年代:1922 |
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Volume 121 issue 1
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Journal of the Chemical Society, Transactions,
Volume 121,
Issue 1,
1922,
Page 001-028
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摘要:
J O U R N A L OF THE CHEMICAL SOCIETY. TRANSACTIONS. A. J. ALLMAND M.C. D.Sc. 0. L. BRADY D.Sc. A. W. CROSSLEY C.M.G. C.B.E., D.Sc. F.R.S. C. H. DESCI~ D.Sc. Ph.D. M. 0. FORSTER D.Sc. Ph.D. F.R.S. I. M. HEILBRON D.S.O. I).Sc. Ph.D. J. T. HICWITT M.A. D.Sc. Ph.D., J. C. IRVINE C.B.E. D.Sc. F.R.S. H. KING D.Sc. F.R. S. T. M. LOWEP C.B.E.,D.Sc. F.R.S. J. W. MCBAIN M.A. Ph.D. J. I. 0. MASSON M.B.E. D.Sc. J. C. PHILIP O.B.E. D.Sc. Ph.D., R. H. PICKAI:D D.Sc. Ph.D. F.R.S. N. V. SIDGWICK M.A. Sc.D. F.R.S. J. F. THORPE C.B.E. D.Sc. F.1t.S. Sir JAMES WALKEH D.Sc. LL.D., F.R.S. F. R. S. fibitor : A. J. GREENAWAY. &sisfzrirt @hifar : CLARENCE SMITH D. Sc. 2JrJsiatant ,&&em : A. A. ELDRIDGE BSc. MARGARET LE YLA B.Sc. 1922 VOL CXXI.Part I. pp. 1-1176. LONDON: GURNEY & JACKSON 33 PATERNOSTER ROW E.C. 4 1922 PRINTED IN GREAT BRITAIN BY RICHARD GUY & SONS LIMITED) BUNGAY SUTFOLK C O N T E N T S PAYERS COMMUNICATED TO THE CHEMICAL SOCIETY. I.-Azomethine Derivatives of the 2- and 4-Hydrosy- a-Naphthaldehydes. By GILBERT T. MORGAN and HARRY GORDON REEVES. . . 1 11.-The Overvoltage of the Mercury Cathode. By EDGAR NEWBERY . . 7 111.-The Mechanism of the Oxidation of Drying Oils as Elucidated by a Study of the True Oxygen Absorption. Part 111. The Action of Driers. By SAMUEL COFBEY . 17 1V.-Catechutannins. Part I. Paullinia Tannin. By MAXIMILIAN NIERENSTEIN . . 23 V.-Researches on the Metallic Carbonyls. By ROBERT LUDWIG MOND and ALBERT EDWARD WALLIS . . 29 V1.-The Action of Nitric Oxide on the Metallic Carbonyls.By ROBERT LUDWIG MOND and ALBERT EDWARD WALLIS . . 32 VI1.-Organo-derivatives of Thallium. Part 111. Some Thalliumdialkyl Salts and the Preparation of Thallium-diary1 Haloids. By ARCHIEALD EDWIN GODDFD . 36 VII1.-The Rate of Solution of Iron in Dilute Sulphuric Acid both when Stationary and under Rotation. By JOHN ALBERT NEWTON FRIEND and JOHN HORACE DENNETT . 41 1X.-The Action of Sulphuryl Chloride on Organic Substances. Part I. Simple Monosubstituted Benzenes. By THOMAS HAROLD DURRANS . . 44 X.-The Formation of Substituted Succinic Acids from Esters of @-Unsaturated Acids. By LUCY HIGGINBOTHAM and ARTHUR LAPWORTH . . 49 XI.-Metallic Derivatives of Nitrophenolic Compounds. Part 111. Nitrophenoxides of thc Alkali Metals.By DOROTHY GODDARD and ARCIEIBALD EDWIN GODDARD . 54 XI1.-Physical Chemistry of the Oxides of Lead. Part 111. Hydrated Lead Monoxide. By SAMUEL GLASSTONE . 58 XII1.-Occurrence of a Crystalline Tannin in the Leaves of the Acer ginnula. By ARTHUR GEORGE PERKIN and YOSHISUKE UYEDA . . 66 X1V.-The Direct Acetalisatioii of Aldehydes. By ROBERT DOWNS HAWORTH and ARTHUR LAPWORTH . 76 PAQ iv CONTENTS. XV.-The Interaction of Aromatic Disulphicles and Sulphuric Acid. By SAMUEL SMILES and ERNEST WILSON RIICCLELLAND . ~VI.-Organo-(3@riva'cives of Bismuth. Part V. Tlio Stability of Halogen Cysno- and Thiocyano-derivatives of Tertiary Aromatic Bismuthincs. By FREDERICK CHALLENGER and JOIIN FREDERICK WILKINSON . XVI1.-Organo-derivatives of Bismuth.Part VI. The Preparation and Properties of 'l'er tiary Aromatic Bis-muthines and their Pnteraction with Organic and Inor-ganic Halogen Compounds. By FEEL~RICK CBLIALLENGER and LESLIE RANDAL nrDGwnY . XVII1.-The Aliphatic Sulphonamides. Part 1. By PERCNAL WALTER CLUTTERBUCK and JULIUS BEREND COHEN . X1X.-The Chemistry of Polycyclic Structures in Relation to their Homocyclic Unsaturated Isornerides. Part 11. Iiztra-annular Tautomerism. By ERNEST I-IAROLD FARMER CERISTOPHER KELK INGOLD and JOCELYN FIELD T I E O ~ ~ E . XX .-Researches on Residual Affinity and Co-ordination. Part VII. Cobaltic Lakes of the Alizarin Series. By GILBERT T. MORGAN and J. D. MAIN SMITH . XX1.-A Corn parison of Three Isomeric Carbocyanines. By WALTXR THEODORE KARL BRAUNHOLTZ .XXI1.-The Velocity of Decomposition of High Explosives in a Vacuum. Part 111. Mercuric Pulminate. By ROBERT CEOSBIE FARMER . XXII1.-A Note on the Constitution of Benzene. Ey RONALD FRASER . XX1V.-The Autoracemisation of Potassium Chromioxalate. BY ERIC KEIGHTLEY RIDEAL and WILLIAM 'I'HOMAS . XXV.-Preparation and Properties of the Bcnzochloro-a-mides. By GEORGE ROBERT ELLIOTT . XXV1.-The Oxidising Properties of Sulphur Dioxide. Part 111. Copper Chlorides. By WILLIAM WARDLAW By THOMAS JAMES DRAXELEY [with FREDERICK WILLIAM By (Miss) . and FREDERIC WILLIAM PINKARD . X.XVII,-The Uitimate Composition of British Coals. SRIlTK] . XXVII1.-The Peroxidic Cornpounds of Coppcr. JOAN ALDRIDGE and MALCOLM PERCIVAL APPLEBEY PAGE SG 91 104 120 128 160 1 GO 174 188 196 202 210 22 1 23 CONTENTS.V PAGE XX1X.-The Velocity of Reaction in Mixed Solvents. Part 11. The Velocity of Saponification of the Ethyl Esters of some Monosubstituted Benzoic Acids. By ALBERT ERIC CASHMORE HAMILTON MCCOMBIE arid HAROLD ARCHIBALD SCARBOBOVGH . XXX.-Phenolcamphorein. By SRI KRISHNA . XXX1.-Organo-derivatives of Thallium. Part IV. Action of Thallium Chlorides on the Grignard Reagent and on Organo-derivatives of Tin Lead and Bismuth. By DOROTHY GODDARD and ARCHIBALD EDWIX GODDARD . XXXI1.-Metallic Derivatives of Nitrophenolic Compounds. Part IV. Some Complex Nitrophenoxides of Magnesium, Silver and Lead. By ARCIE~BALD EDWIN GODDARD and JAMES BERTRAM WARD . XXXII1.-A Critical Examination of the Aromatic Alde-hydes occurring in certain Eucalyptus Oils.By ARTHUR RAMON PENFOLD . XXX1V.-The Products of Nitration of Toluene. By WILLIAM HOWIESON GIBSON REBECCA DUCKHAM and RUTH FAIRB-N . XXXV.-Isomeric Citraconyl Hydrazides. By FREDERICK DANIEL CHATTAWAY and DERIC WILLIAM PARKES . XXXV1.-Some Products of the Reduction of 2-Hydroxy-anthraquinone. By ARTHUR GEORGE PERKIN and THOMAS WILLIAM WHATTAN . XXXVI1.-Reactions of the Phosphazines. By WALTER THEODORE KARL BRAUNHOLTZ . XXXVII1.-The Separation of Miscible Liquids by Distil-lation. Part 11. By ARTHUR FELIX DUFTON . XXX1X.-The Hydrogenation of Ethylene in Contact with Nickel. By ERIC KEIGHTLEY RIDEAL . XL.-The Colouring Matter of the Scarlet Pelargonium. By GEOFFREY SAUNDERS CURREY . XL1.-Chloropicrin as a Reagent for the Diagnosis of Mercaptans and Potential Mercaptans.By SIR PRAFULLA CHANDRA RAY and RADHAKISIIEN DAS XLI1.-The Nitration of m-Nitrotoluene. By OSCAR LISLE BRADY . XLII1.-The Use as a Drying Agent of Phosphoric Oxide treated with Ozone. By JOHN JOB MANLEY . XL1V.-The System Ferric Oxide-Sulphuric Acid-Water. By M~LCOLM PERCIVAL APPLEBEY and SIDNEY HERBERT WILKES . XLV.-Optical Activation of Racemic Acid by I-Malic Acid. By ALEX. MCKENZTE and NELLIE WALKER. . . 243 253 256 262 266 270 283 289 300 30G 305) 319 323 328 33 1 337 34 vi CONTENTS. XLVL-A Rapid Iodometric Estimation of Copper and Iron in Mixtures of their Salts. By IAN WILLIAM WARK . XLVI1.-The Combustion of Complex Gaseous Mixtures.By WILLIAM PAYMAN and RICHARD VERNON WHEELER . XLVII1.-The Quaternary System Ammonium Chloride-Sodium Sulphate-Ammonium Sulphate-Sodium Chloride-Water. By ALBERT CHERBURY DAVID RNETT . XLIX.-Studies on Thallium Compounds. Part I. Ana-lytical. By ARTHUR JOHN BERRY . Artificial Disintegration of the Elements. A Lecture Delivered before the Chemical Society on February 9th 1922. By SIR ERNEST RUTHERFORD F.R.S. . L.-A Theoretical Derivation of the Principle of Induced Alternate Polarities. By ARTHUR LAPWORTH . L1.-An Explanation of the Property of Induced Polarity of Atoms and an Interpretation of the Theory of Partial Valencies on an Electronic Basis. By WILLIAM OGILVY KERMACK and ROBERT ROBINSON . L1I.-The Amphoteric Character of Stannic Hydroxide and its bearing on the Isomerism of the Stannic Acids.By GEORGE ERNEST COLLINS and JOHN KERFOOT WOOD . LII1.-Complex Metallic Ammines. Part VII. Conductivities of Diethylenediaminecobaltic Bromides. By JAMES COOPER DUFF . L1V.-The Cyanine Dyes. Part IV. Cyanine Dyes of the Benzothiazole Series. By W~LLIAM HOBSON MILLS . LV.-The Influence of Protective Colloids on the Corrosion of Metals and on the Velocity of Chemical and Physical Change. By JOHX ALBERT NEWTON FRIEND and REECE HENRY VALLANCE . LV1.-Some Reactions of Benzanthrone. By ARTHUR GEORGE PERKIN and GEORGE DOUGLAS SPENCER . LVI1.-Organo-derivatives of Thallium. Part V. The Pre-paration of Thallium Diary1 Salts. By ARCHIBALD EDWIN GODDARD and DOROTHY GODDARD . LVII1.-The Influence of Nitro-groups on the Reactivity of Substituents in the Benzene Nucleus.Part V. Hetero-nucleal Dinitro-derivatives. By HAROLD BURTON and JAMES KENNER L1X.-The Composition of Paraffin Wax. Part I. By FRANCIS FRANCIS [with JOHN CLIFFORD POPE and LX-The Formation and Stability of spiro-Compounds. The Application of the Dieckmann Reaction By GEORGE ARMAND REGINALD HENRY COYSH] . Part VII. t o Esters of the Glutaric Series. ROBERT KON . PAQE 358 363 379 394 400 416 427 441 450 455 466 474 482 489 496 51 CONTENTS. vii PAGE LX1.-The Dinitrotoluidines. By OSCAR LISLE BRADY, JAMES NELSON EDMCTNDAY and WILLIAM JOSEPH WOODGATE ROLT . LXI1.-The Rotatory Dispersive Power of Organic Com-pounds. Part X. The Preparation and Properties of Pure Ethyl Tartrate.By THOMAS MARTIN LOWRY and JOHN OUTRAM CUTTER . LXII1.-Colouring Matters from 1 2 4 5-Tetrahydroxy-benzene and Related Substances. By DHIRENDRA NATH MUKERJI . LX1V.-The Reaction between Iodine and Sulphurous Acid. By ROBERT MILROY MACACLAY . LXV.-The Oxidation of a-Dinaphthaxanthens. By HEMEN-DRA KUMAR SEN-GUPTA and STANLEY HORWOOD TUCKER LXV1.-Change of Properties of Substances on Drying. By HERBERT BRERETON BAKER . LXVI1.-Piperitone. Part 11. Benzylidene-dE-piperitone. By JOHN READ and HENRY GEORGE SMITH LXVII1.-Piperitone. Part 111. The Oximes of dl-Piperi-tone. By JOHN READ HENRY GEORGE SMITH and MARIE BENTIVOGLIO . LX1X.-Production and Reactions of pp’-Dichlorodiethyl Sulphide. By FREDERICK GEORGE MANN and WILLIAM JACKSON POPE .LXX.-The Constitution of Catechin. Part IV. By MAXIMILIAN NIERENSTEIN . LXX1.-The Molecular Configurations of Polynuclear Aromatic Compounds. Part I. The Resolution of 7-6 6’-Dinitro- and 4 6 4’ 6’-Tetranitro-diphenic Acids into Optically Active Components. By GEORGE HALLATT CHRISTIE and JAMES KENNER . LXXII.-Studies of the Constitution of Soap Solutions. Solutions of Sodium Palmitate and the Effect of Excess of Palmitic Acid or Sodium Hydroxide. By JAMES WILLIAM MCBAIN MILLICENT TAYLOR and MaRy EVELYN LAING Part 11. a’-Bromocamphor. By THOMAS MARTIN LOWRY VICTOR STEELE and HENRY BURGESS. . LXX1V.-Introduction of the Chloroethyl Group into Phenols, Alcohols and Amino-compounds. By GEORGE ROGER CLEMO and WIUM HENRY PERKIN jun .. LXXII1.-New Halogen Derivatives of Camphor. 526 532 545 552 557 568 574 582 594 604 614 621 633 64 viii CONTENTS. PAGE LXXV.-Ring-chain Tautomerism. Part I. The Occur-rence and Effect of Keto-enol Tautomerism between a, Ring Compound and its Open-chain Isomeride. By GEORGE ARMAND ROBERT KON ARNOLD STEVENSON and JOCELYN FIELD THORPE . . 650 LXXV1.-Studies in Catalysis. Part XV. Absorption Spectra of Triethylsulphonium Bromide in Various Solvents in the Short Infra-red Region. By HENRY AUSTIN TAYLOR and WILLIAM CUDMORE MCCULLAGH LEWIS . . 665 LXXVI1.-The Influence of Nitro-groups on the Reactivity of Substituents in the Benzene Nucleus. Part VI. The Elimination of Halogen during the Reduction of Halogen-ated Nitro-compounds.By HAROLD BURTON and JAMES KENNER . . 675 LXXVII1.-The Action of Light on Silver Bromide. By ERNST JOHANNES HARTUNG . . 682 LXX1X.-Purification of Phosphoric Oxide. By GEORGE INGLE FINCH and RAYMOND HAROLD KELSALL PETO . 692 LXXX.-The 25"-Isotherms of the Systems Magnesium NitrateSodium Nitrafe-Water and Magnesium Sulphate-Magnesium Nitrate-Water. By DOUGLAS NORMAN JACKMAN and AGNES BROWNE . . 694 LXXX1.-The Decomposition of Ammonium Nitrate by Heat. By HORACE LEONARD SATJNDERS . . 698 LXXXI1.-Note on the Effect of Electrolytes on the Con-stitution of Soap Solutions as Deduced from Electro-motive Force. By CYRIL SEBASTIAN SALMON . . 711 LXXXII1.-Preparation of p-Nitrophenylhydrazine and other Aromatic Hydrazines. By WILLIAM DAVIES . . 715 ANNUAL GENERAL MEETING .. 723 The Rdle of the Physicist in the Development of Chemical Theory. Presidential Address. Delivered a t the Annual General Meeting March 30th 1922. By SIR JAMES WALKER D.Sc. LL.D. F.R.S. . 735 OBITUARY NOTICES . . 746 Ore Deposits and their Genesis in Relation to Geographical Distribution. A Lecture Delivered before the Chemical Society on December 8th 1921. By JOHN WALTER GREGORY F.R.S. . . 750 LXXXIV. - Benzbisthiazoles. By STEPHEN RATHBONE HOLDEN EDGE . . 772 LXXXV.-Heterogeneous Equilibria The Ternary System Sodium Sulphate-Sodium Cnrbonate-Water. By ALFRED ERNEST DAWKINS . . 77 CONTENTS. ix PAQE LXXXVL-Phototropy of Inorganic Salts. Cuprous Chloride and Bromide. By GOPAL SINGH LXXXVI1.-The Cumulative Effect of the Chlorine Atom and the Methyl and Sulphonyl Chloride Groups on Substitution in the Benzene Nucleus.Part 111. By WILLIAMDAVIES . LXXXVII1.-Pyridinium Salts derived from some Chloro-acetylamino-compounds. By EDWARD DE BARRY BARNETT and JAMES WILFRED COOK . LXXX1X.-The Action of Potassium Iodide and Iodate on ~ome Hydroxy-acids. By SRI KRISHNA and FRANK GEORGE POPE . XC.-Mixed Crystal Formation in Ternary Systems con-taining Water Ammonium Chloride and Ferrous, Cobaltous or Nickel Chloride. By FREDERICK WILLIAM JEFFREY CLENDINNEN . XC1.-An Instance of th? Apparent Effect of the Entering Group on the Position of Substitution in the Benzene Nucleus. By WILLIAM DAVIES . XCI1.-Constitution of Picrorocellin a Diketopiperazine Derivative from Roccella fuciformis.By MARTIN ONSLOW FORSTER and WILLIAM BRISTOW SAVILLE XCII1.-Polynuclear Heterocyclic Aromatic Types. Part I. Some Indenoquinoline Derivatives. By JAMES WILSON -T and ROBERT ROBINSON . XC1V.-The Hydroxybenzoylphloroglucinols. By HIDEJIRO NISHIKAWA and ROBERT ROBINSON . XCV.-Note on 2 3- and 2 5-Dinitro-p-toluidines. By JAMES SCOTT and ROBERT ROBINSON. XCVI.-The Speed of Sulphonation of Phenols. Part I. The Effect of Temperature and the Methyl Group. By ARTHUR FRED CAMPBELL . XCVI1.-The Determination of Surface Tension from the Maximum Pressure in Bubbles. By SAMUEL SUCDEN . XCVII1.-The Action of Amines on Semicarbazones. Part I. Preparation of an Optically Active Semicarbazide. By FORSYTH JAMES WILSON ISAAC VANCE HOPPER and ARCHIBALD BARCLAY CRAWFORD XC1X.-Reactions of Thiosemicarbazones.Part I. Action of Halogen Compounds. By FORSYTH JAMES WILSON and ROBERT BURNS . C.-The Essential Oil from Blumea Malcomii. By JOHN LIONEL SIMONSEN and MADYAR GOPAL RAU . . 782 785 792 798 801 806 816 827 839 844 847 858 866 870 87 X CONTENTS. CI .-Preliminary Note on the Interchange of Alcohol Radicles in Esters. By AKIRA SHIMOMURA and JULIUS BEREND COHEN . CI1.-The Surface Tension of Mixtures of Alcohol and Water at 25'. By Loms LEIGHTON BIRCUMSHAW . CII1.-The Labile Nature of the Halogen Atom in Organic Compounds. Part I. Titanium Reductions of Substi-tuted Nitroparaffins. By THOMAS HENDERSON and ALEXANDER KILLEN MACBETH . C1V.-The Labile Nature of the Halogen Atom in Organic Compounds.Part 11. Action of Hydrazine on Nitrogen-Halogen Compounds and on Bromomalonic Esters. By EDMUND LANGLEY HIRST and ALEXANDER KILLEN WCBETH . CV.-Derivatives of 2-Hydroxybenzanthrone. Part I. By GEOFFREY GORDON BRADSHAW and ARTHUR GEORGE PERKIN . CV1.-Researches on Residual Affinity and Co-ordination. Part VIII. Interaction of Tellurium Tetrachloride and P-Diketones. By GILBERT T. MORGAN and HARRY DUGALD KEITH DREW [with E. A. COOPER] . CVI1.-Properties of Mixtures of Ethyl Ether Sulphuric Acid and Water. By JAMES ROBERT POUND . CVIII .-2 -p -Dimethylaminost yr ylp yridine Met hiodide a New Photographic Sensitiser. By WILLIAM HOBSON MILLS and WILLIAM JACKSON POPE . C1X.-Bromo-derivatives of Glyoxaline. By ISIDORE ELKANAH BALABAN and FRANK LEE PYMAN CX.-The Properties of Ammonium Nitrate.Part 11. Ammonium Nitrate and Water. By IDA L. MILLICAN, ALFRED FRANCIS JOSEPH and THOMAS MARTIN LOWRY CX1.-The Properties of Ammonium Nitrate. Part 111. Ammonium Nitrate and Sodium Nitrate. By REGINALD GEORGE EARLY and THOMAS MARTIN LOWRY . CXI1.-Castelin a New Glucoside from Castela Nichokoni. By Loms PIERRE BOSMAN . CXII1.-Polymorphism of Arscnic. By PORPHYRY NICO-LAEVITCH LASCHTSCHENKO CX1V.-Organo-derivatives of Tin and Lead. Part I. Application of Lead and Tin Tetraphenyls in the Pre-paration of Orgsno-metallic Compounds. By ARCHI-BALD EDWIN GODDARD JULIUS NICHOLSON ASHLEY, and RICHARD BROMLEY EVANS CXV.-The System Potassium Sulphate-Aluminium Sul-phate-Water a t 25". By HUBERT THOMAS STANLEY BRIXTON .. PACE 883 887 892 904 91 1 922 941 946 947 959 963 969 972 978 98 CONTENTS. xi PAGE CXV1.-The Isotope Ratio of New Zealand Boron. By ALEXANDER DONALD MONRO . CXVI1.-The Conversion of Ally1 Alcohol to Glyceryl Chloro-and Bromo-hydrins. By JOHN READ and ERIC HURST CXVII1.-Studies in the Dihydronaphthalene Series. Part 111. The Oxidation and Bromination of 5 8-Dihydro-a-naphthylamine. By FREDERICK MAURICE ROWE and JOHN STANLEY HERBERT DAVIES . CX1X.-The Reactivity of Ammonia. By EDWARD CHARLES CYRIL BALY and HERBERT MAXWELL DUNCAN . CXX.-Researches on Sulphuryl Chloride. Part 11. A New Chlorinating Agent Preparation of Polychloro-derivatives of Benzene. By OSWALD SILBERRAD . CXX1.-The Aldehydosalicylic Acids and their Derivatives.By EDWARD JOHNSON WAYNE and JULIUS BEREND COHEN . CXXI1.-isoQuinoline and the isoQuinoline-Reds. By JOHN EDMUND GUY HARRIS and WILLIAM JACKSON POPE . CXXII1.-A Synthesis of isoBrazilein and certain Related -4nhydropyranol Salts Part 11. Synthesis of iso-Hzematein. By HERBERT GRACE CRABTREE and ROBERT ROBINSON . CXX1V.-A Property of Ethyl Tartrate. By THOMAS STEWART PATTERSON . CXXV.-Capsularin a Glucoside from Jute Leaf. By HARIDASAHA and KUMUD NATH CHOUDHURY . CXXV1.-The Rate of Evolution of Carbon Dioxide from Solution in Presence of Colloids. By ALEXANDER FINDLAY and OWEN RHYS HOWELL . CXXVI1.-The Sulphilimines a New Class of Organic Compounds containing Quadrivalent Sulphur. By FREDERICK GEORGE MANN and WILLIAM JACKSON CXXVIIL-Mercury Compounds of Hydroxybenzaldehydes.By THOMAS ANDERSON HENRY and THOMAS MARVEL SHARP . CXX1X.