solution of the beryllium salt in 10 per cent.acetic acid conlains 1.725 grams, and the corresponding niu miniuinsolution Q.30 gram of the respective anhydrous Phosphates. On gentlyheating the acetic acid solution of beryllium phosphate, it becomesturbid, and near the boiling point a white precipitate of a basicphosphate, of the formula 3Be0,P20,,3H20 + Aq, is deposited; asolution of the aluminium salt at most becomes opalescent.(2.) Cai-bonates.-lOO C.C. of water saturated with carbonic an-hydride at the ordinary pressure dissolves 0.185 gram of anhydrousberyllium oxide, and the solution becomes turbid on agitation or on!ioiling.Under the same conditions, only 0.001 gram of aluminiumoxide passes into solution. The solubility of the beryllium oxide isdue, according to the author, to the formation of an acid carbonate.;5. B. A. A.Magnesium Lead Chloride. By R. OTTO and D. DREWES ( A w . ~ .Pha~n.t., 228, 495-498) .-A hot concentrated magnesium chloridesolution dissolves a considerable amount of lead chloride and deposits,on cooling, a double chloride, PbC12,2MgC12 + 13H20, in small,white, lustrous, indistinct crystais. The salt is exceedingly hypo-scopic ; moisture quickly converts it into a solution of magnesiu152 ABSTRACTS OF CHEMIOAL PAPERS.chloride, holding lead chloride in suspension.chlorides appear to give a similar compound.Electrolysis of Fused Aluminium Fluoride.By A. MINET(Uontpt. reud., 111, 603-606). The composition of the bath whichgives the best results corresponds with the formula 12NaCl +AI,F,,GNaF ; melting point 675" ; temperature at which vapours areevolved, 1035"; sp. gr. at 820" = 1.76; coefficient of expansion5 x 10-4; electrical conductivity at 870" = 3.1. The relation o€the conductivity to the temperature is expressed by the equationCt = 3*1[1 + 0*0022(t - 870")J. For a current of 1200 amphres,the mass of the bath is 20 kilos., the intensity of the current a t thepositive pole is 1 ampere, and the difference of potential between theelectrodes is 5.5 volts.The composition of the bath is kept constantbg the gradual addition of a mixture of aluminium hydroxide,&41,02( OH),, 416.4 parts, cryolite, 210.4 parts, and aluminiuni oxy-fluoride, A12F,,3A1,0,, 238.4 parts.The difference of potential, e, between the electrodes when theelectromotive force is considerably below that required to producedecomposition is expressed by the equation E = KI, I being the in-tensity of the current, and the temperature being constant.S s t'hepoint is approached at which the electromotive force of polarisation isequal to the electromotive force of decomposition of the electrolyte,the diEerence of potential cannot be calcutated by means of anysimple expression. At 870°, the maximum density of the current a tthe electrodes, corresponding with the first, period of electrolysis of thebath specified, varies between 0.02 and 0.03 amp8re.During the second period of electrolysis, when the electromotiveforce is sufficient to produce decomposit'ion, up to a density of1 ampere at the positive electrode, the difference of potential isexpressed by the equation a = e + p l , where e is the electromotiveforce of decomposition, and p is the resistance of the electrolyte. At852', e = 2.15 and p = 0 31 ; at 890", e = 2.40 and p = 0.0044 ; at980°, e = 0.34 and p = 0.0033.For densities of current higher than1 ampBre, the difference of potential cannot be calculated as a functionof the intensity of the current by any simple expression ; it rapidlyattains a value simiiar to that existing in the electric arc.In presence of salts of iron or silicon, within certain limits ofdensity of current at the positive electrode, the salts decomposeaccording to Sprague's law. At 810°, with salta of iron, e = 0.75and p = 0.0093 ; at 840°, with silicou compounds, e = 1.37 andp = 0.0089 ; at 870°, with aluminium salts, e = 2.15 and p = 0.0085.Prepamtion of Chromium from Potassium ChromiumChloride and Magnesium. By E. GLATZEL (Rer., 23, 3127-S130).-Chromium can be quickly prepared in an almost chemicallypure condition in the following mancer :-Potassium dichromate(100 grams) is dissolved in the least possible quantity of water,the solution mixed with hydrochloric acid of sp. gr. 1.124 (400 c.c.),and then 80 per cent. alcohol (100 c.c.) gradually added. The solu-tion of potassium chromium chloride obtained in this way is treatedCalcium and leadJ. T.C. H. MINERALOGICAL CHEMISTRY. 