-The Constitution of Polysaccharides. Part IV. Inulin. By JAMES COLQUHOUN IRVINE ETTIE STEWART STEELE and MARY ISOBEL SHANNON CXXX.-Photocatalysis. Part 11. The Photosynthesis of Nitrogen Compounds from Nitrates and Carbon Dioxide. By EDWARD CHARLES CYRIL BALY ISIDOR MORRIS HEILBRON and DONALD PRYCE HUDSON CXXX1.-The Potassium Salt of Hexahydrodioxydiboron. By RAMES CHANDRA RAY . POPE . . 986 989 1000 1008 1015 1022 1029 1033 1042 1044 1046 1052 1055 I060 1078 108 X i i CONTENTS. CXXXIL-The Reactivity of Doubly-conjugated Unsatur-ated Ketones. Part 111. Unsymmetrical Hydroxy-and Methoxy-derivatives.By JOI-IANNES SYBRANDT BUCK and ISIDOR MORRIS HEILBRON CXXXII1.-Studies of the Constitution of Soap Solutions. Sodium Behenate and Sodium Nonoate. By ORIEL JOYCE FLECKER and MILLICENT TAYLOR . CXXX1V.-The Labile Nature of the Halogen Atom in Organic Compounds. Part 111. The Absorption Spectra of Bromomalonic Derivatives and Nitroparaffins, and their Bearing on the Question of an Oxygen-Halogen Linking. By HUGH GRAHAM and ALEXANDER KILLEN MACBETH . CXXXV.-The Labile Nature of the Halogen Atom in Organic Compounds. Part IV. The Tautomeric Hydrogen Hypothesis and the Removal of the Halogen Atom from Aromatic Nitro-compounds. By ALEX-ANDER KILLEN WCBETH . CXXXV1.-The Behaviour of the Stannic Acids towards Hydrochloric Acid. By GEORGE ERNEST COLLINS and JOHN KERFOOT WOOD .Part I. Intra-nuclear Tautomerism. By CHRISTOPHER KELK INGOLD . Part 11. Synthetic Formation of the Bridged Modification of the Nucleus. By CHRISTOPHER KELK INGOLD . CXXXIX.-Some Properties of Hydrogen Desorbed from Platinum and Palladium. By PAUL ANDERSON . CXL.-The Bromination of Acids in the %-Position. By CHARLES FREDERICK WARD . CXLL-The Chlorinated Dialkyl Sulphides. By WILLIAM JACKSON POPE and JAMES LEONARD BRIERLEY SMITII CXLI1.-The Influence of Solvents on the Velocity of Formation of Quaternary Ammonium Salts. By JAMES ALEXANDER HAWKINS . CXLII1.-The Jnfluence of Substituents on the Formation and Stability of Heterocyclic Compounds. Part I. Hydantoins. By CHRISTOPHER KELK INCOLD SHINI-cm SAKO and JOCELYN FIELD THORPE CXL1V.-Benzopyrylium Salts of Distyryl Ketones.Part I. By JOHANNES SYBRANDT BUCK and ISIDOR MORRIS HEILBRON . CXLV.-2 3 G-Trimethyl Glucose. By JAMES COLQU-HOUN IRVINE and EDMUND LANCLEY HIRST CXXXVIL-The Structure of the Benzene Nhcleus. CXXXVII1.-The Structure of the Benzene Nucleus. . . PAQE 1095 1101 1109 1116 1122 1133 114.3 1153 l l G l 1166 1170 1177 1198 121 CONTENTS. Xiii PAGE CXLV1.-The Quaternary System Potassium Sulphatc-Magnesium Sulphate-Ammonium Sulphate-Water. By ARNOLD WESTON . CXLV1I.-The Dissolution of (idatin. By FRED PAIR-BROTHER and ENOCH SWAN . CXLVII1.-Limits for the Propagation of E’lame in Vapour-Air Mixtures. Part I. Mixtures of Air and One Vapour at the Ordinary Temperature and Pressure.By ALBERT GREVILLE WH~TE . CXL1X.-Use of Iron Pyrites in a Friedel-Crafts’ Reaction. By JOHN ARMSTRONG SMYTHE . CL.-Triethylene Tri- and Tetra-sulphides. Part 11. By SIR PRAFULLA CHANDRA RAY . CL1.-Dyes Derived from Camphoric Anhydride. By ANUKUL CHANDRA SIRCAR and SIKHIBHUSAN DUTT . CLI1.-Thc Hydroferrocyanides and Hydroferricyanides of the Organic Bases. Part I. By WILLIAM MURDOCH CUMMIYG CLIIL-Note on the Effect of a Magnetic Field on Catalysis by Ions in the Presence of a Paramagnetic Salt. By WILLIAM EDWARD GARNER and DOUGLAS NORMAN JACBBIAN CL1V.-The Action of Sulphur on Cuprous Chloride. By FREDERIC WILLIAM PINKARD and WILLIAM WARDLAW CLV.-The Intermolecular Condensation of Methyl Ethyl Ketone in the Presence of Calcium Carbide.By OSCAR BECKER and JOCELYN FIELD THORPE . CLV1.-The Conditions Underlying the Formation of Un-saturated and Cyclic Compounds from Halogenated Open-chain Derivatives. Part IV. Products Formed from Halogen Derivatives of Muconic Acid. The Con-stitution of Muconic Acid. By JUAN PEDIGE CHARLES CHANDRASENA and CHRISTOPHER KELK INGOLD CLVI1.-The Effect of an Electrolyte on Solutions of Pure Soap. Phase-rule Equilibria in the System Sodium Laurate-Sodium Chloride-Water. By JAMES WILLIAM MCBAM and ARTHUR JOHN BURNETT CLVII1.-The Constitution and Rotatory Powers of Mannitol and Fructose Complexes Formed in Solutions Containing Boric Acid and Sodium Hydroxide. By GEORGE VAN BARNEVELD GILMOUR . CL1X.-The Variation of Refractive Index and Density of Benzene with Temperature.By WILLIAM BAYLEY PARKER and GARTHA THOMPSON . . 1233 1237 1244 1270 1279 1283 1287 1298 1300 1303 1306 1320 1333 134 xiv CONTENTS. C'LX.-The Catalytic Oxidation of Saturated Paraffin Hydro-carbons and Fatty Acids. By ARTHUR HENRY SALWAY and PERCY NOEL WILLIAMS . CLX1.-Catalytic Racemisation of Optically Active Acid b i d e s . By ALEX. MCKEXZIE and ISOBEL AGNES SMITH . CLXI1.-A Study of the Rate of Saponification of Oils and Fats by Aqueous Alkali under Various Conditions. By MABEL HARRIET NORRIS and JAMES WILLIAM MCBAIN CLXIIL-Studies in the Anthracene Series. Part 11. By EDWARD DE BARRY BARNETT and JAMES WILFRED CLX1V.-Reciprocal Induced Polarity Effects in Cresols and their Derivatives. Properties of the Isomeric Methoxybenzyl Bromides.By ARTHUR LAPWORTH and JOHN BALD= SHOESMITH . CLXV.-Decomposition of Benzyl Disulphoxide. By JOHN ARMSTRONG SMYTHE CLXV1.-The Dissociation Pressures of Hydrated Double Sulphates. Part I. Hydrated Cupric Alkali Sulphates. By ROBERT MARTIN CAVEN and J o m FERGUSON . CLXVI1.-Experiments on the Synthesis of the Polyacetic Acids of Methane. Part VI. Methanetriacetic Acid and its Unstable Esters. By CHRISTOPHER KELK INGIOLD and EDWARD ARTHUR PERREN CLXVII1.-Studies in Optically Active Dyes. Part I. Camphoreins. By BAWA KARTAR SINGH RAGHUNATH RAI and RATTAN LAL . CLX1X.-Ring-chain Tautomerism. Part 11. The Effect of the gem-Diethyl Group on the Carbon Tetrahedral Angle. By SHANKAR SHRIDHAR DESHAPANDE and JOCELYN FIELD THORPE .CLXX.-The Interaction of Sodium Chloride and Silica. By FRANCIS HERBERT CLEWS and HUGH VERNON THOMPSON . CLXX1.-Formation and Dissociation of some Polyhalogen Compounds of Hydrogen in Aqueous Solution. By PRIYADARANJAN RAY and PULIN VIHARA SARKAR . CLXXI1.-Physical Chemistry of the Oxides of Lead. Part IV. Red Lead and Lead Sesquioside. By SAMUEL GLASSTONE . CLXXII1.-Physical Chemistry of the Oxides of Lead. Part V. The Electromotive Behaviour of Lead Di-oxide By SAMUEL GLASSTONE COOK . . PAGP 1343 1348 1362 1376 1391 1400 1406 1414 1421 1430 1442 1449 1456 146 CONTENTS. xv PAGE CLXX1V.-The Oxidising and Reducing Properties of Sulphur Dioxide. Part I. Mercury Chlorides. By LACHLAN MACQUARIE STEWART and WILLIAM WARDLAW CLXXV.-The Cyanine Dyes.Part V. The Virtual Tautomerism of the Thiocyanines. By WILLIAM HOBSON MILLS and WALTER THEODORE KARL BRAUN-CLXXV1.-The Formation and Stability of spiro-Com-pounds. Part VIII. The Dieckmann-Komppa Re-action. By FRANK DICKENS GEORGE ARMAND ROBERT KON and JOCELYN FIELD THORPE CLXXVII.-2 S-Tetramethyldiaminoacridine. By KIS-HORI LAL MOUDGILL . CLXXVII1.-Brominated isocyanines. By KISHORI LAL MOUDGILL . CLXXIX .-The Viscosity of Cellulose in Cuprammonium Hydroxide Solution. Part I. The Determination of the Viscosity. By REGINALD ARTHUR JOYNER . CLXXX.-The Sorption of Carbonyl Chloride by Beech-wood Charcoal. By HUGH MILLS BUNBURY . CLXXX1.-The Composition of Paraffi Wax. Part 11. By FRANCIS ZRANCIS CYRIL MERCER WATKINS and REGINALD WILFRED WALLINGTON .CLXXXI1.-The R61e of Protective Colloids in Catalysis. Part 11. By THOMAS IREDALE . CLXXXII1.-The Chemistry of Polycyclic Structures in Relation to their Homocyclic Unsaturated Isomerides. Part 111. Intra-annular Tautomerism of a-Campho-lytic Acid. By JUAN PEDIGE CHARLES CHANDRASENA, CHRISTOPHER KELK INGOLD and JOCELYN FIELD THORPE CLXXX1V.-Effect of Attached Groups on the Ease of Formation of the cycZoPentane Ring. By JUAN PEDIGE CHARLES CHANDRASENA and CHRISTOPHER KELK IN-CLXXXV.-The Calculation of the Colour of the Azo-dyes and Related Coloured Substances. By JAMES Mom . CLXXXV1.-Conditions of Formation of Rings attached to the 0- m- and p-Positions of the Benzene Nucleus. Part I. The action of Sodium on o-Phenylenediacetic Ester.By WILLIAM HENRY PERKIN jun. and ALAN FRANCIS TITLEY . CLXXXVI1.-Cevadine. Part 1. By ALEXANDER KILLEN MACBETH and ROBERT ROBINSON . HOLTZ . . GOLD . 1481 1489 1496 1506 1509 1511 1525 1529 1536 1542 1552 1555 1562 157 XVi CONTENTS. CLXXXVII1.-A Synthesis of Pyrylium Salts of Antho-cyanidin Type. By DAVID DOIG PRATT and ROBERT ROBINSON . CLXXX1X.-The Constitution of Polysaccharides. Part V. The Yield of Glucose froin Cotton Cellulose. By JAMES COLQUHOUN IRVINE and EDMUND LANGLEY HIRST . CXC.-Preparation of 0- rn- and pNitrophenoxyacetic Acids and Various Nitrotolyloxyacetic Acids and their Derivatives. By TIioniAs HOSKER MINTON and HENRY STEPHEN . CXC1.-Studies in the Coumaranone Series. Part 11.The Preparation of 4- and 6-Chlorocoumaran-2-ones and their Conversion into 2- and 4-Chloroflavonols respectively and some Derivatives of 0- and p-Chloro-phenoxyacetic Acids. By THOMAS HOSKER MINTON and HENRY STEPHEN . CXCl1.-Tautomerism of Dyads. Part I. Detection of Tautomeric Equilibria in Hydrocyanic Acid. By EDITH HILDA USHERWOOD CXCII1.-Studies in Catalysis. Part XVI. The Inversion of Sucrose by Hydrogen Ion. By THOMAS MORAN and WILLIAM CUDMORE MCCULLAGH LEWIS . CXC1V.-Studies on Hypophosphorous Acid. Part IV. Its reaction with Cupric Chloride. By ALEC DUNCAN MITCHELL . CXCV.-Experiments on the Synthesis of the Polyacetic Acids of Methane. Part VII. isoButylene-ayy’-tricarboxylic Acid and Methanetetra-acetic Acid. By CHRISTOPHER KELK INGOLD and LEWIS CHARLES NICKOLLS CXCV1.-The Alkylhydrazones.By OSCAR LISLE BRADY and GERALD PATRICK MCHUGH CXCVI1.-The Nitro- and Amino-Derivatives of 0- and p-Methoxybenzoic Acids and of a- and p-Methoxy-naphthoic Acids. By VICTOR FROELICHER and JULIUS BEREND COHEN . CXCVII1.-Studies of the Glucosides. Part I. The Con-stitution of Indican. By ALEXANDER KILLEN MACBETIX and JOHN PRYDE . CXCIX.-The Catalytic Decomposifion of Formic Acid on Surfaces of Platinum and Silver. By HAROLD CALVERT TINGEY and CYRIL NORMAN HINSHELWOOD CC.-Imino-aryl Ethers. Part I. N-Phenylbenzimino-m-hydroxyphenyl Ether and the Synthesis of 2 4-Dihy-droxybenzophenone. By ARTHUR WILLIAM CHAPMAN . PAGE 1577 1585 1591 1598 1604 1613 1624 1638 1648 1652 1660 1668 167 CONTENTS.xvii PA-CC1.-Crystalline Glucose-ammonia and isoGlucosamine. By ARTHUR ROBERT LINQ and DINSmw RATTONJI NANJI . CCI1.-Limits for the Propagation of Flame at Various Temperatures in Mixtures of Ammonia with Air and Oxygen. By ALBERT GREVILLE WHITE . CCII1.-The Action of Sodium Methoxide and its Homo-logues on Benzophenone Chloride and Benzylidene Chloride. Part 111. By JOHN EDWIN MACKENZIE . CCIV.-Syntheses of Alkylidenecyanoacetic Acids and of Substituted Succinic Acids. Part I. Acids containing Aromatic Residues. By ARTHUR LAPWORTH and JOHN ALEXANDER MCRAE . . . CCV.-N-Oximino-ethers. Part 11. N-Aryl Ethers of 2 4- and 2 6-Dinitrobenzaldoximes. By FRED BARROW EVAN DALTON GRIFFITHS and EDWARD BLOOM . . CCV1.-The Formation of Derivatives of Tetrahydronaph-thalene from y-Phenyl Fatty Acids.Part II. By ARNOLD STEVENSON end JOCELYN FIELD THORPE . CCVI1.-Researches on Residual Affinity and Co-ordination. Part IX. Cobaltammine Salts of the Nitro-Dyes. By GILBERT T. MORGAN and HERBERT JOSEPH SEYMOUR CCV1II.-The Explosion of Acetylene and Nitrogen. Part 11. By W-M EDWARD GARNER and =CHI-CC1X.-The Adsorption of Uranium-X and its Isotope, Thorium by Basic Ferric Acetate. By ANDREW CHARLES BROWN . CCX.-The Isolation of Muscarine the Potent Principle of Amanita muscaria. By HAROLD Kma . CCX1.-The p-Chlorovinylarsines. By FREDERICK GEORGE Mam and WILLIAM JACKSON POPE . CCXI1.-Catalysis of Hydrogen Peroxide by Finely Divided Platinum. The Influence of Inhibitants. By EDWARD BRADFORD MAXTED .. CCXII1.-Ring-chain Tautomerism. Part 111. The Occur-rence of Tautomerism of the Three-carbon (Glutaconic) Type between a Homocyclic Compound and its Un-saturated Open-chain Isomeride. By CHRISTOPHER KELK INQOLD EDWARD ARTHUR PERREN and JOCELYN FIELD THORPE 0 f(INQ . MATSU MATSITNO -b 1682 1688 1695 1699 1713 1717 1723 1729 1736 1743 1754 1760 176 xviii CONTENTS. CCX1V.-The Preparation of Methylguanidine and of p p-Dimethylguanidine by the Interaction of Dicyanodi-amide and Methylammonium and Dimethylammonium Chlorides Respectively. By EMIL ALPHONSE WERNER and JAMES BELL . CCXV.-Autoreduction of Sulphurous Acid. By GEORGE MACDONALD BENNETT . CCXV1.-A Method for the Preparation of app-Trialkylated Glutaric Acids.By GEORGE ARMAND ROBERT KON and JOCELYN FIELD THORPE . CCXVI1.-The Condensation of Phenols with the Hydro-chlorides of Cyanamides and Carbodi-imides and its Relation to the Hoesch Reaction. By WALLACE FRANK SHORT and JOHN CHARLES SMITH CCXVII1.-The Mathematics of the Dicyclic Colour Theory, and a New Theory of the Structure of the Nitrogen Atom. By JAMES MOIR . CCX1X.-The Equilibria in Aqueous Solutions of the Alkali Metal Bisulphites. By EDWARD CHARLES CYRIL BALY and ROBERT ARTHUR BAILEY . CCXX .-The Formation and Stability of sp iro-Compounds. Part IX. The Influence on Stability of Groups of High Molecular Weight. By STANLEY FRANCIS BIRCH and JOCELYN FIELD THORPE . CCXX1.-The Solubilities of the Alkali Formates and Acetates in Water.By NEVIL VINCENT SIDGWICK and JOSEPH ALFRED HECTOR ROBERTS GENTLE . CCXXI1.-The Solubility of the Alkali Salts of Benzoic and the Hydroxybenzoic Acids in Water. By NEVIL VINCENT SIDGWICK and ELINOR KATHARINE EWBANK . CCXXII1.-The Solubility and Volatility of 3 5-Dinitro-phenol. By NEVIL VINCENT SIDGWICK and THOMAS WESTON JOHNS TAYLOR . CCXX1V.-isoPropylstannonic Acid and its Derivatives. By JOHN GERALD FREDERICK DRUCE CCXXV.-Piperitone. Part IV. The Interaction of dl-Piperitone and Semicarbazide and the Isolation of Pure dl-Piperitone. By JOHN READ and HENRY GEORGE SMITH CCXXV1.-Harmine and Harmaline. Part VI. The Syn-thesis of N-Methyltetrahydronorharmine and the Con-stitution of Harmaline and of the Alkylated Harmines. By WILLIAM OGILVY KERMACK WILLIAM HENRY PERKIN and ROBERT ROEINSON .. . PAOB 1790 1794 1795 1803 1808 1813 1821 1537 1 S44 1853 1859 1863 187 CONTENTS. xix PAQE C CXXVI1.-The Formation of Bromine Derivatives of Carbon Compounds without the Production of Hydrogen Bromide. By BIRAJ MOHAN GUPTA and JOCELYN FIELD THORPE CCXXVII1.-The Reactivity of Alkyl Iodides with Sodium Benzyloxide and the Effect of Temperature on such Reactions. By PERCY CHARLES HAYWOOD . CCXX1X.-The Constitution of the Disaccharides. Part VI. The Biose of Amygdalin. By WALTER NORMAN HAWORTH and GRACE CUMMING LEITCH CCXXX.-Amylases of the Cereal Grains-The " Insoluble " Amylrtse of Barley. By JULIAN LEVETT BAKER and HENRY FRANCIS EVERARD HULTON . CCXXX1.-The System Chromium Trioxide-Sulphur Tri-oxidewater.By LIONEL FELIX GILBERT HAROLD BUCKLEY and IRVINE MASSON CCXXXI1.-Attempts to prepare Red Sulphide Dyes. Part I. By EDWIX ROY WATSON and SIRRIBHUSHAN DTJTT . CCXXXIIL-Dyes Derived from Phenanthraquinone. Part I. Phenanthranaphthazines. By ANUKUL CHANDRA SIRCAR and SIKEIBHUSAN DUTT . CCXXX1V.-Dyes Derived from Phenanthraquinone. Part 11. Naphthaflavindulines. By SIKHIBUSHAN DUTT . CCXXXV.-Researches on Residual Affinity and Co-ordin-ation. Part X. Salicylatotetramminocobaltic Salts and the Constitution of Oxonium Compounds. By GILBERT T. MORGAN and J. D. MAIN SMITH . CCXXXV1.-Thermal Expansion of Gelatin Gels. By ALAN TAFFEL . CCXXXVI1.-Diacetylacetone. By JOHN NORMAN COLLIE and AMY ADA BEATRICE REILLY CCXXXVII1.-Nitro-derivatives of m-Nitrodimethylaniline.By A 4 ~ ~ ~ ~ FORSTER and WILLIAM COTJLSON CCXXX1X.-Preparation and Reactions of Stannous Oxide and Stannous Hydroxides. By FRANK WARD BURY and JAMES RIDDICK PARTINGTON . CCXL.-The Cyanine Dyes. Part VI. Dyes containing a Quinoline and a Benzothiazole Nucleus. The Thioiso-cyanines. By WALTER THEODORE KARL BRAUNHOLTZ and WILLIAM HOBSON M~LLS . By WILLIAM HOBSON MILLS and FRANCES M~RY HAMER . . . . CCXLL-The Quaternary Salts of Quinaldinic Acid. 1896 1904 1921 1929 1934 1930 1944 1951 1956 1971 1984 1988 1998 2004 200 xx CONTENTS. CCXLI1.-The Addition of Ethyl Sodiocyanoacetate and Ethyl Sodiomalonate to Ethyl Muconate. By ERNEST HAROLD FARMER . CCXLIII.3-Dithiobenzoic Acid.By SAMUEL SMILES and DOUGLAS CREESE HARRISON . CCXL1V.-Reactions of Cellulose with Sodium Chloride and other Neutral Salt Solutions. Part I. Preliminary Survey. By HELEN MASTERS . CCXLV.-The Condensation of Aromatic o-Aminosulphonic Acids with isoCyanic Acid. By J o m RICHARD Scorr and JULIUS BEREND COHEN . CCXLV1.-The Interchange of Alcohol Radicles in Esters. Part 11. By AKIRA SHIMOMURA and JULIUS BEREND COHEN . CCXLVI1.-Studies in the Anthracene Series. Part 111. By EDWARD DE BARRY BARNETT JAMES WILFRED COOK and HERBERT HENRY GRAINCIER CCXLVII1.-Inorganic Complex Salts. Crystallographic and Optical Study. Part I. By ISABEL ELLIE KNAGGS CCXL1X.-The Ignition of Gases. Part 11. Ignition by a Heated Surface. Mixtures of Methane and Air. By WALTER MASON and RICHARD VERNON WHEELER .CCL.-Physical Chemistry of the Oxides of Lead. Part VI. The Anodic Behaviour of Lead and Lead Dioxide. By SAMUEL GLASSTONE . CCL1.-The Isomerism of the Oximes. Part X. Cinnam-and Nitrocinnam-aldoximes. By OSCAR LISLE BRADY and CLIFFORD DANE THOMAS . CCLI1.-The Oxime of Mesoxamide (isoNitrosomalonamide) and some Allied Compounds. Part IV. The Ethers of isoNitrosomalonardide isoNitrosomalondimethy1-amide and isoNitrosomalondibenzylamide. By ARTHUR GEOFFREY RENDALL and MARTHA ANNIE WHITELEY . CCLII1.-Adsorption and Catalysis in Fuller’s Earth. By ERIC KEIGHTLEY RIDEAL and WILLIAM THOMAS . CCL1V.-The Solubility of Phenanthrene in Various Organic Solvents. By HERBERT HENSTOCK . CCLV.-The Isomerism of Metallic Oxides. Part I.Lead Monoxide. By MALCOLM PERCIVAL APPLEBEY and ROBERT DOUGLAS REID . CCLVI. - Hydrolysis of p(i! ’ - Dichlorodiethyl Sulphide. Synthesis of Divinyl Sulphidc and the Preparation of a Non-vesicant Isomeride of pp‘-Dichlorodiethyl Sul-phide. By SIDNEY HARTLEY BALES and STANLEY ARTHUR NICEELSON . PAQE 2015 2022 2026 2034 2051 2059 2069 2079 2091 2098 21 10 2119 2124 2129 213 CONTENTS. CCLVI1.-Monothioethylene Glycol. By GEORGE MAC-DONALD BENNETT . CCLVII1.-The Constitution of Acetone Derivatives of Glucose and Fructose. By JAMES COLQTJHOUN IRVINE and JOCELYN PATTERSON Hexadecane-sulphonic (Cetylsulphonic) Acid and other Sulphonates. By MABEL HARRIET NORRIS [with D. H. FAWER and CCLX.-The Labile Nature of the Halogen Atom in Organic Compounds.Part V. The Action of Hydrazine on the Halogen Derivatives of some Esters and Substi-tuted cycZoHexanes. By EDMTJND LANGLEY HIRST and ALEXANDER KILLEN MACBETH . CCLX1.-The Interaction of Aniline and Acraldehyde. By FREDERICK GEORGE MANN . CCLXI1.-The Mechanism of the Formation of Benzoyl-benzoin by Treatment of Benzoylmandelonitrile with an Alcoholic Solution of Sodium Ethoxide. By HERBERT GREENE and ROBERT ROBINSON . CCLXII1.-Quantitative Reduction by Hydriodic Acid of Halogenated Malonyl Derivatives. Part 11. The s. -Tetra-substituted Amides of Bromo- and Chloro-malonic Acid. CCLX1V.-The Chlorination and Bromination of the Toluic Acids and the Preparation of the Phthalaldehydic Acids. By WILLIAM DAVIES and WILLIAM HENRY PERKIN, jun.[with HERBERT CLAYTON] . CCLXV.-Ethyl a-Cyano- p-methylglutaconate and its Methyl Homologues. By EDWARD HOPE . CCLXV1.-The Addition of Hydrogen Cyanide to Derivatives of Glutaconic Acid. Part I. The Addition of Hydrogen Cyanide to Ethyl cc-Cyano- P-methylglutaconate and its Homologues. By EDWARD HOPE and WILFRID SHELDON CCLXVI1.-Reduction of Thorium Oxide by Metallic Tungsten. By THE RESEARCH STAFF OF THE GENERAL ELECTRIC Co. LTD. LONDON (work conducted by COLTN JAMES SMITHELLS) . CCLXVIII. - y - Methylfructoside. By ROBERT CHARLES MENZIES . CCLX1X.-Determination of the Molecular Weight of Substances in Alcoholic Solution from the Elevation of the Flash Point. By ROBERT WRIGHT . CCLXX.-Selective Solvent Action by the Constituenb of Aqueous Alcohol.By ROBERT WRIGHT . CCL1X.-The Constitution of Soap Solutions. M. C. PRICE] . By RALPH WINTON WEST . xxi P A W 2139 2146 2161 2169 2178 2182 2196 2202 2216 2223 2236 2238 2247 225 xxii CONTENTS. CCLXX1.-The Solubility of the Chlorophenols. By NEVIL VINCENT SIDGWICK and $YDNEY LEONARD TVRNER . CCLXXI1.-The Solubility of the Aldehydobenzoic Acids. By NEVIL VINCENT SIDGWICK and HERBERT CLAYTON. CCLXXII1.-The Interaction of Aldehydes or Ketones and Thiocarbamides in the Presence of Acids. Part 11. By JOHN TAYLOR . CCLXX1V.-Intermetallic Actions. The System Alumin-ium-Arsenic. By QASIM ALI MANSURI . CCLXXV.-The Reversibility of the Reaction between Nitrogen Carbon and Sodium Carbonate. By CHRISTO-PHER KELK INGOLD and DANIEL WILSON.CCLXXV1.-The Specific Heats of Gases with Special Reference to Hydrogen. By CHRISTOPHER KELK INGOLD and EDITH HILDA USHERWOOD CCLXXVI1.-The Constitution of the Terpene Present in the Essential Oil from Andropyon Jzuarancusa Jones. By JOHN LIONEL SIMONSEN . CCLXXVII1.-Methylation of Xylose. By ALBERT CAR-RUTHERS and EDMUND LANGLEY HIRST CCLXXIX-The Velocity of Reaction in Mixed Solvents. Part 111. The Influence of Temperature on the Velocity of Saponification of Esters. By HAMILTON MCCOMBIE HAROLD ARCHIBALD SCARBOROUGH and RICHARD HARDCASTLE SETTLE . CCIIXXX.-The Constitution of Carbamides. Part XIV. The Decomposition of Urea by Sodium Hypobromite in Alkaline Solution and an Improved Procedure for the Estimation of Urea by this Means.By EMIL ALPHONSE WERNER . CCLXXX1.-The Ultra-filtration of Soap Solutions Sodium Oleate and Potassium Laurate. By JAMES WILLIAM McBm and WILLIAM JOB JENKINS. Studies in the Composition of Coal. By FREDERICK VINCENT TIDESWELL and RICHARD VERNON WHEELER . CCLXXXII1.-Preparation of Sodium and Potassium Phthalimide. By DALZIEL LLEWELLYN HAMMICK and GEORGE HAZLEWOOD LOCKET . CCLXXX1V.-2 4-Dinitrohenzil. By GERALD BISHOP and OSCAR LISLE BRADY . CCLXXXV.-Mutarotation and Pseudo-mutarotation of Glucosamine and its Derivatives. By JAMES COLQU-. . CCLXXXI1.-On Dopplerite. HOUN IRVINE and JOHN CaMPBELL EARL . PAQE 2256 2263 2267 2272 2278 2286 2292 2299 2305 2318 2325 2345 2362 2364 237 CONTENTS. xxiii PAGE CCLXXXVI.-Salicylidene Derivatives of d- Glucoeamine.By JAMES COLQUHOUN IRVTNE and JOHN CAMPBELL EARL . CCLXXXVI1.-The Mobility of Symmetrical Triad Systems. Part I. The Conditions Relating to Systems Terminated by Phenyl Groups. By CHRISTOPBER KELK INGOLD and HENRY ALFRED PIGGOTT . CGLXXXVII1.-Dyes Derived from ‘‘ Saccharin.” The Sulphamphthaleins. By SIKHIBHUSHAN DUTT . CCLXXX1X.-The Viscosity of Cellulose. Part 11. The Lowering of the Viscosity of CelIulose by Various Reagents. By REGINALD ARTHUR JOYNER . CCXC.-The Sorption of Saturated Vapours by Charcoal. By J o m DRIVER and JAMES BRIERLEY FIRTH . CCXC1.-Attempts to Prepare Red Sulphide Dyes. Part 11. Mercaptan Derivatives of Azo-Dyes. By EDWIN ROY WATSON and SIKHIBHUSHAN DUTT . CCXCI1.-The Form of the Vapour Pressure Curve at High Temperature.Part I. The Curve for Lead. By CHRISTOPHER KELK INGOLD . CCXCII1.-Researches on Residual Affinity and Co-ordin-ation. Part XI. Interaction of Selenium Tetrachloride and P-Diketones. By GILBERT T. MORGAN HARRY DUGALD KEITH DREW and THOMAS VIPOND BARKER . CCXC1V.-The Properties of Ammonium Nitrate. Part IV. The Reciprocal Salt-pair Ammonium Nitrate and Sodium Chloride. By EDGAR PHILIP PERMAN . CCXCV.-The Propagation of Explosion Waves in Gases Contained in Tubes of Varying Cross-section. By COLIN CAMPBELL . CCXCVI.-Action of the Chlorides of Phosphorus on Chloro-dimethyldihydroresorcinol. By LEONARD ERIC HINKEL and WILLIAM DUDLEY WILLIAMS . CCXCVI1.-A Modified Methyl-orange Indicator. By KEN-NETH CLAUDE DEVEREUX HICKMAN and REGINALD PATRICK LINSTEAD .CCXCVII1.-Derivatives of Diphenylthiolbenzene. By SAMUEL SMILES and HUGH GRAHAM. CCXC1X.-Chlorination of Benzoyl Chloride. Part I. By EDWARD HOPE and GEORGE CLIFFORD RILEY . CCC.-The Labile Nature of the Halogen Atom in Organic Compounds. Part VI. The Action of Titanous Chloride and of Ammonia on Representative Halogen Compounds. By IAN ARMSTRONG BLACK EDMUND LANGLEY HIRST, and ALEXANDER KILLEN MACBETH . 2376 2381 2389 2395 2409 241 4 2419 2432 2473 2483 2498 2502 2506 2510 252 xxiv CONTENTS. CCC1.-Derivatives of Methylstmnonic Acid ; Their Bearing upon its Constitution. By HERBERT LAMBOURNE . CCCI1.-A Simplified Method for the Resolution of Methyl-n-hexylcarbinol. By JOSEPH KENYON CCCII1.-Decomposition of Dithiocarbazinates.By SIMA M. LOSANITCH . CCCLV.-Electro-synthesis of Azelaic and Thapsic Acids. By MABEL CARMICHAEL CCCV.-The Action of Bromine Water on Indene. By JOHN READ and ERIC HURST . CCCVI. - Aromatic Sulphonyl Chlorides. By JESSIE STEWART CCCVI1.-Limits for the Propagation of Flame in Vapour-air Mixtures. Part 11. Mixtures of More than One Vapour and Air a t the Ordinary Temperature and Pressure. By ALBERT GREVILLE WHITE . CCCVII1.-The Resolution of Tropic Acid and the Stereo-chemical Configuration of the Cinchona Alkaloids. By HAROLD KING and ALBERT DONALD PALMER . CCC1X.-The Solubility and Volatility of the Nitrobenz-aldehydes. By NEVIL VINCENT SIDGWICK and WILFRED MARSDENDASH . CCCX.-The Formation and Properties of Dithioketones (R,C:S:S) and Dithio-ethers (R,S:S).Part 111. By KWERJI GOSAI NAIK and MAHADEO DATTATRAYA AVASARE CCCX1.-The Triazo-group. Part XXII. Cinnamic Acid Chlorohydrin and its Conversion into a-Triazo- p-hydroxy- p-phenylpropionic Acid. By MARTIN ONSLOW FORSTER and WILLIAM BRISTOW SAVILLE . CCCXI1.-The Labile Nature of the Halogen Atom in Organic Compounds. Part VII. Absorption Spectra of the Halogen Derivatives of Some Cyclic Compounds, and their Bearing on the Question of an Oxygen-Halogen Linking. By HUGH GRAHAM and ALEXANDER KILLEN MACBETH . CCCXII1.-Optical Rotations of the Sugars. Part I. The Aldohexoses and Aldopentoses. By JOHN GWILLIAM MALTBY . 0 CCCX1V.-The System Ammonium Sulphate-Glucinum Sulphate-Water at 25".By HUBERT THOMAS STANLEY BRITTON . CCCXV.-Orientation of the 1 4- and 1 5-Dimethylglyox-dines. Mode of Fission of 5-Aminoglyoxalines. By FRANK LEE PYMAN . PAQR 2533 2540 2542 2545 2550 2555 2561 2577 2586 2592 2595 2601 2608 2612 261 CONTENTS. xxv PAGE CCCXVI .-Bromo- derivatives of 2-Meth ylglyoxaline . By LOUIS LIGHT and FRANK LEE PYMAN CCCXVI1.-Action of Ammonium Nitrate and of Aqueous Ammonia on Copper. Properties of Cu~ric Tetrammine Nitrite and Nitrate. By HENRY BASSETT and REGINALD GRAHAM DURRANT . CCCXVII1.-The Synthesis of m- a-Benzbispyrrole Deriv-atives. By WILLIAM DAVIES and EDGAR HERBERT CUTHBERT HICKOX CCCX1X.-The Molecular Scattering of Light in n-Pentane. By RAMAVENKATASUBBA VENKATESWARAN . CCCXX.-Dyes derived from act’-Dicyanodibenzyl Diketone.By SIKEIIBHUSHAN DUTT and NIRMAL KUMAR SEN . CCCXX1.-Esters of the Hydroxyalkylarylamines. Part I. Acid Sulphuric Esters of the Simple Monohydroxyethyl-arylamines. By KENNETHERBERT SAUNDERS . CCCXXI1.-The Conditions Underlying the Formation of Unsaturated and Cyclic Compounds from Halogenated Open-chain Derivatives. Part V. Products Derived from a-Halogenated P-Methylglutaric Acids. By CHRISTOPHER KELK INUOLD . CCCXXII1.-1 3 4 6-Tetramethyl Fructose. By JAMES COLQUHOUN IRVINE and JOCELYN PATTERSON CCCXX1V.-The Oxidation of Sucrose by Nitric Acid. By FREDERICK DANIEL CHATTAWAY and HINTON JOHN HARRIS . CCCXXV.-The Diazo-reac tion in the Carbazole Series. Carbazole-3-diazoimine and -3-diazonium Salts.By GILBERT T. MORGAN and HUGH NORMAN READ . CCCXXV1.-The Oxidation of Sabinene with Chromyl Chloride. By GEORGE GERALD HENDERSON JOHN MCGREGOR ROBERTSON and DAVID CHRISTIE BROWN . CCCXXVII. - Resorcinolphenylsuccinein. By ARTHUR LAPWORTH and JOHN ALEXANDER MCRAE CCCXXVII1.-The Reactivity of Methyl Groups in Hetero-cyclic Bases. By WILLIAM HOBSON MILLS and JAMES LEONARD BRIERLEY SMITH . CCCXX1X.-Preparation of a-Trioxymethylene and a New Polymeride of Formaldehyde. By DALZIELLEWEUYN HAMMICK and ALFORD REGINALD BOEREE . CCCXXX.-Syntheses of Alkylidenecyanoacetic Acids and of Substituted Succinic Acids. Part 11. Preparation of Acids containing Saturated Aliphatic Residues and the Constitution of the Aliphatic Alkylidenecyanoacetic Esters. By ARTHUR LAPWORTH and JOHN ALEXANDER MCRAE .. . 2626 2630 2640 2655 2663 2667 2676 2696 2703 2709 2717 2722 2724 2738 274 xxvi CONTENTS. CCCXXXI.-The Interaction of Diazonium Salta and Phenols. By FREDERICK DANIBL CHATTAWAY and HENRY ROWLAND HILL . CCCXXXI1.-The Behaviour of the Stannic Acids towards Solutions of Alkaline Hydroxides. By GEORGERNEST COLLINS and JOHN KERFOOT WOOD . The Significance of Crystal Structure. A Lecture delivered before the Chemical Society on October 26th 1922. By SIR WILLIAM H. BRAGU K.B.E. F.R.S. . CCCXXXII1.-The Purification of Methyl Alcohol by means of Sodium Hypochlorite. By ROBERT CHARLES MENZIES . . CCCXXX1V.-The Additive Formation of Pour-membered Rings. Part I. The Synthesis and Division of Deriv-atives from 1 3-Dimethindiazidine. By CHRISTOPHER KELE INGOLD and HENRY ALFRED PIGGOTT CCCXXXV.-The Composition of Paraffin Wax. Part 111. By FRANCIS FRANCIS CYRIL MERCER WATKINS and REUINALD WILFRED WALLINUTON . CCCXXXV1.-The Mechanism of the Bromination of Phenol in Aqueous Solution. By HARRY BAINES . CCCXXXVI1.-The Equilibrium in Systems Composed of Water and Alcohols Methyl Alcohol Pinacone, Glycerol and Erythritol. By NICOLAI ANTONOVICH PUSHIN and ALEXANDRA ALEXANDROVNA GLAGOLEVA . CCCXXXVII1.-The Equilibrium in the System m-Dinitro-benzeneurethane. By NICOLAI ANTONOVICH PUSHIN and ALEXANDRA FIOLETOVA . CCCXXX1X.-Formation of y-Alkylidene Derivatives from Ethylidenemalonic Ester. By LUCY HIGGINBOTHAM and ARTHUR LAPWORTH . CCCXL.-The Isoelectric Condition of Gelatin By SIDNEY OWEN RAWLINU and WALTER CLARK CCCXL1.-The Adsorption of Radium-B and Radium-C by Ferric Hydroxide. By JOHN ARNOLD CRANSTON and ROBERT HUTTON . Part 11. Potassium Platinibromide. By EBEN HENRY ARCHI-BALD and WILLIAM A. GALE CCCXLII1.-Researches on Residual Afhity and Co-ordin-ation. Part XII. Cobaltammine and Ferric Lakes of Dinitrosoresorcinol. By GILBERT T. MORGAN and JOHN EWART Moss . . . CCCXLI1.-The Hydrolysis of Platinum Salts. . PAQE 2756 2760 2766 2787 2793 2804 2810 2813 2822 2823 2830 2843 2849 285 CONTENTS. xxvii PAQE CCCXL1V.-Researches on Residual Affiity and Co-ordin-ation. Part XIII. Cobaltammine and Chromic Lakes of the Azo-salicylic Acids. By GILBERT T. MORGAN and J. D. MAIN SMITH . CCCXLV.-Boundary Lubrication and Chemical Constitu-tion. The Optically Active Carbinols of the Formula C,H,*CH(OH)*C,H2,+1. By IDA DOUBLEDAY . CCCXLV1.-Vat Dyes of the Azo-series. By DHIRENDRA NATH MUKERJI . CCCXLVI1.-Researches on Residual &ity and Co-ordination. Part XIV. Interactions of Metallic Salts and Dimethyldithiolethylene. By GILBERT T. MORGAN and WILFRID LEDBURY . WAR MEMORIAL . . OBITUARY NOTICES TRUST DEED ESTABLISHING THE HARRISON MEMORIAL PUND 2866 2875 2879 2882 2894 2898 291
ISSN:0368-1645
DOI:10.1039/CT92221FP001
出版商:RSC
年代:1922
数据来源: RSC
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2. |
II.—The overvoltage of the mercury cathode |
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Journal of the Chemical Society, Transactions,
Volume 121,
Issue 1,
1922,
Page 7-17
Edgar Newbery,
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摘要:
NEWBERY THE OVERVOLTAQE OF THE MERCURY CATHODE. 7 11.-The Overvoltage of the Mercury Cathode. By EDGAR NEWBERY. IN a recent communication by Dunnill (T. 1921 119 1081) a careful and detailed description is given of the interesting behaviour of a mercury cathode. Unfortunately the range of current density and the time employed were so limited that many important phenomena were overlooked. Only one of the three overvoltage 8 NEWBERY THE OVERVOLTAOE OF THE MERCURY CATEODE. of mercury was observed and although the small variations of this one value under slight changes of conditions were exhaustively studied the much greater changes produced by extreme conditions were not obtained. Some of the results recorded differ materially from those obtained by the present author and certain far-reaching conclusions were drawn which seem scarcely justified by the limited range of observations.With the view of explaining these dis-crepancies and testing these conclusions the following work was undertaken. The conditions were made as far as possible identical with those of Dunnill’s work but were considerably extended in many directions in order to obtain a fuller insight into the whole problem. E X P E R I M E N T A L . A glass vessel was taken having a cross section of approximately 10 sq. cm. and carefully purified mercury poured in tfo a depth of 1.5 cm. contact being made by a platinum wire sealed into the end of a glass tube and dipping to the bottom of the mercury. The anode consisted of a stout platinum wire 1 crn. long sealed into another glass tube and supported at varying distances (usually about 1 cm.) from the mercury surface.It was found that the position of the anode had little or no effect on the overvoltage, although the diameter of the ring free from visible bubhles was greatly affected by this motion. The electrolyte was N-sulphuric acid and a mercurous sulphate-mercury electrode in acid of the same strength was used as reference electrode. The jet of this electrode vessel (1 rum. in diameter) could be adjusted to any position with regard to the surface of the mercury, and it was soon found that important data as to the effect of change of position of this jet had been omitted from Dunnill’s description. In his work the jet is described as just touching the mercury surface immediately below the anode In such a position it naturally interferes with the lines of flow of the current but this may be a matter of little importance.Of much greater importance is the fact that there is a remarkably steep potential gradient in the immediate neighbourhood of the mercury surface during the passage of the current and the motion of the electrode jet through one millimetre in a vertical direction may alter the measured potential by more than one hundred millivolts. Depressing the jet 1 cm. under the mercury surface may change this potential by nearly one volt. Again if the jet actually touches the metal a new metal-electrolyte surface is introduced and it is by no means certain that the metal thus imprisoned is in the same condition or has the same single potential as the surrounding metal.In addition to all this th NEWBERY THE OVERVOLTAGE OF THE MERCURY CATHODE. 9 tendency for gas bubbles to collect in the capillary is very marked, due to the imprisonment of metal saturated with hydride or super-saturated with hydrogen. The metallic solution when thus released from the severe electric strain of the surrounding medium at once liberates its hydrogen in the capillary tube and a new metal-gas surface is formed having its own single potential which duly appears among the factors present in the resultant measurements. It is evident therefore that the expedient of allowing the electrode jet to touch the mercury surface is a most dangerous one and results thus obtained must be treated with the greatest caution.In the experiments here described the electrode jet (unless stated to the contrary) was supported about one millimetre above the mercury surface. When a commutator is used the position of the jet in the electrolyte and the relative position of the leading-in wire to the mercury cathode have no effect on the measurements, whereas both these factors affect the results obtained without a commutator. Such factors have nothing to do with true over-voltage and their presence therefore indicates a considerable error in the resultant measurements. The following table illustrates the variation in measurements due to the position df the jet from the standard electrode with respect to the mercury surface. The current was 36 milliamperes and the commutator speed 1500 revs.per minute. 1omm. lmm. lmm. 1omm. above. above. 0. below. below. With commutator ...... 0.40 0.40 0.40 0.37 0.18 Without commutator ... 