153with potassium chloride (160 grams), the filtered solution evaporatedto dryness, the residue heated until anhydrous, freed from the greenportions, which are produced by the decomposition of the double salt,then powdered, and mixed with magnesium filings (50 grams). Thismixture is heated, for about half an hour, to a bright-red heat, in aclosed Hessian crucible in a wind-furnace, care being taken that thepotassium chloride does not volatilise completely, otherwise the chrom-ium is partially oxidised. The melt is separated from the super-ficial layer of chromium oxide, treated with water, and the finelydivided metal freed from salts and unchanged magnesium by washingit with water, then boiling it with dilute nitric acid, and again wash-ing with water, all the washing being done by decantation. Theyield of the metaI, dried at iOO", is about 27 grams.Chromium, prepared in this way, is a light-grey, crystalline, non-magnetic powder of sp. gr. 6.7284 at 16"; it can be melted in aDeville's furnace, but only with great difficulty, and after beingmelted it shows a silvery fracture. Two analyses of the powdershowed that it contained 99.33 to 99.37 per cent. of chromium, andthat it was free from silver and magnesium. F. S. K

ISSN:0368-1769    

DOI:10.1039/CA8916000148

出版商:RSC    

年代:1891

数据来源: RSC

摘要:

MINERALOGICAL CHEMISTRY. Mi n e r a 1 o gi c a 1 C h em i s try. 153 Selenium and Tellurium Minerals from Honduras. Bg E. S. DANA and H. L. WELLS (Amer. J. Sci., 40, 78--82).-The authors received a number of specimens of minerals containing selenium and tellurium from El Plomo mine, Ojojama District, Honduras. Two of these have proved to be of unusual interest. The first occurs in massive forms, with hexagonal cleavagt, of a blackish-grey colour, dissemi- nated through a gangue consisting chiefly of quartz and barytes. After deducting 65-68 per cent. of gangue, the analytical results obtained were as follows :- Se. Te. Total. 29-31 70.69 200.00 The mineral is obviously an isomorphous mixture of selenium and tellurium, and is of great interest in that it is the nearest approach to native selenium which has yet been found.The authors propose to call this mineral Xelen-tellurium. In conr?ection with the hex- agonal cleavage of this mineral, it is interesting to n0t.e the recent observations of Muthmann (Zeit. f. Kryst., 17, 356), showing the existence of an allotropic form of metallic selenium in hexagonal- rhombohedra1 crystals, closely isomorphous with tellurium. In the analysis, the separation of selenium and tellui-ium was effected by the method of Divers and Shimose (Trans., 1885, 439). The second mineral is obviously an oxidation product of a greenish- yellow colour. Analysis shows it to be a normal ferric tellurite of VOL. LX. m3 54 ABSTRACTS OF CHEMICAL PAPERS. the composition Fe2O3,3Te0, + 4H20. That the mineral is a ferric tdlurite is evident since it gives off no chlorine when boiled in hydro- chloric acid, nor does it give any reaction for ferrous iron when dis- solved in cold hydrochloric acid.Two other tellurium-iron minerals have been described, namely, Gen th’s feryoteZZurite and Hillebrnad’s emwonsits (Abstr., 1887, 344). The former is a fcrroue tellurite widely different in appearance from the Honduras mineral, for which the authors, therefore, propose the name of Dui-denite, after the gentleman to whom they are indebted for the material used. In a note appended to the paper, W. F. Hillebrand gives the results of a repetition of the analysis OE enimonsite, which upholds the accu- racy of his former analysis, and seems to prove that the two minerals arc distinct.B. El. B. Fluorspar from Quinci6. By H. BECQUEREL and H. MOISSAN (Compt. rend., 111, 669--672).-See this vol. p. 148. New Variety of Zinc Sulphide. By J. D. ROBE~~TSON (Amw. J. Sci., 40, 160-161).--8 peculiar variety of zinc sulphide has been found in south-eastern Kansas, remarkable from the fact t h a t it is nearly pure white and completely amorphous. Itl is found in the centre of the town of Galena, Cherokee Go., Kansas. When taken from the mine, it is soft, full of water, and resembles white lead ground in oil. Evidence points to the existence of a large body of this peculiar ore in the mine. An analysis of a dried sample yielded : Insol. matter. Zn. S. Fe20,,. Total. 2.52 63-70 30.77 2-40 99.39 The water contained iu the original sample showed a slight, amount of sulphuric acid. This sulphide was evidently formed by the pi*ecipitat,ion of zinc sulphate, resulting from the oxidation of blende, by hydrogen sulphide or an alkaline sulphide. Contributions to Mineralogy.By F. A. GENTH (Amer. J. Sci., 40, 114-120).-1. Tetradyn2ite.-This mineral occurs, in crystals suggesting an orthorhombic form, near Bradshaw City, Ayizona. After subtracting 15.6 per cent. of quartz and 1.8 per cent. of ferric oxide, the analysis gave: B. H. B. S. To. Bi. Total. 4.50 33.25 62.23 99-98 These results give a formula analogous to that of bismuthinite. 2. Iron Pyrites.