0.70 0.67 0.58 0.41 0.08 The mercury in this case had been previously subjected to a high current density but had been kept for forty-eight hours before the above readings were taken. In order to obtain the high values (which were the only ones observed by Dunnill) this mercury was treated with a current of 68 milliamperes for half an hour when the expected jump of potential occurred and the above set of observa-tions was repeated. Current and commutator speed as before. Jet 10 mm. 1 mm. lmm. 1omm. above. above. 0. below. below. With commutator ...... 0-81 0.81 0.81 0.80 0.56 Without commutator ...1.13 1.10 1.07 0.98 0.45 Current increased to 68 milliamperes. With commutator ...... 0.82 0-82 0.82 0-80 0.50 Without commutator ... 1.28 1.20 1-09 1-03 0.60 These figures illustrate very clearly how at least one source of serious error is eliminated by the use of a commutator namely, B 10 NEWBERY TEE OVERVOLTAGE OF THE MERCURY CAqHODE. that due to change of position of the electrode jet in the electrolyte. When the jet is thrust far down into the mercury the standard electrode practically becomes an independent cell the negative electrode being formed by the surface of the mercury which enters the jet. This mercury is in contact with an unsaturated solution of mercurous sulphate and is therefore of uncertain potential. Also the position of the platinum connexion to the battery materially affects this potential which is consequently very variable and of little theoretical interest.The steep potential gradient at the surface of the mercury cathode disappears the instant the current is interrupted and this fact supplies one of many proofs which could be given of the existence of a gas film of high resistance on the surface. All the above figures are averages of four complete sets of readings. Effect of Commutator Velocity. This has been discussed in detail in a communication sent to the Journal of the American Chemical Society early in August last but the mercury electrode was not among thosq chosen. The figures given by Dunnill indicate a curve (overvoltage-commutator speed) 80 much steeper than any obtained with other electrodes that one is forced to the conclusion either that the rate of decomposition of the mercury overvoltage compounds is enormously greater than those of other metals or that these figures are seriously affected by a mechanical defect in the commutator used.In order to settle this point a very careful and extended series of observations was taken (about 200 readings in all) the same current densities being used as those given by Dunnill namely 36 and 68 milliamperes per 10 sq. cm. The commutator was 1.5 inches in diameter having only two sections and these were separated by ivory plugs inch thick. It was constructed with a solid steel flywheel 6 inches in diameter and 5 inch thick on the same shaft which ensured steady running and was driven by a 200 volt motor with a rheostat in series.The rheostat was carefully calibrated to give speeds of from 250 to 1500 revs. per minute and these speeds were checked from time to time during the course of the work. Before use special care was taken to ensure that when the centre brush was on the ivory plug no current could pass in either direction. As will be seen later it appears probable that neglect of this precaution has led to the abnormal results obtained by Dunnill. Two sets of results were obtained a t a current of 36 milliamperes, one with the mercury in the high and the other in the low over voltage condition these conditions being quite easily obtained at any time but not always easy to maintain. The following table gives the averages from about twenty sets of readings current density being given in milliamperes per 10 sq.em. and commutator speed in revolutions per minute. Commutator speeds. r Current. Direct. 1500 1250 1000 750 500 250 A . 36 1.08 B. 36 0.83 C. 68 1.15 0.9 0.8 d OS7 M 8 B 0-6 0.5 0.4 0.82 0.815 0-SO 0.77 0.71 0.62 0-45 0.45 0-45 0.445 0.44 0.42 0.835 0.83 0.52 0.80 0.i5 0.68 FIG. 1. -. €3 /-- - I L --A I-_-250 500 750 1000 1250 1500 Commutator speeds. The curves in Fig. 1 illustrate these results graphically. It is evident that at the highest speed used the curves have already approached very near to a maximum and extrapolation to infinite speed will give values not far removed from those observed at 1500 revs. per minute. In fact curve A reaches 0.825 volt curve B 0-45 volt and curve C 0.84- volt when this extrapolation is carried out-values which are widely different from those obtained by the " direct " method.On comparing these results with those of Dunnill it will be observed that although his lowest commutator speed is identical with the highest here used he obtains rises of 0.1 to 0-2 volt. It B* 12 NEWBERY THE OVERVOLTAGE OF THE MERCURY UATHODE. appears highly probable therefore that his results have been vitiated by a defective commutator. If a perfectly clean break is not made from the main circuit before the potentiometer circuit is connected some fraction of the main current is “ dragged over ” and greatly affects the potentiometer readings.* These curves are of interest in that they show not only the great instability of the compounds responsible for the high overvoltage of mercury but also (curve B) the comparative stability of the compound producing the lower overvoltage.Eflect of Time. The whole of Dunnill’s work seems to have been done with mercury in the high overvoltage condition. This condition is usually but not always shown by pure fresh mercury electrodes and is the stable state at low current densities. Since the highest current density he used was 7.8 milliamperes per sq. cm. and this only for a short time he did not have an opportunity of observing the remark-able time effects previously described by the present author (Zoc. cit.). The following table shows the effect of time with low current density on the total back E.M.P.of mercury which had been kept for twenty-four hours in contact with the electrolyte but with no current flowing. Area of cathode 10 sq. cm. ; current 68 milliamperes; no com-mutator used. Timeinmins. 1 2 3 4 5 10 15 20 25 30 40 60 60 Back R.M.P. 0-78 0.79 0-79 0.80 0-80 0.81 0.82 0.83 0-86 1.15 1-20 1.23 1.24 After an interval of one hour with no current flowing the same cathode was used a t the same current density but with a com-mutator speed of 1500 revs. per minute. The results were as follows : Timeinmins. 1 2 3 4 5 10 15 20 25 30 40 50 60 Overvoltage 0.67 0.74 0.77 0.79 0.80 0.83 0-84 0.85 0-85 0.85 0.85 0.85 0-85 These results are illustrated graphically in Fig. 2. It is evident that curve B is really a repetition of the latter part of curve A with the disturbing influence of transfer resistance removed.The position and steepness of the rapidly rising portion of the curve are chiefly determined by the previous history of the electrode. * The present author on one occasion wasted three days’ work obtaining anomalous and irreproducible results before locating this source of trouble-in this case a single h e strand of wire from the brush disarranged by an unauthorieed person rotating the commutator backwards NEWBERY THE OVERVOLTAGE OF THE MERCURY CATHODE. 13 Mercury which has been kept in contact with the electrolyte for some hours acquires an overvoltage of about 0.4 volt and both the time required to change this value and the flattening of the rapidly rising portion of the curve are increased by long keeping.An illustration of an extreme case of this kind is seen in curve C which was obtained under the same conditions as curve B except that the cathode had been kept undisturbed for a week. As might be expected the time effect occurs more rapidly when a commutator is not used. At high current densities the change to low values occurs very rapidly. A cathode was showing a back E.M.F. of nearly 2 volts with a current density of 68 milliamperes when the current was FIQ. 2. 1.2t I 1.1 1.01 0.6 0.5 0.4 10 20 30 40 50 60 Tiine in minutes. suddenly increased to 1000 milliamperes. In three minutes the back E.M.P. had fallen to 0.55 volt measured without a commutator and - 0.02 volt with a commutator. This rapid fall of overvoltage sometimes occurs after the application of a high current density even although the current has been greatly reduced in the meantime -a peculiar type of delayed action.An interesting time effect is observed not only with mercury electrodes but also with nearly all metals when the commutator velocity is varied. At high speeds there is a general tendency for the measured overvoltage to increase with time up to a definite maximum. At low speeds there is a similar tendency to decrease with time to a somewhat less definite minimum. If the maximum has been attained a t a high speed and the commutator velocity is suddenly reduced the measured overvoltage remains at its high value for an appreciable time and then falls gradually. This experiment may be carried to extremes by short-circuiting th 14 NEWBERY THE OVERVOLTAGE OF THE MERCURY CATHODE.commutator for some time which is equivalent to running it at an infinite speed and removing the short-circuiting plug the instant before taking a reading. Values obtained in this way agree very well with those obtained by extrapolation of the overvoltage-commutator speed curves and thus afford additional evidence for the trustworthiness of those values. Effect of Current Density. The very limited range of current density used by Dunnill (11 to 78 milliamperes per 10 sq. cm.) gives a most unsatisfactory im-pression of the real effect of current density. I n the work here described an attempt was mdde to determine the effect of current density on mercury in both the high and very low (zero) overvoltage states.The latter is quite easy but the former can only be done by very rapid working at the higher current densities owing to the great tendency of the electrode to change suddenly to the latter condition. By starting with an unused electrode and working at high speed two complete series were obtained both without and witlh a commutator. The values with the commutator agreed within 0.01 volt whilst those without the commutator varied by 0.08 volt at the same current densities. Within thirty seconds after com-pleting these series the expected overvoltage fall occurred although the current density was low at the moment. Two further series were then taken and are shown in column B in the following table. Column A shows the average values obtained in the first series.Current density is given in milliamperes per 10 sq. cm. Com-mutator speed 1500 revs. per minute. Current Density. With Commutator. A . B. 20 0.75 0.08 40 0.76 0.06 100 0.70 0.05 200 0.65 0.03 400 0.61 0.03 1000 0.57 0.03 2000 0.56 0.01 Without Commutator. A. B. 1.01 0.49 1.04 0.54 1.12 0.58 1-16 0.66 1.26 0.77 1.42 1.03 The Three Overvoltages of Mercury. From the work described it is evident that mercury shows three fairly definite overvoltages-high (0.8 volt or more) low (0-4 volt approximately) and zero-corresponding with the bivalent uni-valent and zero-valent (no compound formed) states respectively. The fist state is produced by and is permanent at low current densities and is generally shown by fresh mercury.The seaon NEWBERY THE OVERVOLTAGE OF THE MERCURY CATHODE. 15 state is shown by mercury which has been kept for some time in contact with dilute acid and appears to be unstable when current is flowing. It may be due to the formation of traces of mercurous salt adsorbed on the mercury surface and also carried into the body of the mercury by movements due to change of surface tension. This salt on decomposing would tend to give the hydride correspond-ing with univalent mercury and therefore the lower overvoltage. The third state is permanent at high current densities and when once acquired takes a considerable time for its removal. Its sudden appearance is accompanied by an equally sudden change in the size of the bubbles of gas liberated from large to very small.A Proposed Addition to the Previous Theory of Overvoltage. The author has felt for a long time that his attempted explanations of the remarkable fall of overvoltage and of transfer resistance at high current densities have been very unsatisfactory. The present work has suggested another idea which not only appears much more reasonable at first sight but also affords an explanation of the change of size of the gas bubbles and of the effect of stirring the electrolyte which was quite inexplicable on the basis of the older theory alone. At low current densities the ions in the solution in the neighbour-hood of the electrodes are at a distance from each other which is large compared with their own dimensions. At very high current densities this condition no longer holds and the ions close to the electrode surface are packed so closely that an electron shot out from the electrode into an ion within range may travel with such velocity and produce such disturbance within the atom thus struck that the electron on the opposite side of the atom becomes loose enough to be seized by another ion close to the fist ion but further away from the electrode.At extreme current densities the electrical tension near the electrodes is very high and this action will therefore become more general and more extended into the electrolyte. But this action involves the discharge of ions at a distance from the electrode. The tendency to the formation of a gas film and the production of high pressures will therefore be greatly reduced and hence transfer resistance falls.At the same time the reduction of the pressure will allow of the decomposition of the overvoltage compounds without inducing their re-formation and the over-voltage will therefore fall. The extremely minute bubbles seen under these conditions are a natural consequence of thia discharge in the electrolyte and the high degree of ionisation of the eacaping gas (T. 1914,105 2429) also follows 16 NEWBERY THE OVERVOLTAQE OF THE MERCURY CATHODE. Rapid stirring of the electrolyte a t high current densities will tend to disturb the packing of the ions along the lines of force and will therefore lessen the distance discharge thus producing a rise of overvoltage. At low current densities similar stirring will tend to remove the obstructing gas film thus producing a fall of over-voltage.Both these phenomena were observed by the author in 1913 but until now he was able to offer no adequate explanation of them. The idea of chemical action at a distance from the electrode is not new and has been applied in the electrolytic manufacture of white lead but in this case the ions themselves are considered to be so closely packed that they form in one sense a conducting plate carrying the current from the electrode out into the electrolyte. Conclusions. It is evident from the work described that Dunnill’s conclusion that “ the direct method gives more accurate results ” cannot be upheld if the term “ overvoltage ” is to be confined to its legitimate objeckthe reversible portion of the total back electromotive force of an electrode.The commutator method is certainly liable to an error due to the very rapid decomposition of the overvoltage com-pounds but this error is trifling compared with the very large effects produced by transfer resistance. Furthermore this small error may be completely eliminated by the simple expedient of extra-polation to infinite commutator speed. The statement on p. 1087 that “it would be difficult to give a direct proof of the presence of this film ” (of gas on the electrode) is hard to understand. So far as the author is aware this has never before been questioned and is the usual text-book explanation of the phenomena of polarisation in a simple cell. The appearance of visible gas bubbles is in itself a direct proof of the supersaturation of the electrode surface with gas.Any denial of the existence of a gas film would introduce insuperable difficulties in explaining the simple phenomena of polarisation gas electrodes etc. The surface tension phenomena described by Dunnill are interest-ing but appear to have no very direct connexion with the over-voltage of the cathode as similar values are obtained whether the ring is present or not. The sudden appearance of the ring during an experiment coincides with no marked change of overvoltage, and the size of the ring is dependent on the position and shape of the anode. A small point not mentioned by Dunnill is that, althoush the mercury surface inside the ring appears to be travelling outwards the small gas bubbles are often observed travelling from the walls of the containing vessel inwards towards the ring.I THE MECHANISM OF THE OXIDATION OF DRYING OILS ETC. 17 conclusion it appears highly probable that Dunnill’s unsatisfactory results with a commutator are due to a defective apparatus but his reasoning is also influenced by two questionable statements at the commencement of his paper-the first that the surface of metallic mercury can be reproduced exactly is open to serious doubt, whilst the second that the properties of the surface are unchanged during the passage of the current is disproved both by his own work and by the experiments here described. Xummry. 1. The overvoltage and the direct potential difference of a mercury cathode have been measured under wide variations of current density time commutator speed etc. 2. Although the rate of decomposition of the overvoltage hydrides of mercury i s high a very close approximation to the true over-voltage is obtained when the commutator speed is not less than 1500 revs. per minute and an exact estimate may be made by extrapolation to infinite speed. 3. No approximation to true overvoltage can be obtained without the use of a commutator. 4. Mercury shows three distinct overvoltages corresponding with the bivalent univalent and non-valent conditions. Directions are given whereby any one of these conditions may be obtained at will. 5. An extension of the previous theory of overvoltage is suggested which will account for the lowering of overvoltage and transfer resistance a t high current densities the diminished size of the gas bubbles under similar conditions and the variable effect of stirring the electrolyte at different current densities. PHYSICAL CHEMISTRY DEPARTMENT, UNIVERSITY OF CAPE TOWN. [Received November lst 1921.
ISSN:0368-1645
DOI:10.1039/CT9222100007
出版商:RSC
年代:1922
数据来源: RSC
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III.—The mechanism of the oxidation of drying oils as elucidated by a study of the true oxygen absorption. Part III. The action of driers |
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Journal of the Chemical Society, Transactions,
Volume 121,
Issue 1,
1922,
Page 17-23
Samuel Coffey,
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摘要:
THE MECHANISM OF THE OXIDATION OF DRYING OILS ETC. 17 111.-The Mechanism of the Oxidation of Drying Oils as Elucidated by a Xtudy of the True Oxygen Absorption. Part 111. The Action of Driers. By SAMUEL COFFEY. A METHOD having been devised for obtaining the true oxygen absorption values of drying oils (T. 1921 119 1152) it was deter-mined to employ it in an attempt to elucidate the action of driers 18 COFFEY THB MECHANISM OF THE The rate of oxidation of linseed oil is affected by heat and sun-light and further by certain metals and their salts which are known as ( ( driers ” or (‘ siccatives.” Fokin ( J . Russ. Phys. Chern. Xoc., 1907 39 609) suggested that their action was catalytic* because (a) there appeared to be no stoicheiometric relation between the quantity of drier and the amount of oxygen absorbed and ( b ) the reaction curve appeared to be logarithmic of the form m 1 a t t a - x’ k = ,- + - log ~ where t is the period of induction where absorption is proportional to time.Also t is diminished by a large amount of drier; hence he suggested that this stage corresponds with molecular autoxida-tion and that probably molecular and atomic oxidation proceed simultaneously. Later ( J . Russ. Phys. Chem. Soc. 1908 40 276) he suggested that the oxidation of linseed oil was a process of molecular autoxidation accompanied by a decomposition of the products of the reaction into volatile and complex substances. He also supposed that the absorption could be carried out without the formation of volatile products if metallic oxides were present, but as will be shown later this is erroneous.He considered that his results showed that the oxidation in films and in solution in the presence of driers proceeded by the same two stages namely, x1 = k,t for the induction period. dx -2 = E (a - x,) after the induction period. According to Fokin Ostwald’s formula for autoxidation does not dt2 hold and also the reaction is probably one of function of the drier being represented by AO + B = A0 + BO, (Oil.) where A denotes a metal. Ingle also ( J . Soc. Chern. Ind. 1917 36 379) autoxidation the has put forward a catalytic hypothesis according to which the basic (lead) oxide first hydrolyses the oil and then acts catalytically by forming an unstable peroxide. Orloff ( J . Russ.Phys. Chem. SOC. 1910 42 658; 1911, 43 1509) found that linoxyn was unsaturated that the correct apparent oxygen absorption value was 16-16 per cent. and that, with a cobalt drier setting took place when the absorption was 12 per cent. He found that the equation for the reaction approxi-mated to the empirical equation dx _ - dt - ’ ( A - x (B + x), * Mulder (1867) assumed driers to be catalysts OXIDATION OB DRYING OILS ETC. PART 111. 19 where A is the total amount of oxygen absorbed and B is a constant. Thus Fokin and Orloff consider that the action of driers is catalytic and that the apparent oxidation curve approximates after a time to that of a unimolecular reaction. If the action of driers is purely catalytic that is if they act in no other way than as oxygen carriers then it can be assumed that the true oxygen absorption for a given oil is a constant quantity, no matter what the drier may be and no matter what its concen-tration.Unfortunately apparently no data exist on this point save perhaps those of Lippert (2. angew. Chem. 1898 11 412, 431) which show that the maximum apparent oxygen absorp-tion gradually decreases as the amount of drier increases. As all this work however deals with apparent oxygen values the figures are of little use.* According to Fokin the following metals and their salts act as driers the most active being placed &st :-Co Mn Cr Ni Fe Pt Pd Pb Ca Ba Bi Hg U Cu Zn; the metals following lead are only " weak " driers. In this investigation litharge red lead manganese borate lead acetate and cobalt oxide were taken as being a fair representation of the numerous driers used commercially.E X P E R I M E N T A L. The same linseed oil was used as in the determination of the true oxygen absorption of oil alone and the apparatus was that fully described in Part I of this research (Zoc. cit.). The true oxygen absorption of the oil was 28.7 per cent. and its iodine value 184.1. The drier in each case was ground as finely as possible. A known amount of oil was placed on a filter-paper in the way already described (Zoc. cit. p. 1154) and the drier was deposited on each surface of the oil fdm in a thin uniform layer by allowing it to fall on the paper in a fine cloud from a height of about 30 cm. Care was taken to cover the surface of the oil as completely as possible but on the other hand a relatively thick iiIm of drier was avoided.The prepared paper was quickly placed in the absorption apparatus which was then flooded with hydrogen, heated to the desired temperature and finally flooded with oxygen. The subsequent procedure wa,s exactly that described for the determination of the oxygen absorption of the oil in the absence of a drier (Zoc. cit.). The results obtained with the above driers are given in Table I. * Fahrion (Chem. Zeit. 1904 28 1196) overlooks this fact in his discussion of the subject 20 COFFEY THE MECHANISM OF THE TABLE I. True oxygen absorption in the presence of driers. Oxygen Oxygen Weight absorption. Weight absorption. of oil. Per of oil. Per Drier. Gram.cent. Drier. Gram. cent. Cobalt oxide 0.5515 24.0 Red lead 0.5648 17.7 9 9 0.6988 26-4 9 9 0.5964 17.4 Mean 9 9 0.5879 27-4 9 9 0.6120 16.8 17" Y 7 0.9356 27.3 9 9 0.7360 17.1} 9 9 0.7738 17.1 } 0.6382 21.8 Litharge 0.5030 17.9 Lead acetate 0.7306 23.9 0.5670 17.0 "" 0.5630 26.0 99 0-6245 17.1 9 9 0.5841 26-4 Manianese borate 0-6537 22.2 9 9 0.6740 23-6 99 0.6430 23.0 Cobalt Oxide.-The black " chemically pure " oxide was ignited before use. The drier was very dense and some difficulty was experienced in obtaining a good distribution without using a relatively thick layer. The results are all lower than the true oxygen absorption for the oil alone but no constancy is obtained. This may be due to the inferior distribution. Litharge.-This was a good sample free from metal or peroxide.It was extremely fine and was exceptionally easily deposited on the oil surface. The distribution was particularly good and as far as could be seen was all that could be desired. These results are again lower than those obtained without a drier being about 0.6 of this value and approaching the recognised apparent oxygen value for the oil alone namely 18 per cent. but they differ from those obtained with cobalt oxide in that with the exception of the first value they are quite constant a t 17.1 per cent. Manganese Borate.-This was a sample of the commercial article. Although thoroughly ground it was extremely difficult to distribute it satisfactorily. The results are again lower than those obtained without the drier. Red Lead.-This drier like the monoxide was extremely fine, and the distribution excellent being both thin and uniform.The deposits on the papers after oxidation were still bright red. These values are again much lower than those obtained without a drier, and are fairly constant at 17.1 per cent. the same value as for lit harg e . Lead Acetate.-The recrystallised hydrate Pb( C,H,02)2,3H20, was used. In this case it was very difficult to secure a good dis-tribution and the results therefore are not trustworthy. They show however that the amount of oxidation in the presence of lead acetate is smaller than that in the absence of the drier OXIDATION OF DRYING OILS ETC. PART III. 21 The Oxidation Curves. Fig. 1 shows the curves obtained for the oil alone and for the oil with cobalt oxide and with litharge or red lead as the drier.In the case of the lead oxides the reaction curves are coincident over FIG. 1 . Oxidation curves for linseed oil with and withut a drier. Time in hours 22 THE MECHANISM OF THE OXIDATION OF DRYING OILS ETO. their whole length. In the presence of the drier there is practically no period of induction but the time required for complete oxidation is the same as that required for the oil alone without the induction period. In the presence of a drier therefore only the induction period is shortened the rate of the main oxidation being unaltered. Since however the induction period for oil alone is extremely large a t the ordinary temperature the " accelerating " effect of a drier becomes explicable.The method of experiment in this investigation might possibly be criticised on the ground that the low oxygen absorption in the presence of driers may be due to the compound forming a protective layer on the oil surface thereby preventing its oxidation. This objection appears to be negatived however by the following facts : (a) the values for the oxides of lead are quite constant ( b ) com-plete oxidation takes place and (c) the reaction curves although indicating a smaller oxygen absorption do not run parallel to the curve for oil alone. Also as will be seen from Fig. 1 the curves deviate even more than the curve for oil alone from the simple logarithmic curve suggested by Fokin and others. Discussion of Results and Conclusions. From the foregoing results it is evident that the presence of a drier modifies the course of the oxidation of linseed oil because in every case the oxygen absorption recorded is lower than that observed when no drier is present and the reaction curves are different.Analogous results were obtained by Morrell (T. 1918, 113,111) in his investigation of the oxidation of the cerium salts of linolenic and a-elaeostearic acids. According to these results, a-elaeostearic acid an isomeride of linolic acid in the presence of a cerium drier absorbs only one molecule of oxygen and not two. The oxidation of linolenic acid however appears to be far more complex. The acid used was doubtless a mixture of the a- and P-isomerides and as has been shown in Part I1 of this work this would introduce undesirable complications (T.1921 119 1408). His results show however that in all probability the oxidation of cerium linolenate is not so extensive as that of free linolenic acid. If in the case of linolic acid with lead oxide as a drier the oxygen absorption also amounts to one molecule then this accounts for 5.54 per cent. of the absorption of oxygen by the oil employed in these experiments (compare T. 1921 119 1411). This leaves 11.56 per cent. for the or-linolenic acid which means that in the presence of this particular drier the acid absorbs exactly six atoms of oxygen. This supposition has received no direct experimenta NIERENSTEIN CATECHUTANNINS. PART I. 23 confirmation but in the light of the results given in Part I1 and in Morrell’s work it would seem to be very probable.It is also interesting to note that in the presence of a drier the amount of carbon dioxide evolved during the oxidation is approxi-mately the same as for the oil alone. Owing to the basic properties of the drier however an accurate estimation of the volatile products was not possible. In the presence of driers (PbO) no trace of hydrogen peroxide could be detected. In the light of the above evidence although the drier may remain unchanged-an assumption that has yet to be verified-it does not act as a catalyst in the strictest sense because it obviously changes the course of the reaction. Thus the large amount of work which has been carried out in the presence of driers and based upon the assumption that the latter are true catalysts is not comparable with that done on oil alone. The author takes this opportunity to express his great indebted-ness to Professor F. S. Kipping F.R.S. in whose laboratory the experiments were carried out for his constant advice during this work and also to the Commissioners of the 1851 Exhibition for a scholarship which enabled him to complete the investigations. ORGANIC CHEMICAL LABORATORY, THE UNIVERSITY, LEIDEN (HOLLAND). [Received October 27th 1921.