-The occurrence of cobalt arsenate with the octa- hedral crystals of iron pyrites at the French Creek iron mines, Pennsylvania, suggested an analysis of the latter, which gave t t e following results :- S.As. Cu. Ni. Co. Fe. Total. 54.08 0 20 0.05 0.18 1-73 44.24 100.50MINERALOQ~CAL CHEMISTRY. 1.55 3. Quartz, Pseudomorphous after 8tibnite.-Specimens from Durango, Mexico, were found to contain stibnito completely altered into a yellowish-white quartz. 4. Gold in Turquoise.-In many collections, specimens of gold en- closed in a bluish-green mineral are represented as turquoise with gold from Los Cerillos, New Mexico. Specimens analysed by the author are proved l o contain no turquoise; i n one case, the gold- bearing mineral was a chromiferous clay, and in the other, quartz admixed with c hrysocolla. 5. Zircon.-With the masses of monazite, a t Mars Hill, Madison Co., North Carolina, large crystals of zircon, with a sp. gr. of 4.507, occasionally occur.On analysis, the following resuits were ob- tained :- Si02. 250,. Fe203. Loss on ignition. To t?d. 31.83 63-42 3-23 1.20 99.68 6. ScnpoZite.-At the Elizabeth mine, French Creek, Pennsylvania, small crystals of scapolite occasionally occur, filling cavities of grey garnet, associated with magnetite, pyrites, and remnants of the essonite Erom the alteration of which it appears to have been dc- rived. The scapolite is coloui*less to white ; it has a sp. gr. of 2.675, and on analysis gave the following results (‘I) :- COO. SiO,. AlnOs. Fen03. MgO. CaO. Nn@. I. 2-63 52-30 23.68 0.58 0.05 12.36 6.29 TC. 1.71 41.42 18-09 10.81 0.59 ‘LCi.19 - Loss by K,O. ignition. MnO. Total. I. 0.77 1.50 - 100*16* 11. - 0.51 0.88 100.20 The second analysis is of the gray garnet which also results from the alteration OE essonite.7. Titunifei-ous Garnet. -A variety oE garnet from the Jones mine, Green River, North Carolina, gave, on analysis, the followiny re- sults :- Loss on SiO,. TiO,. Al,O,. Fe,O,. FeO. MgO. CaO. ignition. Total. 35.56 4.58 4.43 20.51 1-88 0.17 31.90 0.55 99-58 8. Allunite.-T he author analysed two specimens of allanite with SiO,. Tho?. TiO,. CeO,(LaDi),O,. Y,Os. Al,03. Fe203. the following results :- c~py--J ~..31.67 0.33 - 23-98 0.36 12.20 4-42 b. 32.04 - 0.1’2 12.91 10.24 0.33 14.02 7.17 Loss on FeO. MnO. MgO. CaO. ignition. Total. Sp. gr. U. 10.89 2.52 2.08 9-37 2.25 10007 30.546 b. 7-52 0-37 7.47 11.34 2.63 100.16 3.491 * 100.06 in original. w i d156 ABSTRACT6 OF OHEMIGAL PAPERS. a. Colonr, velvet-black-; b.Deep brownish-black. 9. Lettsomite.--The author has anal-ysed syecimens of this rare material from two new localities : t,he Copper Mountain mine, near Morenci, Arizona, and Copperopolis, Tintic District, Utah. In both cases, the analysis gives results closely agreeing with those demanded by the formula Cu4A1,( OH),,SO, + 2H20. B. H. B. Synthesis of Rubies. By E. FEEMY and B.VERNEUIL (Compt. ~e92d.~ 111, 668--669).--Tbe authors have made several important modi6ca- tions in their process for the manufacture of artificial rubies, and are now able to obtain much larger crptals. The alumina i n addition to the small quantity of chromium is made alkaline with potassium carbonate, which facilitates the formation of the crystals but does not enter into their composition.It is advantageous not to mix all the materials but to keep the alumina separate from the fluorides of the alkaline earths, and in this way the mineralisation is effected by the inteyaction of the gases and vapours. The time of heating i$ extended to not less than a week ; gas furnaces are used in place of coke, and the crucibles have a capacity of several litres, and arc capable of producing as much as three kilos. of rubies at each operation. Natural rubies are found which in parts have the colour of the sapphire. Similar crystals are obtained aniongst the artificial pro- ducts, and there can therefore be little doubt that the colours of the ruby and the sapphire are both due to chromium, probably in different states of oxidation. The artificial rubies have been used as pivots in watches, and are not inferior t o the natural stones in hardness.C. H. B. Curious Occurrence of Vivianite. By W. L. DUDLEY (Amcr. J. Sci., 40, 120-12l).-Two miles above Eddyrille, Kentucky, ‘‘ blue roots ” were discoyered embedded in a stratum of clay i n such position as t o indicate that they were in the place of their growth. The blue mineral, which has almost wholly replaced the woody fibre of t h e roots, is of a, deep-blue colour. It is earthy and very friable, and gave, on analysis, the following results :- HZO HSO A120,. Fe203. FeO. CaO. MgO. P@,. at 100’. at 230’. Tot.al. 17-74 9.35 24-58 0.59 0.43 27.71 10-59 7.24 100.07 These results seem to indicate that the ferrous iron in the. mineral is combined with the phosphoric anhydride to form vivianite, and if the double mol.of vivianite, 2(Fe3P208 + 8H20), be subtracted, there remains an almost dehydrated double mol. of turquoise, A18P402, + IOH,O, in which 1 mol. of ferric oxide has replaced one of alumina. B. H. B. Dihydrothenardite. By V. MARKOVNJKOFF ( J . RUSS. Chem. SOC. ~ 22, 26--27).-Owing to an inexplicable mistake, a new mineral, dihydrothenardite, Na,S04 + 2H20, was described by the authol- (Ahstr., 1868, 794), whereas a renewed investigation shows that it. isMINERALOGICAL CHEMISTRY. 157 -~ Si02 . .. NiO.. .. MgO . . . Fe203. . . Cr203 .. MnO . . . m,o3 .. Ha0 . a . Totals L. -- astrachanite (hydrated sulphnts of sodium aud magnesium) contain- ing a considerable quantity oE thenardite. Connellits from Cornwall. By S.L. PENFIELD (Anzer. J. #&., 40, 82--86).-Connellite is of special interest to the author, owing to its apparently close rclation to the new mineral spnngolite, recently described by him (Abstr., 1890, 1073). On examining a specimen from Camborne, the author found that the habit of the xystals agrees well with the general description given by Maskelyne in 1863. The analysis, in which the author places great confidence, gave the following results :- SOP C1. CuO. H20. Loss at 100". Total. Less 0. 4.9 7.4 72.3 16.8 0.4 101.8 1.7 B. B. 36.25 46.30 9 '00 0' 14 _- 3-20 - - The ratio is not very satisfactory, unless it is assumed that, some OH is isomorphous with the C1, in which case the formula may be written CU,,(C'I,OH),SO,~,~~H~O. The mineral is very similar to spangolite in composition, both minerals being very basic sulphato- chlorides. B.H. B. 34.78 35-80 20.57 43.79 43-54 15 '56 2 '75 2 -65 0 '81 6.30 10.73 49 *03 - 3 -82 - 0 -19 trace 12-43 8 .00 10.32 -. - - - Nickel Ores from New Caledonia. By T. MOORE (C'hem. Nezcs, 62, 180--181).-The ore known as garnierit,e is found in or near serpentine masses or mountains, either as cerrreriting material in agglomerations of rounded serpentine pebbles or as an interstitial deposit between thin layers of qunrh, steatite, and various hydrated magnesium silicates. The associated minerals vary, but comprise quartz, magnesium silicates, and iron oxides ; sometimes one pre- dominates, sometimes another, the others being even absent; it is also accompanied at times by chrome-iron ore and surrounded by a f errugino u s earth.The colour of garnierite varies from pale-green in poor ores to warm dark-green in the richer ones, and passes through almost imperceptible shades to light- and chocolate-browns. It crumbles gradually to powder, on exposure to weather, the brown more readily Green ores. 35 *55 48.38 5 *02 1 *41 1 -09 0.15 8 .85 100 '45 - -- 36 '24 44 '94 8 -75 0 '21 1 '03 - - 8 -98 100 *15 -- Brown ores. I Ferruginous I brown ore. 99.89 I 100'02 1 100.91 I 100.17158 ABSTRACTS OF CEEMICAL PAPERS. Bhan the green varieties ; in all forms it dissolves readilyin hot hydro- chloric acid, leaving a non-gelatinous silica. I n the table (p. l57), are given numbers, corrected for quartz, obtained in thc analysis of samples of pure ore ; samples previously analysed by other workers appear to have been contaminated with gangue :- Samples 1 and 2 were a fine, brilliant grass-green; hardness, 2-3 ; sp. gr.3 ; streak, light-green ; lustre, waxy and slightly t,rans- lucent at their edges. Before the blowpipe, the coloiir becomes dark olive-green, or red in presence of much iron. 3, 4, and 5 were various shades of brown, streak yellow to brownish-yellow, fracture conchoidal with resinous lustre, sp. gr. and hardness the same as green ore, but were rather more brittle. From these numbers, both kinds of ore seem to approach very nearly to a hydrated silicate of the composition 7Ni0,6SiQ2,aH2O, part of the nickel beimg replaced by magnesia, iron oxide, or alumina. The ores represented by sample 6 are light-brown in colour, resembling limonite, are easily marked by the nail, and do not seen1 to belong to the same class as the others just described.Minerals occurring near Port Henry, New York. By J. I?. KEMP (Amer. J. Sci., 40, 62--G4).-At the abandoned Pease quarry, a short distance north-west of Port Henry, a face of white, crystalline limestone has been laid bare, and in this occur streaks of hornblende,. plagioclase, muscovite, and quartz, but containing as well a great abundance of yellowish-brown titanite crystals ; fine brown tour- malines also occur. West of this quarry is another, where flux is being obtained for local furnmes. The rock, a crystalline limestone, con- tains small, hexagonal tables of graphite disseminated through it. Occasionally lemon-yellow calcite is found, with fine crystals of clear calcite of great crjstallographical interest as being good illustrations of oscillatory forms.Further west is the Treadway quarry in ophi- calcite, containing streaks of pjrrhotite, phlogopite, brown tourma- line, and well-crystallised light-brown treniolite. The abandoned quarry six miles north-west of Poi3t Henry, the source of the well- known tourmaline crystals, is probably a felspathic mass either iii gneiss or in granite, and cut by t.hree narrow dykes of altered‘ diabase. Great masses of biotite and fine specimens of rose-quartz are also met with. The so-called Lover’s Pit at Mineville is affording crystals and cleavage masses of magnetite of unusual size and ex- cellence. B. H. B. 1). A. L. Fayalite in the Obsidian of Lipari.By J. P. IDDINS and S. L. PENFIELD (Amer. J. Xci., 40, 75-78).