ISSN:0368-1645
DOI:10.1039/CT9222100017
出版商:RSC
年代:1922
数据来源: RSC
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4. |
IV.—Catechutannins. Part I. Paullinia tannin |
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Journal of the Chemical Society, Transactions,
Volume 121,
Issue 1,
1922,
Page 23-28
Maximilian Nierenstein,
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NIERENSTEIN CATECHUTANNINS. PART I. 23 IV.-Catechutannins. Part I . Paullinia Tannin. By MAXIMTT~AN NIERENSTEIN. IT has recently been suggested by Freudenberg (Ber. 1920 53, [B] 1417; compare Lowe J. pr. Chem. 1868 [i] 105 33 75; Etti Nonutsh 1889,10,467) that the catechutannins are amorphous dehydration products of catechin. As evidence in support of this view Freudenberg quotes Kirmsse (Arch. Phurm. 1895 236 122), who during the course of an investigation of guarana a paste obtained from the seeds of Puulli~zia cupuna H. B. & K. was able to isolate a crystalline catechin in addition to amorphous guarana tannin.* A deduction based on this observation cannot * For a summary of the literature of catechutannins in general and of guarana and paullinia tannins in particular see Perkin and Everest “The Natural Organic Colouring Matters,” 1918 and Dekker “ Die Gerbetoffe,” 19 13 respectively 24 NIERENSTEIN CATECHUTANNINS.PART I. be taken seriously since the manufacture of guarana involves a series of vigorous processes including the roasting of the seeds (compare Planchon and Collin ‘‘ Les Drogues simple d’origine v&g&tale,” 1898 2 576). It is therefore very probable that the catechin found by Kirmsse in guarana is a disintegration product of guarana tannin. The results obtained by the author are in every respect opposed to Freudenberg’s theory since paullinia tannin is found to be a crystalline substance consisting of one molecule of dextrose and two molecules of gambier-catechin * carboxylic acid. The latter acid is not identical with the synthetic gambier-catechin carboxylic acid previously described (Annalen 1913 396 194).As these two acids are probably isomerides it is proposed provisionally, to employ the prefix cc for the synthetic acid and for the acid occurring in paullinia tannin. The present investigation shows that the two molecules of P-gambier-catechin carboxylic acid in paullinia tannin form a depside (compare Fischer Ber. 1913 46 3253) since the methylo-deriv-ative prepared by the action of diazomethane on paullinia tannin, yields tetramethyl glucose on hydrolysis (compare T. 1921 119, 284). As paullinia tannin contains a free carboxyl group and when hydrolysed with emulsin yields both P-gambier-catechin carboxylic acid and dextrose it becomes also evident that this tannin is a normal glucoside (compare Fischer and Strauss Ber.1912 45, 2467) and not an acyl derivative of glucose as assumed by Fischer in the case of gallotannin. Our incomplete knowledge of gambier-catechin makes it impossible to discuss the constitutions of p-gambier-catechin carboxylic acid and paullinia tannin hence a t present an empirical formula only is assigned to the latter : QeC,H1l 0 5 C,,H,O( OH) ,*CO*O-C 15HsO( OH),*CO,H It should be noted that the methylo-derivative of paullinia tannin, on hydrolysis yields in addition to tetramethyl glucose penta-methoxy- and trirnethoxy- p-gambier-catechin carboxylic acid. The * The catechin found by Kirmsse in guarana is obviously gambier-catechin although he gives no melting point for his product (compare A.G. Perkin and Yoshitake T. 1902 81 1163 1173). Freudenberg’s suggestion (“ Die Chemie der natiirlichen Gerbstoffe,” 1920) of the special name paullinia-catechin for this substance is consequently not required. t The graphical formula previously assigned to a-gambier-catechin carb-oxylic acid (Zoc. cit. p. 195) is withdrawn as it was based on the catechin formula of Kostanecki and Lampe (Ber. 1906 39 4007) which has since become untenable (T. 1920 117 973) NIERENSTEIN CATECHUTANNINS. PART I. 25 latter acid gives a pronounced green coloration with alcoholic ferric chloride thus showing that in paullinia tannin the catechol nucleus in one molecule of p-gambier-catechin carboxylic acid is combined directly with the other molecule of p-gambier-catechin carboxylic acid and also with dextrose.E X P E R I M E N T A L . Preparation of Paullinia Tannin. The seeds of Paullinia cupana are extracted in a Soxhlet apparatus with (1) ether and chloroform to remove chlorophyll and fats and ( 2 ) ethyl acetate. The tannin is removed from the latter extract by shaking with a solution of sodium hydrogen carbonate saturated with carbon dioxide. The acidified aqueous solution is again extracted with ethyl acetate the extract dried over anhydrous sodium sulphate and the residue obtained on evaporation dissolved in hot water. The cold solution is shaken with 3 to 5 grams of fat-free caseinogen in order to remove any amorphous tannin (compare T. 1919 115 1330). The filtrate to which a few drops of chloroform are added is allowed to stand in the cold.Crystal-lisation commences after three to four days paullinia tannin separating in small needles. These are filtered and recrystallised several times from water chloroform being added each time. The average yield from 500 grams of the seeds is 12 grams which may be increased to 16 grams on concentrating the filtrates (Found * : C,,H,,0,8*C0,H requires C = 56-2 ; H = 4-4 ; C0,H = 5.5 per cent. Found fM in alcohol = 795,820,516 843 ; M in water = 956, Paullinia tanizin crystallises from water in gray-coloured needles, which melt a t 199-201" carbon dioxide being evolved. At 130°, i t loses two molecules of water of crystallisation (Found : H,O = 4.2 4.3. Calc. H,O = 4.2 per cent.) ; the anhydrous product melts a t 259-261" with evolution of carbon dioxide and decomposition.The tannin is soluble in alcohol ethyl acetate, or acetio acid but not in any other organic solvent. Paullinia tannin gives all the typical colour tests of the catechutannins and C = 55.9 56.3 56.0; H = 4.6 4.4 4.5; C0,H 'f = 5-7 5.6 5.3. 872 840 536. Calc. fM = 812). * Dried at 130". t By the method of Baumann and Kux (2. anal. Chem. 1893 32 129). Preliminary experiments with phloroglucinolcarboxylic acid protocatechuic and 2 3-dihydroxybenzoic acids gave good results by this method which was however found not to be trustworthy in the case of gallic acid and pyrogallolcarboxylic acid 26 NIERENSTEZN CATECHUTANNMS. PART I. is precipitated by gelatin * and alkaloids. The crystalline sodium and potassium salts are obtained by neutralisation of the tannin with the corresponding carbonates.They crystallise from water ; they do not melt below 320" (Found Na = 3-2,2*9. Calc. Na; = 2.7 per cent. Found K = 6.1. Calc. K = 5-7 per cent.). The dextrose content of paullinia tannin is estimated in the same manner as in gallotannin (T. 1921 119 279) (Found dextrose = 21.6, 21.8 22.3 21.9. Calc. dextrose = 22-2 per cent.). The dex-trosazone (m. p. and mixed m. p. 202-204") was also prepared (Found N = 15.9. Calc. N = 15.6 per cent.). Paullinia tannin gives the following optical data t [a]: - 74.4" (10 per cent. solution in water) ; [a?; - 39.1" (8 per cent. solution in alcohol) ; [a]:; - 48-1" (6 per cent. solution in acetone) ; [a] - 56.8" (8 per cent.solution in pyridine). All solutions exhibit muta-rotation which is most evident in the case of the pyridine solution. The rotation falls from [a]" - 56.8" to - 11.4" in sixteen minutes and to - 5.6" in forty minutes when it becomes constant. Action of Emulsin on Paullinia Tannin. To a solution of 10 grams of paullinia tannin in 200 C.C. of water 0.3 gram of emulsin (from bitter almonds) in 75 C.C. of water and 5 C.C. of chloroform are added. The solution on keeping a t 37" for eight days deposits a mass of crystals which are filtered off. The filtrate freed from unchanged paullinia tannin with the aid of lead acetate and hydrogen sulphide contains dextrose which is identified as the dextrosazone (m. p. and mixed m. p. 201-203"). The solid formed by the action of emulsin crystallises from water in small pointed needles and is optically inactive p-gambier-catechin carboxyEic acid which melts at 252-253" carbon dioxide being evolved (Found j C = 57.3 57.5; H = 4-8 4.4.C,,H,,O, requires C = 57-5; H = 4.2 per cent.). The acid is soluble in alcohol ethyl acetate or acetic acid but not in any other of the usual organic solvents. On heating an alcoholic solution of the acid with pyridine for several hours (compare T. 1916,109,593) gambier-catechin is readily obtained. The latter on crystallisation from distilled water melts a t 175-177" which is the melting point * Freudenberg'B statement (Ber. 1920,53 [B] 236) that gambier-catechin is precipitated by gelatin is not correct as repeated observations in this laboratory have shown.His observation is also contrary to all previous data on this point (compare for example Procter " Leather Industries Laboratory Book," 1908 p. 130). j- I 2 4.4 for all optical observations given in this paper. $ Dried at 100" in a vacuum NIERENSTEIN CATECHUTANNINS. PART I. 27 given by A. G. Perkin and Yoshitake (T. 1902 81 1163) for gambier-catechin. This melting point is not depressed when the substance is mixed with authentic gambier-catechin (Found * : C = 62.0; H = 4-9. Calc. C = 62.1 ; H = 4.8 per cent.). The acetyl derivative was also prepared. It melted correctly a t 126125" and showed no depression when mixed with authentic penta-acetyl-gambier-catechin. Diazomethane converts p-gambier-catechin-carboxylic acid into the corresponding pentamethoxy methyl ester which crystallises from light petroleum in long needles melting a t 74" (Found t : C = 63.3; H = 6.5.C,,H,,O requires C = 63.2; H = 6.2 per cent.). When oxidised with potassium permanganate in alkaline solution veratric acid is obtained (m. p. and mixed m. p. 179-180') (Found C = 59.1 ; H = 5.8. Calc. C = 59.3; H = 5.5 per cent.). I n this connexion it is interesting to note that the methyl ester of pentamethoxy-a-gambier-catechin carboxylic acid (m. p. 92") previously described (Eoc. cit.) gives under similar con-ditions m-hemipinic acid and not veratric acid. The inactive p-gambier-catechin carboxylic acid yields a crystal-line strychnine salt long pointed needles from water which melt at 222-223" (Found N = 4.5. Calc. N = 4.2 per cent.).The quinine salt however was found to be the most suitable for the resolution of the acid. The two optically active forms are obtained on fractional crystallisation the salt of the d-form being less soluble than that of the 1-form. The free acids are obtained by decompos-ing thc qiijnine salts with sodium hydroxide in the cold. d- ~-G'umtier-catehin carboxylic acid crystallises from water in microscopic needles which melt a t 249-251" carbon dioxide being evolved (Found $ C = 57.6 ; H = 4.5. Calc. C = 57.7 ; H = 4-2 per cent.). The rotatory power in water (5 per cent. solution) is [ctK + 12.6"; in alcohol (7 per cent. solution) [a]r + 17.6". I-p-Gambier-catechin carboxylic acid crystallises from water in fairly large needles which melt a t 258-261" carbon dioxide being evolved (Found $ C = 57-3; H = 4.3.Calc. C = 57.5; H = 4.2 per cent.). The rotatory power in water (5 per cent. solution) is [ c c ] ~ " - 22.4'; in alcohol (6 per cent. solution) [ a ] r - 31.6". Methylated Paullinia Tannin. Thc methylo-derivative is obtained in excellent yield by the action of diazomethane on an ethereal suspension of paullinia tannin. It crystallises from dilute alcohol or acetone in small needles which melt a t 126-127" [Found t C = 60.2 60.3 60.1 ; H = 6.6 6.5, t Dried in a vacuum over paraffin. * Dried at 100'. $ Dried at 130' 28 NIERENSTEIN CATECHUTANNINS. PART I. 6.4 ; OMe = 43-2,43*0 43.1. C38H2307 (OMe)13 requires C = 60.6 ; H = 6.3; OMe = 43.1 per cent.]. It is soluble in all the usual reagents with the exception of water.The rotatory power in alcohol (5 per cent. solution) is [alga - 31.8" ; in benzene (8 per cent. solution) [a]:6' - 26.4" ; in chloroform (6 per cent. solution) [a]:' - 37.7"; in s-tetrachloroethane (7 per cent. solution) Hydrolysis of Methylated Paullinia Tannin.-Eight grams of the methylo-derivative are hydrolysed in a sealed tube with 100 C.C. of glacial acetic acid as described in the case of methylafed gallo-tannin (T. 1921 119 284). The semi-crystalline solid formed consists mainly of trimethoxy-p-gambier-catechin carboxylic acid, which crystallises from alcohol in small needles melting at 174-175" (Found * C = 60.5; H = 5.5. C1,H2,0 requires C = 60.6; H == 5.3 per cent.). On methylation with diazo-methane it is quantitatively converted into methyl pentamethoxy-(3-gambier-catechin carboxylate (m.p. and mixed m. p. 74"). The acetic acid filtrate gives on addition of water a bulky precipitate, which consists mainly of pentamethoxy-P-gambier-catechin carboxylic acid. It crystallises from alcohol acetic acid or ethyl acetate in pointed needles which melt a t 196-197" (Found * C = 62.2; H = 6.3. C2,M,,08 requires C = 62.4; H = 6.0 per cent.). Diazomethane converts it quantitatively into the methyl ester (m. p. and mixed m. p. 74"). The remaining filtrate contains tetramethyl glucose which is isolated in exactly the same manner as used in the case of methylated gallotannin. It melts at 91-93" and the melting point is not depressed by admixture with authentic tetramethyl a-glucose (Found OMe = 52-2. Calc. OMe = 52.6 per cent.). [E]F - 47.1". This investigation has with many interruptions been in progress since 1908 during which time the author has had the collaboration of Messrs. C. W. Spiers M.Sc. and R. Barr B.Sc. for which he wishes to thank them. He also wishes to acknowledge the help of the late K. C. R. Daniel B.Sc. The author is also indebted to the Director of the Servica Sanitario of Maneos North Brazil for a liberal supply of material used in this investigation and t o the Colston Society of the University of Bristol for a grant in aid of this research. THE UNIVERSITY BRISTOL. [Received November 22nd 1921.1 * Dried at 130"
ISSN:0368-1645
DOI:10.1039/CT9222100023
出版商:RSC
年代:1922
数据来源: RSC
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5. |
Front matter |
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Journal of the Chemical Society, Transactions,
Volume 121,
Issue 1,
1922,
Page 029-032
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J O U R N A L OF THE CHEMICAL SOCIETY. TRANSACTIONS. QommabE of @xrbluatiarr : A. J. ALLMAND M.C. D.Sc. 0. L. BRADY D.Sc. A. W. CROSSLEY C.M.G. C.B.E., D. Sc. F. R. S. C. H. DESCE D.Sc. Ph.D. M. 0. FORSTER D.Sc. Ph.D. F.R.S. I.BI.HEILBBoN,D.S.O. D.Hc.,Ph.D. J. T. HEWIIT M.A. D.Sc. Ph.D., J. C. IRVINE C.B.E. D.Sc. F.R.S. H. KING D.Sc. F.R.S. T. M. LGWRY C.R.E. D.Sc. F.R.S. J. W. MCBAIN M.A. Ph.D. J. I. 0. MASSON M.B.E. D.Sc. J. C. PHILIP O.B.E. D.Sc. Ph.D., R. H. PICKARD D.Sc. Ph.D. F.R.S. N. V. SIDGWICK M.A. Sc.D. F.R.S. J. F. THORPE C.B.E. D.Sc. F.R.S. Sir JAMES WALKEY. D.Sc. LL.D., F.11.S. F.R.S. dbior : A. J. GREENAWAY. @r;sistztnt Qbifax : CLARENCE SMITH D.Sc. 3F;sktairt &rbtxtr : A. A. ELDRIDGE B.Sc. MARGARET LE PLA B.Sc. 1922. Vol. CXXI. Part II. pp. 1177-end. LONDON: GURNEY dz JACKSON 33 PATERNOSTER HOW E.C.4. 1922 PRINTED IN GREAT BRITAIN BY RICHARD CLAY & BONS LIMITED, BUNGAY SUFFOLK
ISSN:0368-1645
DOI:10.1039/CT92221FP029
出版商:RSC
年代:1922
数据来源: RSC
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VI.—The action of nitric oxide on the metallic carbonyls |
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Journal of the Chemical Society, Transactions,
Volume 121,
Issue 1,
1922,
Page 32-35
Robert Ludwig Mond,
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32 MOND AND WALLIS THE ACTION OF V1.-The Action of Nitric Oxide on the Metallic Carbon yb. By ROBERT LUDWIG MOND and ALBERT EDWARD WALLIS. SINCE the discovery of the first of the metallic carbonyls by Mond, Langer and Quincke (T. 1890 57 749) up to the present time, many experiments have been made to induce the metallic carbonyls to enter into a chemical combination. Hitherto all these attempts have failed complete decomposition of the carbonyl invariably resulting ; and the absence of such compounds makes it increasingly difficult to form a satisfactory theory as to the molecular structure of these remarkable compounds. Berthelot who examined the action of numerous reagents on nickel carbonyl (Compt. rend. 1891 112 1347) states that when nitric oxide gas is mixed with nickel carbonyl vapour or is passed into t,he liquid carbonyl a blue compound of complex composition is obtained.We have endeavoured to ascertain the composition of this compound. If a 1 pei' cent. solution of the carbonyl in chloroform or xylene is treated with nitric oxide gas at room temperature it is coloured an intense blue. If in the absence of air the solution is then evaporated a pale blue powder is obtained. This powder ha.s an odour of almonds is insoluble in water or other common solvent, and is immediately decomposed by dilute sulphuric acid with the evolution of oxides of nitrogen. From a st,ronger solution or from pure nicker carbonyl nitric oxide slowly deposits the blue compound. It may be filtered washed with chloroform and dried in a current of carbon dioxide at a temperature not above 60" NITRIC OXIDE ON THE METALLIC CARBONYLS.33 If the temperature reaches go" the powder decomposes with brilliant incandescence. The analysis of the compound was rendered very difficult by the fact that from very large amounts of carbonyl only a few centigrams of the blue powder could be obtained. I n addition to this difficulty nickel carbonyl is rapidly decomposed by the faintest trace of moisture hydroxides or basic carbonates of nickel being produced. The compound or mixture of compounds contained from 37 to 42 per cent. of nickel 15 to 16 per cent. of nitrogen and 10 t o 15 per cent. of moisture. Even after repeated analysis we are unable to state definitely the composition of the compound as we have never succeeded in obtaining it in a pure state.The behaviour of the blue compound towards reagents and the violence with which it decomposes at 90" in an atmosphere of inert gas suggest that it is a compound of nickel and nitric oxide such as Ni(NO),, and that this dissociates a t 90" with subsequent violent reaction of the products. Sabatier and Senderens (Cornpt. rend. 1892 114, 1429) observed that finely divided nickel and nitric oxide react with incandescence at 150". Nitric Oxide and Cobalt Tetracarbonyl. The fact that it is comparatively easy to decompose cobalt tetracarbonyl into the tricarbonyl and carbon monoxide shows that one of the carbon monoxide radicles is only slightly attached to the tetracarbonyl molecule. Hence it seemed probable that it should be possible to replace the slightly bonded radicle by another group.Slowly a t room temperature but almost instantaneously at 40", nitric oxide gas reacts with cobalt tetracarbonyl to form a cherry-red liquid with the evolution of carbon monoxide. We prepared several cubic centimetres of the liquid as follows :-Pure dry nitric oxide was slowly passed through a tube of the carbonyl a t 40". The brown crystals of the carbonyl were rapidly converted into a deep red liquid the vapour of which had a deep red colour. The tube was then heated a t 60" and the liquid dis-tilled in a current of nitric oxide into a cooled receiver. The exit gases were collected measured and analysed 3.1309 grams of Co(CO) gave 2.7112 grams of the red liquid 0.3612 gram of residual Co(CO), and 407.6 C.C.of carbon monoxide (at N.T.P.). Now the 0.3612 gram of Co(CO) resulted by the evolution of 56.4 C.C. of carbon monoxide from 0.4317 gram of Co(CO),. Therefore the 2.7112 grams of the red liquid were obtained by VOL. OXXI. 0 Such in fact proved to be the case 34 MOND AND WALLIS THE ACTION OF the action of nitric oxide on 2.6992 grams of Co(CO), with the evolution of 351.2 C.C. of carbon monoxide or exactly one-fourth of the carbon monoxide in the carbonyl. The yield of liquid was 100.5 per cent. of the weight of the carbonyl reacting with the nitric oxide. Obviously therefore the reaction between nitric oxide and cobalt tetracarbonyl is represented by the following equation : Co(CO) + NO = Co(CO),*NO +- CO. The liquid was analysed (Found Co = 33.41 ; CO = 50.09 ; The red liquid is therefore cobalt izitrosotricarboiayZ Co(CO),*NO.Properties of Cobalt Nitrosotricarbony1.-This substance is a cherry-red mobile liquid very volatile and remarkably stable under water in which it is insoluble. It is miscible in all proportions with alcohol benzene ether chloroform etc. It may be dist'illed in a current of inert gas a t 50-60" with only slight decomposition into cobalt tricarbonyl and nitric oxide. The density a t 14" is 1.5126 and the melting point - 1-05". Only 0-5 C.C. was available for the determination of the boiling point and the usual procedure could not be followed. We therefore used the method of O'Dowd and Perkin (Trans. Faraday SOC., 1908 4 95). This gave excellent results and we found the boiling point of the nitroso-carbonyl to be 78.6" a t 761 mm.The molecular weight as determined by Victor Meyer's method, is 171.7 [Co(CO),*NO requires M = 1731. The vapour pressure is as follows :-NO = 17-30 per cent.). Vapour pressure Vapour pressure Temperature. in mm. of mercury. Temperature. in mm. of mercury. 14" 77 4 5 O 251 23 100 56 361 36 171 66 517 Above 66" the compound slowly decomposes. Nitric Oxide and Cobalt Tricarbonyl. Up to 60" nitric oxide did not react with cobalt tricarbonyl. At 75-80" there appeared to be very slight reaction but the amount of the product was too small to be collected. Nitric Oxide and Iron Carbonyls. The reaction of nitric oxide with cobalt tetracarboiiyl led us to examine the different iron carbonyls with the following results NITRIC OXIDE ON THE METALLIC CARBONYLS.35 There is no reaction between nitric oxide and diferrononacarbonyl a t temperatures up t o 60". At 63" slight reaction occurs and beads of red liquid appear. At loo" the reaction is complex. At first the liquid pentacarbonyl containing some tetracarbonyl, appears and after a time the whole decomposes with much violence. At 70-85" the reaction is regular ; the solid iron carbonyl gradually disappears as the red liquid is formed. In our early experiments we observed that only a small amount of carbon monoxide was evolved and therefore the reaction taking place could not as we had expected be represented by the equation Fe(CO)5*Fe(CO)4 + 4NO = Fe(CQ),*Fe(NO) + 4CO. Further on repeated distillation of the red liquid the colour dis-appea,red and pure pentacarbonyl remained in bulk almost equal to that of the original liquid.In the distilling flask was found a small amount of brown powder which appeared to be a compound of iron and nitric oxide. Several experiments gave the following results :-Carbon monoxide evolved = 1 1 -4-1 1.8 per cent. Yield of the red liquid = 92-95 per cent. [Found Fe = 30 ; NO = 4.34 ; CO = 65-60. C,O1,NFe requires Fe = 33.0 ; NO = 4.4 ; CO = 62.6 per cent.]. The reaction between nitric oxide and diferrononacarbonyl must therefore be represented by the equation ZFe,(CO) + NO = FeN0,3Fe(CO) + 3CO. The theoretical yield would be 92.6 per cent. with the evolution of 11.5 per cent. of carbon monoxide. The composition differs by 3 per cent. in iron and in carbon monoxide from the analysis of the red liquid but greater accuracy could not be expected owing to the difficulties of manipulation, with the very small amounts of liquid available for analysis. The properties of this iron nitroso-carbonyl are very similar to those of the cobalt compound. We have not as yet determined its boiling point freezing point etc. THE LABORATORY, CobluE BANK SEVENOAXS KENT. [Received November 18th 1921.1 c