-The Lipari Islands have long been celebrated for their acid laws and pumices. The chief interest in connection with these rocks attaches itself to the fayalife crystals in the cavities, which hare not been noticed hitherto. They are not abundant, but occur i n several localities, Laving been found by J. P. Iddings at Forgin Vecchia, and in the obsidian stream on Volcano, and having been noted in specinieris lrom Monte della Guardia. The crjstals at Forgia Vecchia are very thin plates, the <*rystallographicnl measurements of which are given in detail by theORQANIC CEIEMISTRP 159 authors. The optical properties not only agree with orthorbombic symmetry, but also with the determinations made on the fayalite from Obsidian Cliff, in the Yellowstone Pmk (this vol., p.26). The chemical composition, too, is the same in both cases, namely, ortho- silicate of iron. The occurrence of fayalite in the liollow spherulites and lithophysaa in the obsidian OE the Lipari Islands, whilst not SO abundant as in that of the Yellowstone Park, is identical. It is associated in the same manner with tridyrnite and alkali felspurs, and its development is due to the same causes in the two regions. Two New Meteoric Irons. By l?. P. VENABLE (Amer. J. &i., 40, 161-163).-1. A mass is reported to have fallen in 1846 at Deep Springs Farm, in Rockingham Co., North Carolina. It is now in the possession of the State Museum. The weight of the mass was 11.5 kilos.It had the shape of a rhomboid, and was coated with oxidation products, giving it a dull-reddish colonr. The surface is irregularly pitted. On being polished and etched, it faintly exhibited Widmanstatten figures. It belongs to the class of sweating meteor- ites, beads of deliquesced ferric chloride appearing on the surface. The analysis gave- Fe. Y. SiOB. C1. Ni. Co. Total . 87*01 0.04 0.53 0.39 11.69 0.79 200.95 2. A meteoric iron was found in 1889 in Henry Co., Virginia, B. H. B. It weighed 1.7 kilos., and the detached pieces, mainly crust, 0.28 kilo. The iron contains a considerable amount of ferric chloride, and rapidly crumbles. On polishing one of the sides, the Widrnanst'atten figures came out plainly, no etching being necessary. The analysis gare the following results :- Fe.C1. SO2. P. Co. Ni. Total. 90.54 0.35 0.04 0.13 0.94 7-70 99.70 B. H. B.MINERALOGICAL CHEMISTRY.Mi n e r a 1 o gi c a 1 C h em i s try.153Selenium and Tellurium Minerals from Honduras. Bg E.S. DANA and H. L. WELLS (Amer. J. Sci., 40, 78--82).-The authorsreceived a number of specimens of minerals containing selenium andtellurium from El Plomo mine, Ojojama District, Honduras. Two ofthese have proved to be of unusual interest. The first occurs in massiveforms, with hexagonal cleavagt, of a blackish-grey colour, dissemi-nated through a gangue consisting chiefly of quartz and barytes.After deducting 65-68 per cent. of gangue, the analytical resultsobtained were as follows :-Se. Te. Total.29-31 70.69 200.00The mineral is obviously an isomorphous mixture of selenium andtellurium, and is of great interest in that it is the nearest approachto native selenium which has yet been found.The authors proposeto call this mineral Xelen-tellurium. In conr?ection with the hex-agonal cleavage of this mineral, it is interesting to n0t.e the recentobservations of Muthmann (Zeit. f. Kryst., 17, 356), showing theexistence of an allotropic form of metallic selenium in hexagonal-rhombohedra1 crystals, closely isomorphous with tellurium. In theanalysis, the separation of selenium and tellui-ium was effected by themethod of Divers and Shimose (Trans., 1885, 439).The second mineral is obviously an oxidation product of a greenish-yellow colour. Analysis shows it to be a normal ferric tellurite ofVOL.LX. 3 54 ABSTRACTS OF CHEMICAL PAPERS.the composition Fe2O3,3Te0, + 4H20. That the mineral is a ferrictdlurite is evident since it gives off no chlorine when boiled in hydro-chloric acid, nor does it give any reaction for ferrous iron when dis-solved in cold hydrochloric acid. Two other tellurium-iron mineralshave been described, namely, Gen th’s feryoteZZurite and Hillebrnad’semwonsits (Abstr., 1887, 344). The former is a fcrroue telluritewidely different in appearance from the Honduras mineral, for whichthe authors, therefore, propose the name of Dui-denite, after thegentleman to whom they are indebted for the material used.In a note appended to the paper, W. F. Hillebrand gives the resultsof a repetition of the analysis OE enimonsite, which upholds the accu-racy of his former analysis, and seems to prove that the two mineralsarc distinct.B. El. B.Fluorspar from Quinci6. By H. BECQUEREL and H. MOISSAN(Compt. rend., 111, 669--672).-See this vol. p. 148.New Variety of Zinc Sulphide. By J. D. ROBE~~TSON (Amw. J.Sci., 40, 160-161).--8 peculiar variety of zinc sulphide has beenfound in south-eastern Kansas, remarkable from the fact t h a t it isnearly pure white and completely amorphous. Itl is found in thecentre of the town of Galena, Cherokee Go., Kansas. When takenfrom the mine, it is soft, full of water, and resembles white leadground in oil. Evidence points to the existence of a large body ofthis peculiar ore in the mine. An analysis of a dried sampleyielded :Insol.matter. Zn. S. Fe20,,. Total.2.52 63-70 30.77 2-40 99.39The water contained iu the original sample showed a slight,amount of sulphuric acid. This sulphide was evidently formed bythe pi*ecipitat,ion of zinc sulphate, resulting from the oxidation ofblende, by hydrogen sulphide or an alkaline sulphide.Contributions to Mineralogy. By F. A. GENTH (Amer. J. Sci.,40, 114-120).-1. Tetradyn2ite.-This mineral occurs, in crystalssuggesting an orthorhombic form, near Bradshaw City, Ayizona.After subtracting 15.6 per cent. of quartz and 1.8 per cent. of ferricoxide, the analysis gave:B. H. B.S. To. Bi. Total.4.50 33.25 62.23 99-98These results give a formula analogous to that of bismuthinite.2. Iron Pyrites.-The occurrence of cobalt arsenate with the octa-hedral crystals of iron pyrites at the French Creek iron mines,Pennsylvania, suggested an analysis of the latter, which gave t t efollowing results :-S.As. Cu. Ni. Co. Fe. Total.54.08 0 20 0.05 0.18 1-73 44.24 100.5MINERALOQ~CAL CHEMISTRY. 1.553. Quartz, Pseudomorphous after 8tibnite.-Specimens from Durango,Mexico, were found to contain stibnito completely altered into ayellowish-white quartz.4. Gold in Turquoise.-In many collections, specimens of gold en-closed in a bluish-green mineral are represented as turquoise withgold from Los Cerillos, New Mexico. Specimens analysed by theauthor are proved l o contain no turquoise; i n one case, the gold-bearing mineral was a chromiferous clay, and in the other, quartzadmixed with c hrysocolla.5.Zircon.-With the masses of monazite, a t Mars Hill, MadisonCo., North Carolina, large crystals of zircon, with a sp. gr. of 4.507,occasionally occur. On analysis, the following resuits were ob-tained :-Si02. 250,. Fe203. Loss on ignition. To t?d.31.83 63-42 3-23 1.20 99.686. ScnpoZite.-At the Elizabeth mine, French Creek, Pennsylvania,small crystals of scapolite occasionally occur, filling cavities of greygarnet, associated with magnetite, pyrites, and remnants of theessonite Erom the alteration of which it appears to have been dc-rived. The scapolite is coloui*less to white ; it has a sp. gr. of 2.675,and on analysis gave the following results (‘I) :-COO. SiO,. AlnOs. Fen03. MgO.CaO. Nn@.I. 2-63 52-30 23.68 0.58 0.05 12.36 6.29TC. 1.71 41.42 18-09 10.81 0.59 ‘LCi.19 -Loss byK,O. ignition. MnO. Total.I. 0.77 1.50 - 100*16*11. - 0.51 0.88 100.20The second analysis is of the gray garnet which also results fromthe alteration OE essonite.7. Titunifei-ous Garnet. -A variety oE garnet from the Jones mine,Green River, North Carolina, gave, on analysis, the followiny re-sults :-Loss onSiO,. TiO,. Al,O,. Fe,O,. FeO. MgO. CaO. ignition. Total.35.56 4.58 4.43 20.51 1-88 0.17 31.90 0.55 99-588. Allunite.-T he author analysed two specimens of allanite withSiO,. Tho?. TiO,. CeO,(LaDi),O,. Y,Os. Al,03. Fe203.the following results :-c~py--J~..31.67 0.33 - 23-98 0.36 12.20 4-42b. 32.04 - 0.1’2 12.91 10.24 0.33 14.02 7.17Loss onFeO.MnO. MgO. CaO. ignition. Total. Sp. gr.U. 10.89 2.52 2.08 9-37 2.25 10007 30.546b. 7-52 0-37 7.47 11.34 2.63 100.16 3.491* 100.06 in original.w i 156 ABSTRACT6 OF OHEMIGAL PAPERS.a. Colonr, velvet-black-; b. Deep brownish-black.9. Lettsomite.--The author has anal-ysed syecimens of this rarematerial from two new localities : t,he Copper Mountain mine, nearMorenci, Arizona, and Copperopolis, Tintic District, Utah. In bothcases, the analysis gives results closely agreeing with those demandedby the formula Cu4A1,( OH),,SO, + 2H20. B. H. B.Synthesis of Rubies. By E. FEEMY and B.VERNEUIL (Compt. ~e92d.~111, 668--669).