ISSN:0368-1645
DOI:10.1039/CT9222100032
出版商:RSC
年代:1922
数据来源: RSC
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7. |
VII.—Organo-derivatives of thallium. Part III. Some thalliumdialkyl salts and the preparation of thalliumdiaryl haloids |
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Journal of the Chemical Society, Transactions,
Volume 121,
Issue 1,
1922,
Page 36-40
Archibald Edwin Goddard,
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摘要:
36 GODDARD ORQANO-DERIVATIVES OF THALLIUM. PART III. VI1.-Organo-derivatives of Thallium. Part 111. Some Thalliumdiallcyl Salts and the Preparation of Thalliumdiar yl Haloids. By ARCHIBALD EDWIN GODDARD. I N a previous communication (Goddard T. 1921 119 672) it was shown that thalliumdialkyl haloids reacted readily with silver salts. This has now been utilised in the preparation of thallium-diethyl nitrite and lactate the former showing a similar stability to the corresponding nitrate. Since the author was unable to obtain thalliumdiisopropyl iodide it was thought possible that the larger the aliphatic group attached to the thallium the less stable the compound might become. To test this the thallium-diethyl salts were prepared from the formate up to the n-octoate, and the series shows a fall of melting point with rise of molecular weight and an increase of solubility.The formate however was not obtained pure for analysis but the specimen gave a melting point 240-241". The salts were prepared by the action of thallium-dialkyl hydroxides on the respective acids (see Cahours and Demar-vay Compt. rend. 1879 88 1112). The thalliumdiethyl acetate, m. p. 232-233" appears to be purer than that obtained by Hartwig (Ber. 1874 7 298) which melted a t 212". Three salts in the aromatic series namely thalliumdiethyl p-nitro-benzoate p-iodo benzoate and m-bromobenzoate have also been obtained. Magnesium isobutyl and isoamyl iodides react with thallic chloride in a similar manner to magnesium isopropyl iodide, causing quantitative reduction to thallous iodide.Concentrated hydrochloric acid thionyl chloride ammonia gas, and mercuric chloride do not react with thalliumdiethyl chloride, but iodine trichloride even in the cold violently attacks the corre-sponding bromide with the production of thallous iodide. This appears to be due to the action of chlorine in the presence of iodine, since solid iodine added to a boiling aqueous solution of thallium-diethyl bromide has practically no action. Meyer and Bertheim (Ber. 1904 37 2051) by the action of mag-nesium phenyl bromide on thallic chloride obtained a compound stated to be thalliumdiphenyl bromide which could not be prepared pure for analysis. It was also stated that on heating with fuming nitric acid for several hours in a sealed tube at 300" the substance was not completely decomposed.The author has now obtained thalliumdiphenyl chloride which does not melt a t 288" in a pur GODDARD ORCANO-DERIVATIVES OF THALLIUM. PART 111. 37 state and finds that it is decomposed by fuming nitric acid even in the cold and claims therefore that this is the f i s t organo-derivative of thallium in the aromatic series to be produced. The product was obtained by the interaction of triphenylbismuthine and thallic chloride in cold anhydrous ether. Considerable difficulty was experienced in purifying the compound this probably being due to a secondary reaction which produced small quantities of thallium-phenyl dichloride and inorganic derivatives of thallium the reaction being represented as t,aking place in two stages : 1.2(C,H5),Bi + TlC1 = 2(C6H5),BiC1 + (C,H5),T1C1. 2. (C,H5),T1C1 -+ TlCl = 2CGH5*T1C1,. The reaction represented by the second equation is a t present under investigation. The compound thus formed is identical in properties with that produced from mercury diphenyl and thallic chloride in ethereal solution Triphenylstibine and thallic chloride however react quantitatively and immediately in the cold in accordance with the cquation : (C,H,),Sb + TlCl = (C,H5),SbC1 + TlC1. I n the case of triphenylarsine a precipitate of yellow scales will be obtained after some time ; the reaction is still under investigation. E X P E R I M E N T A L . Thalliumdiethyl Nitrite.-Two grams of thalliumdiethyl iodide and 0.9 gram of silver nitrite were shaken in 70 C.C.of acetone, and the mixture was kept over-night. The precipitated silver iodide was filtered off and extracted with acetone these washings being added to the main filtrate; this on evaporation yielded 1.0 gram of large transparent plates which did not melt a t 290" (Found :. N = 4.54; T1 = 66.14. C,H,,O,NTl requires N = 4.64; T1 = 66-17 per cent.). The nitrite is completely soluble in hot pyridine and insoluble in other organic solvents. Thalliumdiethyl Lactate.-This was prepared in the way described above 1.5 grams of silver lactate being employed. The product (1.5 grams) after four crystallisations from alcohol gave small plates which suddenly decomposed without melting at 2676" (Found T1= 58.13. C,H,,O,Tl requires T1 = 58.04 per cent.). The lactate is soluble in cold water acetone or alcohol and easily soluble in boiling chloroform toluene or ethyl acetate.Thulliumdimethyl Acetate.-By acidifying the hydroxide derived from 2.0 grams of tha,lliumdimethyl iodide with acetic acid and concentrating the solution 1.2 grams of long elongated plates were deposited m. p. 293" (Found T1= 70-17 C,H,O,Tl require 38 GODDARD ORQANO-DERIVATIVES OF THALLIUM. PART III. T1 = 69.56 per cent.). The salt is very soluble in water alcohol, or acetone less soluble in ether or petroleum. Thulliumdiethyl Acetate.-By the interaction of the hydroxide from 3.42 grams of thalliumdiethyl bromide and 0-70 gram of acetic acid 0.8 gram of short whitje needles was obtained. After two crystallisations from water these melted a t 232-233" (Found : T1 = 63.25.C,H,,O,Tl requires T1 = 63.47 per cent.). The solubility of this salt is the same as the above. ThZZiumdiethyl Propionate.-Using in this case 0.5 gram of pro-pionic acid 0.9 gram of fine short needles was obtained on concen-tration rc1. p. 228-229" (Found C = 24-70; H = 4.65; T1 = 60.09 60.54. C,H1502Tl requires C = 25-14; H = 4-51 ; T1 = 60.66 per cent.). The salt is completely soluble in hot alcohol, ethyl acetate toluene or acetone in cold pyridine or chloroform, moderately soluble in hot ether or carbon tetrachloride and slightly soluble in light petroleum. Thlliumdiethyl Valerate.-By the interaction of the hydroxide from 3.42 grams of thalliumdiethyl bromide and 1.07 grams of valeric acid 1.9 grams of small needles were Obtained m.p. 215" (Found C = 29.20; H = 5-21 ; T1= 56.00 56-04. C,Hl,02T1 requires C == 29.85 ; H = 5-27 ; T1 = 56.11 per cent.). The salt is completely soluble in cold alcohol ether pyridine chloroform or hot carbon tetrachloride moderately soluble in cold toluene, acetone or ethyl acetate and insoluble in light petroleum. Thlliumdiethyl Hexoate.-Prepared in the way described above, from 2 grams of the bromide and 0.73 gram of the acid 1.2 grams of product were obtained which on crystallisation from acetone and light petroleum gave transparent needles half an inch in length, softening a t 182" and melting a t 190" (Found T1 = 54-04. C,,H2,0,T1 requires T1= 54-02 per cent.). With the exception of its solubility in light petroleum it agrees in all respects with the valerate.Thulliumdiet7qyZ n-0ctoate.-By means of 0-89 gram of n-hexoic acid a hard solid mass (1-3 grams) insoluble in water was obtained. This was crystallised twice from light petroleum when long trans-parent needles m. p. 159" were deposited (Found T1 = 50.23, 50.03. C,2H250,T1 requires T1 = 50.27 per cent.). The salt resembles the hexoate in its solubility. Thulliumdiethyl p-Nitrobenxoate.-To the hydroxide from 2 grams of thafiumdiethyl bromide was added 0.98 gram of p-nitrobenzoic acid and the mixture was boiled and concentrated. The resulting solid 1.2 grams was crystallised twice from chloroform when micro-scopic needles were obtained m. p. 213" (Found N = 3.59; TI = 47.19. C,,H1,O,NTl requires N = 3.27; T1 = 47.59 per cent.). The salt is completely soluble in cold pyridine moderatel GODDARD ORQANO-DERIVATIVES OF THALLIUM.PART 111. 39 soluble in alcohol or chloroform slightly soluble in carbon tetra-chloride toluene ethyl acetate or acetone and insoluble in etlher or light petroleum. Thulliumdiethyl p-Iodobenxoate.-l*45 Grams of p-iodobenzoic acid being employed 2.0 grams of small white needles containing iodine were deposited. These decomposed with slight explosion a t 220" (Found T1= 39-70. CllH1,O,IT1 requires T1= 40.03 per cent.). The solubility is similar to that of the above nitro-compound. Thullizcmdiethyl m-Bromobenxoate.-This was prepared in the usual manner from 1-18 grams of ?n-bromobenzoic acid. The small white needles (1.6 grams) obtained after two crystallisations from water melted with considerable gas evolution at 220" (Found : T1 = 43-49.The above compound is insoluble in acetone but otherwise resembles the nitrobenzoate. C,,H,,O,BrTl requires T1 = 44.10 per cent.). Action of Iodine Trichloride on Thulliumdiethyl Bromide. To a suspension of 1.45 grams of the bromide in 40 C.C. of light petroleum 1.7 grams of iodine trichloride were slowly added and an immediate liberation of iodine was noticed. After remaining over-night the whole was boiled and filtered. All free iodine having been washed from the residue the latter was found to be thallous iodide (Found I = 61.91. Calc. I = 61.64 per cent.). The same result was obtained when the reaction was carried out in the cold. Action of lMagnesium isoAmyl Iodide and of Magnesium isoButyl Iodide on Thallic Chloride.A solution prepared from 28.0 grams of isoamyl iodide and 3.2 grams of magnesium in dry ether was slowly added to a solution of 7.13 grams of thallic chloride in t,he same solvent. After standing half an hour the solution was decomposed but no trace of organic matter was found in the residue and 6-95 grams of thallous iodide were isolated. As the original thallic chloride should have yielded 7-61 grams quantitative reduction had occurred. The same result was obtained when magnesium isobutyl iodide was used. Action of Triphenylbismuthine on Thullic Chloride. Sufficient dry ether was added to 5.0 grams of triphenylbis-inuthine to effect solution followed by 3-54 grams of thallic chloride in the same solvent. A white precipitate was immediately throw 40 GODDARD ORQANO-DERIVATIVES OF TEALLIUM.PART III. down and after remaining for a short time the whole became solid. The precipitate was filtered off and repeatedly shaken with acetone until the extract gave no solid on evaporation. The residue thus obtained (3-75 grams) was organic and contained thallium but was not pure for analysis. Purification was carried out by crystallising from pyridine then boiling with glacial acetic acid and further crystallising from pyridine the product being thoroughly washed with boiling acetone (Found T1 = 51.44 51.51 51.71 ; C1 = 9.26, 9.01. C,,H,,ClTl requires T1 = 51.84; C1 = 9-01 per cent.). T'humdiphenyl chloride crystallises from pyridine in colourless, microscopic needles which do not melt a t 288" and are slightly soluble in boiling acetic acid alcohol ethyl acetate or chloroform, and insoluble in ether acetone or light petroleum.The above acetone extracts on evaporation gave 4-0 grams of diphenylchlorobismuthine (m. p. 185-186") but no unchanged bismuthine and traces of inorganic thallium products. Preparation of Thalliumdiphenyl Chloride by means of Mercury To a solution of 2-8 grams of mercury diphenyl in 50 C.C. of dry ether 2-5 grams of thallic chloride in the same solvent were added, when a lvhite precipitate was immediately thrown down. After remaining for several hours this was filtered off and extracted with benzene in a Soxhlet apparatus. The benzene removed some mercury phenyl chloride in. p. 250" and the residue after purifica-tion was analysed (Found T1 = 51.51 ; C1 = 9.09. Calc., T1 = 51.84; Cl -= 9-01 per cent.). Diphenyl. Action of Triphenylstibine on Thallic Chloride. To a solution of 5-25 grams of the stibine in 50 C.C. of toluene, 3-1 grams of thallic chloride in 4.8 C.C. of ether were added. An almost white precipitate was immediately thrown down which was filtered off after twenty-four hours. The residue (3.2 grams) was found to be thallous chloride. The filtrate on evaporation, yielded 3.6 grams of triphenylstibine dichloride (m. p. 143") no unchanged stibine being obtained. The process is therefore merely one of chlorination by thallic chloride. The author is indebted to the Research Fund of the Chemical Society for a grant which has partly defrayed the expenses of this investigation. THE UNIVERSITY, EDOBASTON BIRMINGHAM. [Received November 5th 1921.
ISSN:0368-1645
DOI:10.1039/CT9222100036
出版商:RSC
年代:1922
数据来源: RSC
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VIII.—The rate of solution of iron in dilute sulphuric acid both when stationary and under rotation |
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Journal of the Chemical Society, Transactions,
Volume 121,
Issue 1,
1922,
Page 41-44
John Albert Newton Friend,
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THE RATE OF SOLUTION OF IRON IN DILUTE SULPHURIC ACID. 41 VII1.-The Rate of Xolution of Iron in Dilute Sulphwic Acid both when Xtutionary and under Rotation. By JOHN ALBERT NEWTON FRIEND and JOHN HORACE DENNETT. IT having recently been observed that iron does not rust when exposed to the action of water and air in rapid motion (Friend, T. 1921 119 932) it appeared of interest to determine whether or not the rate of solution of iron in acids is likewise retarded by movement. A study has therefore been made of the action of dilute sulphuric acid on Kahlbaum's pure electrolytic iron foil under varying conditions. The work is not yet completed having been temporarily suspended in consequence of the departure of one of the authors; but it was thought desirable to place on record the results so far obtained in view of their important bearing on recent researches on corrosion.Influence of Temperature. Almost nothing is known as to the quantitative effect of rise of temperature on the rate of solution of iron in acid. Small pieces of foil 5 x 2.6 sq. cm. in area were suspended from glass hooks in large jars containing 600 C.C. of N-sulphuric acid and kept at various temperatures for seventy-five minutes. The plates were then removed washed dried and weighed. The results were as follows : Loss in Relative weight. rate of Temp. Gram. Mean loss. solution. 2.3 0-0050 0.0055 1.83 13.0 0.0170 0.0197 6-57 28.7 0-03% 0-0346 11.5 O0 0.003 (talc). - 1.00 0.0060 0-0224 0-0337 45.0 0.0830 0.0786 26.2 58-5 0-2296 0-1893 63-1 0.0742 0-1490 The rate of solution is taken as unity at O" the value being calculated by extrapolation from the curve.The values of the relative rates of solution when plotted against the temperature are seen to lie on a hyperbolic curve analogous to that recently found by Seligman and Williams ( J . Xoc. Chem. Ind. 1916 35 665) representing the rate of solution of aluminium in nitric acid with rise of temperature. C 42 FRIEND AND DENNETT THE RATE OF InJluence of Acid Concentration. This was determined at about 15" by allowing similarly sized plates of foil to the preceding to hang from glass hooks each in four litres of sulphuric acid. The losses in weight after thirty-four hours were regarded as a measure of the rate of solution. The results were as follows : Normality of acid ......0.5 1 2 3 4 6 Loss in weight of iron ... 0.0338 0.0547 0.0961 0'0511 0-1380 0.1531 A remarkable feature is the The experiments have In The results are shown in Fig. 1. breaks in the curve with 2N- and 3N-acid. been repeated several times but always with the same result. FIG 1. 1 L J 7 2 3 4 5 Normality of sulphuric acid. the case of cast iron a maximum rate of solution has been found near this concentration the exact point varying a little with the com-position of the metal. Some results obtaincd by Messrs. Catch andl Hargest working in the authors' laboratory are indicated by the broken line in the figure. The cast iron contained graphite 2.75; combined C 0.55 ; Si 2.28 ; Mn 0.69 ; S 0-076 ; P 1-04 per cent.The coincidence between these maxima is interesting and no satis-factory explanation for either is apparent. Injluence of Notion. The apparatus finally adopted is shown in Fig. 2 and consisted of a 1/4 H.P. electric motor capable of giving 1700 revs. per min. Its pulley was connected by a small leather driving-belt with one screwed on to a gun-metal axle the lower end of which carried th SOLUTION OF IRON IN DILUTE SULPHURIC ACID ETC. 43 iron foil in the form of a disk 7.5 cm. in diameter. This disk was fixed with a nut on to the axle contact with both nut and axle being prevented by the use of rubber washers. The axle was supported verti-cally by a rigid clamp free rotary motion being obtained with ball bearings as in a cycle hub. By using various sizes of pulleys speeds ranging from 145 to 4000 revs.per minute were obtainable. These were read off a t intervals during the experiments from a speedometer. The lower end of the axle carrying the iron disk was lowered into a glass tank, the internal walls of which possessed raised vertical ribs-a device that greatly reduced the tendency of the liquid to swirl round with the rotating disk. The experiments lasted for thirty minutes each and the volume of liquid was the same in every FIG 2. FIG. 3. 0 1000 2000 3000 4000 Recolulions per minute. case namely 1 litre. The amount of iron dissolved was estimated by titration with permanganate. Before each experiment the iron disk was carefully polished with emery the same disk being used c* 44 DWRXANS THE AOTION OF SULPHURYL CHLORIDE throughout in order to avoid fluctuations due to chemical and physical differences in the metal so characteristic of different specimens of even the purest forms of iron.The results are shown graphically in Fig. 3. It will be observed that : 1. The different concentrations of acid yield almost identical results at the same velocities. 2. The rate of solution is directly proportional-within the error of experiment-to the velocity of rotation. Even a t 4000 revolu-tions corresponding with a rim velocity of 35 miles per hour, there is no sign of falling off in the rate of solution. Evidently, therefore solution of iron in acid is a different process from the corrosion of iron in aerated water. In the latter case corrosion ceases at a velocity of 3 to 5 miles per hour. Infzuence of Colloids. A few experiments have been carried out on the rate of solution of stationary iron in sulphuric acid in the presence of protective colloids such as gum acacia. It is found that dilute solutions of this gum greatly retard the solution of the metal just as they have been shown (Friend Zoc. cit.) to retard the corrosion of iron in neutral solution. Mr. Trobridge working in the authors’ laboratory, has shown that a similar retardation occurs with hydrochloric acid so that this action of the colloids appears to be general. CHEMISTRY DEPARTMENT, BIRMINGHAM MUNICIPAL TECHNICAL SCHOOL. [Received November 12th 1921.