--Tbe authors have made several important modi6ca-tions in their process for the manufacture of artificial rubies, and arenow able to obtain much larger crptals.The alumina i n additionto the small quantity of chromium is made alkaline with potassiumcarbonate, which facilitates the formation of the crystals but doesnot enter into their composition. It is advantageous not to mix allthe materials but to keep the alumina separate from the fluorides ofthe alkaline earths, and in this way the mineralisation is effected bythe inteyaction of the gases and vapours. The time of heating i$extended to not less than a week ; gas furnaces are used in place ofcoke, and the crucibles have a capacity of several litres, and arccapable of producing as much as three kilos. of rubies at eachoperation.Natural rubies are found which in parts have the colour of thesapphire.Similar crystals are obtained aniongst the artificial pro-ducts, and there can therefore be little doubt that the colours of theruby and the sapphire are both due to chromium, probably in differentstates of oxidation.The artificial rubies have been used as pivots in watches, and arenot inferior t o the natural stones in hardness. C. H. B.Curious Occurrence of Vivianite. By W. L. DUDLEY (Amcr. J.Sci., 40, 120-12l).-Two miles above Eddyrille, Kentucky, ‘‘ blueroots ” were discoyered embedded in a stratum of clay i n such positionas t o indicate that they were in the place of their growth. The bluemineral, which has almost wholly replaced the woody fibre of t h eroots, is of a, deep-blue colour. It is earthy and very friable, andgave, on analysis, the following results :-HZO HSOA120,. Fe203.FeO. CaO. MgO. P@,. at 100’. at 230’. Tot.al.17-74 9.35 24-58 0.59 0.43 27.71 10-59 7.24 100.07These results seem to indicate that the ferrous iron in the. mineralis combined with the phosphoric anhydride to form vivianite, and ifthe double mol. of vivianite, 2(Fe3P208 + 8H20), be subtracted, thereremains an almost dehydrated double mol. of turquoise, A18P402, +IOH,O, in which 1 mol. of ferric oxide has replaced one of alumina.B. H. B.Dihydrothenardite. By V. MARKOVNJKOFF ( J . RUSS. Chem. SOC. ~ 22, 26--27).-Owing to an inexplicable mistake, a new mineral,dihydrothenardite, Na,S04 + 2H20, was described by the authol-(Ahstr., 1868, 794), whereas a renewed investigation shows that it.iMINERALOGICAL CHEMISTRY. 157-~Si02 . ..NiO.. ..MgO . . .Fe203. . .Cr203 ..MnO . . .m,o3 ..Ha0 . a .Totals L.--astrachanite (hydrated sulphnts of sodium aud magnesium) contain-ing a considerable quantity oE thenardite.Connellits from Cornwall. By S. L. PENFIELD (Anzer. J. #&.,40, 82--86).-Connellite is of special interest to the author, owingto its apparently close rclation to the new mineral spnngolite, recentlydescribed by him (Abstr., 1890, 1073). On examining a specimenfrom Camborne, the author found that the habit of the xystals agreeswell with the general description given by Maskelyne in 1863. Theanalysis, in which the author places great confidence, gave thefollowing results :-SOP C1. CuO. H20.Loss at 100". Total. Less 0.4.9 7.4 72.3 16.8 0.4 101.8 1.7B. B.36.2546.309 '000' 14_-3-20--The ratio is not very satisfactory, unless it is assumed that, someOH is isomorphous with the C1, in which case the formula may bewritten CU,,(C'I,OH),SO,~,~~H~O. The mineral is very similar tospangolite in composition, both minerals being very basic sulphato-chlorides. B. H. B.34.78 35-80 20.5743.79 43-54 15 '562 '75 2 -65 0 '816.30 10.73 49 *03- 3 -82- 0 -19 trace12-43 8 .00 10.32-. - --Nickel Ores from New Caledonia. By T. MOORE (C'hem.Nezcs, 62, 180--181).-The ore known as garnierit,e is found in ornear serpentine masses or mountains, either as cerrreriting material inagglomerations of rounded serpentine pebbles or as an interstitialdeposit between thin layers of qunrh, steatite, and various hydratedmagnesium silicates.The associated minerals vary, but comprisequartz, magnesium silicates, and iron oxides ; sometimes one pre-dominates, sometimes another, the others being even absent; it isalso accompanied at times by chrome-iron ore and surrounded by af errugino u s earth.The colour of garnierite varies from pale-green in poor ores towarm dark-green in the richer ones, and passes through almostimperceptible shades to light- and chocolate-browns. It crumblesgradually to powder, on exposure to weather, the brown more readilyGreen ores.35 *5548.385 *021 *411 -090.158 .85100 '45---36 '2444 '948 -750 '211 '03 --8 -98100 *15--Brown ores.I Ferruginous I brown ore.99.89 I 100'02 1 100.91 I 100.1158 ABSTRACTS OF CEEMICAL PAPERS.Bhan the green varieties ; in all forms it dissolves readilyin hot hydro-chloric acid, leaving a non-gelatinous silica. I n the table (p. l57), aregiven numbers, corrected for quartz, obtained in thc analysis of samplesof pure ore ; samples previously analysed by other workers appear tohave been contaminated with gangue :-Samples 1 and 2 were a fine, brilliant grass-green; hardness,2-3 ; sp. gr. 3 ; streak, light-green ; lustre, waxy and slightly t,rans-lucent at their edges. Before the blowpipe, the coloiir becomes darkolive-green, or red in presence of much iron.3, 4, and 5 were various shades of brown, streak yellow tobrownish-yellow, fracture conchoidal with resinous lustre, sp.gr. andhardness the same as green ore, but were rather more brittle. Fromthese numbers, both kinds of ore seem to approach very nearly to ahydrated silicate of the composition 7Ni0,6SiQ2,aH2O, part of thenickel beimg replaced by magnesia, iron oxide, or alumina.The ores represented by sample 6 are light-brown in colour,resembling limonite, are easily marked by the nail, and do not seen1to belong to the same class as the others just described.Minerals occurring near Port Henry, New York. By J. I?.KEMP (Amer. J. Sci., 40, 62--G4).-At the abandoned Pease quarry,a short distance north-west of Port Henry, a face of white, crystallinelimestone has been laid bare, and in this occur streaks of hornblende,.plagioclase, muscovite, and quartz, but containing as well a greatabundance of yellowish-brown titanite crystals ; fine brown tour-malines also occur.West of this quarry is another, where flux is beingobtained for local furnmes. The rock, a crystalline limestone, con-tains small, hexagonal tables of graphite disseminated through it.Occasionally lemon-yellow calcite is found, with fine crystals of clearcalcite of great crjstallographical interest as being good illustrationsof oscillatory forms. Further west is the Treadway quarry in ophi-calcite, containing streaks of pjrrhotite, phlogopite, brown tourma-line, and well-crystallised light-brown treniolite. The abandonedquarry six miles north-west of Poi3t Henry, the source of the well-known tourmaline crystals, is probably a felspathic mass either iiigneiss or in granite, and cut by t.hree narrow dykes of altered‘diabase.Great masses of biotite and fine specimens of rose-quartzare also met with. The so-called Lover’s Pit at Mineville is affordingcrystals and cleavage masses of magnetite of unusual size and ex-cellence. B. H. B.1). A. L.Fayalite in the Obsidian of Lipari. By J. P. IDDINS and S.L. PENFIELD (Amer. J. Xci., 40, 75-78).-The Lipari Islands havelong been celebrated for their acid laws and pumices. The chiefinterest in connection with these rocks attaches itself to the fayalifecrystals in the cavities, which hare not been noticed hitherto. Theyare not abundant, but occur i n several localities, Laving been foundby J.P. Iddings at Forgin Vecchia, and in the obsidian stream onVolcano, and having been noted in specinieris lrom Monte dellaGuardia. The crjstals at Forgia Vecchia are very thin plates, the<*rystallographicnl measurements of which are given in detail by thORQANIC CEIEMISTRP 159authors. The optical properties not only agree with orthorbombicsymmetry, but also with the determinations made on the fayalitefrom Obsidian Cliff, in the Yellowstone Pmk (this vol., p. 26). Thechemical composition, too, is the same in both cases, namely, ortho-silicate of iron. The occurrence of fayalite in the liollow spherulitesand lithophysaa in the obsidian OE the Lipari Islands, whilst not SOabundant as in that of the Yellowstone Park, is identical. It isassociated in the same manner with tridyrnite and alkali felspurs, andits development is due to the same causes in the two regions.Two New Meteoric Irons. By l?. P. VENABLE (Amer. J. &i.,40, 161-163).-1. A mass is reported to have fallen in 1846 atDeep Springs Farm, in Rockingham Co., North Carolina. It is nowin the possession of the State Museum. The weight of the mass was11.5 kilos. It had the shape of a rhomboid, and was coated withoxidation products, giving it a dull-reddish colonr. The surface isirregularly pitted. On being polished and etched, it faintly exhibitedWidmanstatten figures. It belongs to the class of sweating meteor-ites, beads of deliquesced ferric chloride appearing on the surface.The analysis gave-Fe. Y. SiOB. C1. Ni. Co. Total .87*01 0.04 0.53 0.39 11.69 0.79 200.952. A meteoric iron was found in 1889 in Henry Co., Virginia,B. H. B.Itweighed 1.7 kilos., and the detached pieces, mainly crust, 0.28 kilo.The iron contains a considerable amount of ferric chloride, andrapidly crumbles. On polishing one of the sides, the Widrnanst'attenfigures came out plainly, no etching being necessary. The analysisgare the following results :-Fe. C1. SO2. P. Co. Ni. Total.90.54 0.35 0.04 0.13 0.94 7-70 99.70B. H. B

ISSN:0368-1769    

DOI:10.1039/CA8916000153

出版商:RSC    

年代:1891

数据来源: RSC