ISSN:0368-1645
DOI:10.1039/CT9222100041
出版商:RSC
年代:1922
数据来源: RSC
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9. |
IX.—The action of sulphuryl chloride on organic substances. Part I. Simple monosubstituted benzenes |
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Journal of the Chemical Society, Transactions,
Volume 121,
Issue 1,
1922,
Page 44-49
Thomas Harold Durrans,
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44 DWRXANS THE AOTION OF SULPHURYL CHLORIDE IX.-The Action of Xulphuryl Chloride on Organic Substances. Part I. Simple Monosubstituted Benzenes. By THOMAS HAROLD DURRANS. SULPHURYL chloride reacts readily with a large number of organic substances generally functioning either as a chlorinating or as a dehydrating agent. Its action as a chlorinating agent is frequently, but not always similar to that of chlorine and sometimes to that of phosphorus pentachloride whilst in its dehydrating action it resembles sulphur trioxide. Thus in the absence of a catalyBt i ON ORGANIC SUBSTANCES. PART I. 45 chlorinates benzene toluene phenol anisole phenetole or aniline, and with salts of acids such as sodium benzoate or acetate it yields the corresponding acid anhydride and acid chloride (compare Dubois Bull.Acud. roy. Belg. 1876,42 126 ; Wohl D.R.-P. 139552 ; Wenghoffer Ber. 1877 10 441; Peratoner Guxxetta 1894 24 i, 236). Although a large amount of work has already been done in this connexion there is a lamentable lack of information regarding the action of sulphuryl chloride on the organic substances in common use. This investigation is designed to contribute a small addition to our existing knowledge in this direction. The conditions of experiment have been those obtaining when the organic substance is boiled under atmospheric pressure for several hours with a large excess of sulphuryl chloride; consequently the products isolated represent the final products to be obtained in such circumstances the isolation of any intermediate product not having been aimed at.The table shows briefly the results obtained : Organic Substance. Benzaldehyde Phenylacetonitrile Acetophenone Benzophenone Nitrobenzene Sodium benzenesulphonate Sodium phenoxide (aqueous) Triphenyl phosphate Sodium phenylacetate Benzamide ?S 9s (anhydrous) Y ? , m presence 4 Product. Benzoyl chloride. Phenyldichloroacetonitrile. ww-Dichloroacetophenone. No action. Y Y ?P Y Y 9 ) p - Chlorophenol. 2 3 4 6-Tetrachlorophenol. No action. 3f iron Tri-p-chlorophenyl phosphate. Phenylacetic anhydride and phenyl-Traces of benzonitrile only. acetyl chloride. Phenylethyl alcohol yields an unstable product probably a mixture of phenylethyl sulphate and phenylethyl chloride the reaction being similar to that with benzyl alcohol (Behrend J .p r . Chem. 1877 [ii] 15 23). E X P E R I M E N T A L . Benzaldehyde.-Sulphuryl chloride (5 moh.) was distilled on to benzaldehyde (1 mol.); no sensible reaction took place. The mixture was slowly distilled until the excess of sulphuryl chloride was removed the residue being distilled under reduced pressure. After repeated distillation a fraction b. p. 195-200"/760 mm., was obtained (benzoyl chloride boils a t 198") the only other substance present in any appreciable quantity being benzaldehyde ; a small amount of tarry matter was formed (Found C1 = 24-69. Calc., C1 = 25-27 per cent.) 46 DURRANS THE ACTION OF SULPHURYL CHLORIDE The substance was identified with benzoyl chloride by conversion into benzoic acid and ethyl benzoate.The action of sulphuryl chloride on benzaldehyde is therefore similar to that of chlorine, but differs in that the simultaneous formation of traces of benzyl chloride does not appear to take place. PhenyEacet0nitriZe.-This substance (1 mol.) was treated with sulphuryl chloride (5 mols.) as- in the foregoing experiment ; the residual liquid distilled at llS0/2O mm. The fraction was highly lachrymatory but otherwise almost! devoid of odour. It would not solidify when cooled to -15" (Found C1 = 38.52. C,H,*CCI,.CN requires C1 = 38.18 per cent.). The substance when boiled with alcoholic sodium hydroxide solution immediately deposited sodium chloride and evolved first a slight odour of hydrocyanic acid and then one of ammonia. On pouring t{he mixture into water and acidifying benzoic acid was deposited ; this twice crystallised from water melted a t 120.5".The acid was further identified by means of a mixed-melting point determination and of its ethyl ester b. p. 213". The substance heated on a steam-bath with an equal weight of 75 per cent. sulphuric acid for three hours yielded on cooling a precipitate of benzoic acid. It is clearly phenyldichloroacetonitrile and is identical with the substance obtained by Claisen (Ber. 1879, 12 626). Acetophenone.-Sulphuryl chloride (3 mols .) was slowly distilled on to acetophenone (1 mol.) and a vigorous reaction ensued. When this had subsided the excess of sulphuryl chloride was slowly distilled off; tIhe residual liquid distilled a t 124-140"/12 mm. By repeated fractional distillation a fraction boiling a t 121-122" I 10 mm.and at 245"/760 mm. was obtained which could not be made to solidify even a t - 10" (Found C = 50.12 ; H = 3.16; C1 = 38.45. C,H60Cl requires C = 50.79; H = 3.17; C1 = 37.68 per cent.). When the substance was boiled for several hours with N/10-aqueous-alcoholic silver nitrate only a trace of silver chloride was formed this probably arising from an impurity in the substance. The substance was not oxidised by chromic acid mixture but yielded readily to alkaline permanganate solution a faint odour of chloro-form being evolved. This chloroform probably arose from a trace of the trichloride C6H,*CO*CC1, the presence of which would account for the slightly high chlorine content. From the mixture obtained by the alkaline permanganate oxidation benzoic acid was isolated in good yield.The chief substance resulting from the reaction between aceto-phenone and sulphuryl chloride is therefore ww-dichloroaceto ON ORGANIC SUBSTANCES. PART I. 47 phenone and is identical with the ketone obtained by Gautier (Ann. Chim. Phys. 1888 [vi] 14 348). Sodium Phenoxide.-The action of sulphuryl chloride on the sodium salts of certain acids is to produce the acid anhydride and the acid chloride. It was thought possible that with sodium phenoxide diphenyl et,her or phenyl sulphate might result. There was also the possibility that in aqueous solution a reaction. similar to the Schotten-Baumann reaction might take place whilst a fourth possibility was that its action would be similar to that with phenol, where p-chlorqhenol is obtained.Two experiments were therefore conducted. A large excess of sulphuryl chloride was slowly distilled on to carefully dried sodium phenoxide a very vigorous reaction taking place. The excess of sulphuryl chloride was distilled off and the solid remaining extracted with benzene. After the removal of the benzene from the extract a liquid remained which had an initial boiling point of about 150'/17 mm. A fraction b. p. 190-210'/ 17 mm. was collected and this solidified on cooling. The residue was black and evolved hydrogen chloride. The solid was insoluble in sodium carbonate solution but readily soluble in sodium hydroxide solution from which it was precipi-tated on acidifying. It did not contain sulphur and was therefore not phenyl sulphate.Crystallised three times from ether it melted a t 65-66'. Its benzoyl derivative had m. p. 116" (compare Zincke and Wallbaum AnnnEen 1891,261,246) (Found C = 31.2 ; H = 1.22 ; C1 = 61.4. C,H,OCI requires C = 31.0 ; H = 0.86 ; C1 = 61.2 per cent.). The fractions of lower boiling point obtained in small yield were redistilled and a small fraction b. p. about 217'/760 mm. was obtained (p-chlorophenol boils a t 217'). This on cooling and seeding with a crystal of p-chlorophenol solidified immediately and after drying on a porous tile had m. p. 40". The substance was identified with p-chlorophenol. The substances produced by the action of sulphuryl chloride on anhydrous sodium phenoxitfe are therefore p-chlorophenol and a tetrachlorophenol probably the 2 3 4 6-isomeride obtained by Zincke and Schaum (Bey.1894 27 549). The reaction in aqueous solution was conducted as follows : ninety-four grams of phenol were dissolved in a solution of 40 grams of sodium hydroxide in 200 grams of water and the excess of phenol was removed by boiling under diminished pressure. Seventy grams of freshly-distilled sulphuryl chloride were then added to the cold solut'ion with shaking and cooling in iced water. An oil formed and was separated dried and distilled the b. p 48 THE ACTION OF SULPHURYL CHLORIDE ETC. PART. I. 86"/22 mm. rising to 145"/16 mm. The distillate which solidified on cooling was dissolved in sodium carbonate solution and a small portion of insoluble oil (phenol) removed by extraction with ether ; on acidifying an oil was obtained which had b.p. 215-217" (p-chlorophenol boils at 217") and m. p. 42". The substance was identified with p -c hlorophenol. Triphnyl Phosphte.-Sulphuryl chloride is almost entirely without action on triphenyl phosphate when boiled with it under atmospheric pressure (compare Peratoner Gaxxetta 1898 28 i, 197) but in the presence of quite small quantities of iron tri-p-chlorophenyl phosphate is readily formed. No reaction having been found to take place between triphenyl phosphate and sulphuryl chloride under the usual conditions an addition of 1 per cent. of 60-mesh iron filings was made and the mixture heated under reflux for ten hours. After the excess of sulphuryl chloride had been distilled off the residue was poured into water well washed and neutralised.The solid after crystallis-ing three times from alcohol melted at 113" (Found C = 49.95 ; H = 3-00; C1 = 24.46. C,,H,,O,Cl,P requires C = 50.29; H = 2-79; C1 = 25.08 per cent.). The substance was hydrolysed with 2N-alcoholic sodium hydroxide the product poured into water acidified extracted wit,h benzene and the extract distilled. The main fraction after removal of the benzene boiled at 210-220" and when seeded with p-chloro-phenol solidified (m. p. 40"). Dried on porous tile and reprecipitated from sodium carbonate solution the substance melted at 43" (Found C1 = 27.22. It follows therefore that the substance obtained by the action of sulphuryl chloride on triphenyl phosphate in the presence 'of iron is tri-p-chlorophenyl phosphate.Benxamide.-Sulphuryl chloride (9 mols .) was distilled on to benzamide (1 mol.) no apparent reaction ensuing. The sul-phuryl chloride was very slowly distilled off and the residue distilled under reduced pressure. A small early fraction was obtained and the contents of the distillation flask then solidified. The solid, crystallised twice from benzene had m. p. 124-125" and b. p. 290" and was therefore unchanged benzamide (Found C = 69.61 ; H = 5.67. The early fraction from the distillation had b. p. 80"/15 mm. and an odour similar to that of benzaldehyde. It dissolved in hot water and was redeposited on cooling. When it was boiled with sodium hydroxide solution ammonia was slowly evolved and on acidifying, benzoic acid was deposited (m.p. 120"). The substance is evidently benzonitrile (Found N = 13.57. Calc. N = 13.59 per cent.) Calc. C1 = 27.63 per cent.). Calc. C = 69.4; H = 5.79 per cent.) FORMATION OF SUBSTITUTED SUCCINIC ACIDS FROM ESTERS ETC. 49 formed by the dehydration of the benzamide. Sulphuryl chloride therefore does not attack benzamide except to a small extent to form benzonitrile. Xodium PhenyZacetate.-Freshly-distilled sulphuryl chloride (1.5 mols.) was slowly run on to anhydrous sodium phenylacetate (m.. p. about 150"). The excess of sulphuryl chloride was removed in the cold under diminished pressure and the residue distilled as far as possible a fraction boiling up to 100"/12 mm. being obtained. The solid remaining in the flask was extracted with benzene and the extract distilled.After the removal of the benzene a fraction, b. p. 130-168"/12 mm. was obtained which solidified. The solid, twice crystallised from benzene had m. p. 75". 1.235 Grams, boiled with AT-aqueous-alcoholic sodium hydroxide consumed 9.8 c.c. equivalent to 1.245 grams of phenylacetic anhydride. On acidifying a more concentrated similar solution phenylacetic acid was deposited which twice crystallised from water had m. p. 76". The early fraction boiling up to 100"/12 mm. was redistilled and a small fraction b. p. 93-96"/12 mm. obtained which fumed slightly in the air. This substance on hydrolysis yielded phenyl-acetic acid m. p. 76" and was evidently phenylacetyl chloride (Found C1 = 23.06. The products of the reaction between sulphuryl chloride and anhydrous sodium phenylacetate are phenylacetic anhydride and phenylacetyl chloride. Calc. C1 = 22.98 per cent.). I have to express my indebtedness to Mr. F. Hall of this laboratory for most kind assistance in conducting the combustions necessary for this investigation. THE DYSON PERRINS LABORATORY, OXFORD. [Received June 16th 1921.
ISSN:0368-1645
DOI:10.1039/CT9222100044
出版商:RSC
年代:1922
数据来源: RSC
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X.—The formation of substituted succinic acids from esters ofαβ-unsaturated acids |
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Journal of the Chemical Society, Transactions,
Volume 121,
Issue 1,
1922,
Page 49-54
Lucy Higginbotham,
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摘要:
FORMATION OF SUBSTITUTED SUCCINIC ACIDS FROM ESTERS ETC. 49 X.-The Formation of Substituted Succinic Acids from Esters of up- Unsaturated Acids. By LUCY HIGGINBOTHAM and ARTHUR LAPWORTH. IT was shown by Bredt and Kallen (Annulen 1896 293 350) that hydrogen cyanide forms compounds with alkylidenemalonic esters, addition taking place at the ethylenic linking and numerous instances of similar additions to the molecules of @-unsaturated ketones and nitriles have since been found. These may all be re 50 RIGGINBOTHAM AND LAPWORTH THE FORMATION OF garded as special instances of a general type of additive process represented as follows : > C = < - X - Y + H * ( C N ) -+ >Y-kH-X-Y, where the attached signs are used to indicate what have been termed the " polarities " of the atoms or groups concerned (compare Fry, 2.physikal. Chem. 1911 76 386 398 591; J . Am,er. Chem. SOC., 1908,30,34 ; 1912,34,664 ; 1914,36,284 et,c. Hancke arid Koess-ler J . Amer. Chem. Xoc. 1918 40 1726. Compare also Vorliinder, Ber. 1919 52 [B] 263 ; Annual Reports 1920 16 88 ; Manchester Memoirs [Trans. Munch. Lit. and Phil. Xoc. 1930 31). The atom Y is regarded as the " key-atom " (Munch. Memoirs loc. cit.) and is usually bivalent oxygen or tervalent nitrogen. Although hitherto the hydrogen cyanide additive process has been observed only in such cases where - X - Y is represented by the >CO of ketones and carboxylic derivatives and by the - CiN group of nitriles there is good reason t,o believe that union of X and Y by a double or treble linking is not essential since the addition of sodium hydrogen sulphite (which otherwise is certainly regulated by the same laws as the addition of hydrogen or potassium cyanide) takes place to the ethylenic linking of cinnamyl alcohol, C,H,*CH :CEI*CH OH.It is probable however that a doubly or trebly linked arrangement of X and Y is the most effective. There are other conditions which also greatly influence the ease CN + - f 7 + --of the additive process. Thus for example the " key-atoms " in certain positions often increases alkylidenecyanoacetic acids, presence of two reactivity as in +-which absorb hydrogen cyanide at the ethylenic linking under conditions in which the corresponding nitriles or unsubstituted acids do not react appreciably (P. 1904 20 246).Again whilst as the present authors have found the esters of alkylidenemalonic acids react very rapidly with cold solutions of potassium cyanide the free acids (or rather their salts since the free acids cannot exist in presence of potassium cyanide) do so relatively slowly if a t all. This observation is quite in accordance with the view that the hydrogen cyanide additive process is regulat.ed mainly by the speed a t which cyanidion att'aches itself to the unsaturat,ed molecules, for it is evident that t h e addition of hydrogen cyanide to the ionise SUBSTITUTED SUCCINIC ACIDS FROM ESTERS ETC. 51 salt of an unsaturated carboxylic acid would then tend to be depressed by the mutual repulsions between the cyanidions and the unsaturated anions of the salt of the carboxylic acid ; and it seems quite probable that the addition takes place almost exclusively to the un-ionised molecules of the salt.The addition of hydrogen cyanide to the simple ap-unsaturated acids their salts esters or amides has not hitherto been observed. The considerations to which aftention hams been directed in the preceding paragraph rendered it probable that the addition was likely to be effected most readily by using the esters or amides of the acids rather than the free acids or their salts. The authors have confirmed this and incidentally found that surprisingly high yields of mono-substituted succinic acids are obtained by boiling the esters of unsaturated acids of the type Alk*CH:CH-CO,H with aqueous alcoholic solutions of potassium cyanide.In the initial stage of the process no doubt the additive product is formed in accordance with the equation Alk*CH:CH*CO,Et + KCN + H20 = AZk*CH(CN)*CH,*CO,Et + KOH, but partial hydrolysis of the product ensues owing to the potassium hydroxide formed and ammonia is rapidly evolved. No special attempts have been made to isolate the intermediate products, but the crude products were a t once further hydrolysed. In this way crotonic acid yielded methylsuccinic acid and Aa-nonenoic acid gave hexylsuccinamic acid both in excellent yield. The yields of substituted succinic acid are not nearly so good when there are two alkyl groups instead of one on the P-position or if the alkyl group is replaced by an aryZ group but small quantities of phenyl-succinic acid and of as-dimethylsuccinic acid were obtained from the ethyl esters of cinnamic acid and pp-dimethylacrylic acid respectively.E X P E R I M E N T A L. Methylsuccinic Acid from (a) Ethyl Crotonate and (b) Sodium Crotonate. (a) Ethyl crotonate (5 grams) was dissolved in alcohol (20 c.c.) and heated on the steam-bath wiOh potassium cyanide (3 grams; 1 md.) dissolved in water (6 c.c.). Some ammonia was evolved and the solution became yellow. After four hours excess of barium hydroxide solution was added and the boiling continued until ammonia ceased to be evolved. The whole was evaporated to dryness and then heated with concentrated nitric acid in order to decompose any crotonic acid. After removing excess of nitric aci 52 HIQQINBOTHAM AND LAPWORTH THE FORMATION OF and working up the residue by extraction with ether 5 grams of orystalline solid were obtained which after sha.king with chloroform and recrystallisation formed colourless prisms melting a t 110" and had all the properties of methylsuccinic acid.The equivalent determined by titration with standard alkali, was 65.3 whilst a dibasic acid C5HsOa requires 66. The identification of the acid was completed by preparing from it the anilic acid and the anil which melted at 150" and 101.5-103" respectively. Substitution of boiling amyl alcohol for ethyl alcohol in the above synthesis in the hope of increasing the speed of reaction by use of a higher temperature led to very unsatisfactory results. With methyl alcohol as solvent the yield of methylsuccinic acid from 5 grams of ethyl crotonate was only 3 grams.( b ) Five grams of crotonic acid just neutralised with 40 per cent. aqueous sodium hydroxide were boiled with 3.3 grams of potassium cyanide in 10 C.C. of water during which time much ammonia was evolved. After ten hours excess of sodium hydroxide was added and the heating continued in order to hydrolyse any nitrile or amide present On working up the product and destroying unchanged orotonic acid by means of nitric acid 0.7 gram of methylsuccinic acid waa obtained. n- Hexylsuccinic Acid from Ethyl Aa-Nonenoate. Nonenoic acid was prepared from heptaldehyde by Harding and Weizmann's method (T, 1910 97 299) and converted into its ethyl ester. The ester (4.6 grams) was dissolved in ethyl alcohol (20 c.c.) and heated to boiling for five and a half hours after addition of potassium cyanide (2 grams) dissolved in water (8 c.c.).Ammonia was slowly evolved during the whole period. Excess of 30 per cent. aqueous sodium hydroxide was then added and the boiling continued for about an hour when evolution of ammonia ceased. The alkaline solution after cooling was acidified with dilute sulphuric acid and the resulting white precipitate (4 grams) of hexylsuccinamic acid, C6H13*CH( CO*NH,)*CH,-CO,H filtered off. This product crystal-lised from dilute alcohol in long needles melting at 125-126" and its equivalent was found to be 200 the number theoretically required for a monobasic acid C10H1903N being 201. n-Hexylsuccinic acid was prepared from the amic acid by boiling for about twenty minutes with 40 per cent.sulphuric acid the solid acid which separated on cooling being recrystallised from dilute nitric acid It melted a t 83-84' and its identification was com-pleted by converting into its anhydride and its anilic acid whic SUBSTITUTED SUCCINIC ACIDS FROM ESTERS ETC. 53 melted a t about 53" and at 120-121" respectively (compare Thorpe and Higson T. 1906 89 1470 who give the melting points of these two derivatives as 57" and 122" respectively). The foregoing method is probably the most satisfactory one for preparing n-hexylsuccinic acid which is otherwise rather trouble-some to obtain in pure condition. as-Dimethylsuccinic Acid from Ethyl p-Dimethylacrylute. Potassium cyanide (2.5 grams) dissolved in water (8 c.c.) was added to a solution of ethyl pp-dimethylacrylate (5 grams) in alcohol (20 c.c.) and the whole heated for six hours on the steam-bath.Excess of aqueous barium hydroxide solution was then added, and the whole boiled for several hours then acidified with excess of concentrated hydrochloric acid and evaporated to dryness, during which process the odour of dimethylacrylic acid was very evident. The residue on extraction with ether yielded only 0.5 gram of as-dimethylsuccinic acid melting at 136-137"; it was identified by means of its sparingly soluble calcium salt and by the properties c/f its anilic acid which corresponded precisely with those ascribed to it by Auwers (Annalen 1896 292 189). On repeating the above synthesis but prolonging the action of the potassium cyanide to three and a half days and hydrolysing the product for four hours with excess of 30 per cent.aqueous sodium hydroxide solution the yield of crude solid dimethylsuccinic acid obtained was 1.4 grams-approximating to 30 per cent. of the quan tity theoretically possible. P a-Dimethylacrylic ester thus appears to react with potassium cyanide much more slowly than does ethyl crotonate or nonenoate. Phenylsuccinic Acid from Ethyl Cinnamate. Ethyl cinnamate reacts almost as slowly with potassium cyanide as does ethyl Pp-dimethylacrylate. After heating 5 grams of the cstcr with 1.8 grams of potassium cyanide in 5 C.C. of water and 20 C.C. of alcohol hydrolysing the product with baryta and working up the resulting acids by acidification extraction with ether and distillation with steam to remove unchanged cinnamic acid rather less than 1 gram of phenylsuccinic acid (m.p. 166". Equivalent = 96.2; calc. equiv. = 97) was obtained. Summary. Methylsuccinic acid and n-hexylsuccinic acid are readily obtained in excellent yield by heating the ethyl esters of crotonic acid an 54 UODDARD AND GFODDARD METALLIC DERIVATIVES Aa-nonenoic acid respectively with aqueous-alcoholic potassium cyanide and hydrolysing the crude products. The esters of pp-dimethylacrylic acid and cinnamic acid react slowly with this reagent and give relatively poor yields of as-dimethylsuccinic acid and phenylsuccinic acid respectively. Sodium crotona.te reacts slowly with aqueous potassium cyanide solution and some methylsuccinic acid may be obtained from the product. The work is being continued. The authors desire to acknowledge their indebtedness to the Department of Scientific and Industrial Research for a grant with the aid of which the work has been carried on. ORGANIC CHEMICAL LABORATORIES, THE UNIVERSITY MANCHESTER. [Received December lst 1921.
ISSN:0368-1645
DOI:10.1039/CT9222100049
出版商:RSC
年代:1922
数据来源: RSC
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