摘要:

Z OF THE CHEMICAL SOCIETY. darnmitha of @ublicrrfim : Chairman N. V. SIDGWICK M.A. Sc.D. F.R.S. H. B RAKER C.B.E D.Sc. F.R.S. E. C. C. RALP C.B.E. F.R.S. H. RASSETT D.Sc. Ph.D. 0. L. BEADY D.Sc. A. W. CECOSSLRY,’ C.M.G. D.Sc., H. W. DUDLEY O.B.E. M.Sc.,Ph.D. U. R. EVANS M.A. J. J. Fox O.B.E DSc. C. S. GIBSON O.B.E. M.A. W. N. HAWOETH D.Sc. Ph.D. I. M. HEILBRON D.S.O. D.Sc. T. A. HENRY D.Sc. F.R.S. T. M. LOWRY C.B.E. D.Sc. F.R.S. J. W. MCBAIN Ph.D. F.R.S. H. MCCOMBIE D.S.O. U.C. D.Sc. W. H. MILLS Sc.D. F.R.S. T. S. MOORE &LA. B.Sc. G. T. MORQAN O.B.E. D.Sc. F.R.S. J. C. PHILIP O.B.E. D.Sc. F.R.S. R. H. PICKARD D.Sc. F.R.S. T. S. PEICE O.K.E. D.Sc. F.R.S. F. L. PYMAN D.Sc. F.R.S. J. F. THORPE C.B.E. D.Sc. F.R.S. W. P. WYNNE D.Sc. F.R.S.J. I. 0. BIASSON M.B.E. D.Sc. Qbitor : CLARENCE SMITH D. Sc. aitbexer : MARGARET LE PLA B.Sc. 1924. Vol. CXXV. Part I. pp. 1-1403. LONDON: GURNEY & JACKSON 33 PATERNOSTER ROW E.C. 4. 1924 PRINTED IN GREAT BRITAIN BY RICHA~W CLAY & SONS. LXNITIW), BUNOAY SUF’YOLK C O N T E N T S PAPERS COiVIMUNICATED TO THE CHEMICAL SOCIETY. 1.-A Synthetic Fat containing a Methylglucoside Residue. By JAMES COLQUHOUN IRVINE and HELEN SIMPSOH GILCHRIST 11.-The Condensation of Mannitol with Olive Oil. By JAMES COLQUHOUN bMNE and HELEN SIMPSON GILCHRIST . IlI.-The Constitution of Polysaccharides. Part VII. Esparto Cellulose. By JAMES COLQTTHOTM IRVINE and EDMMUND LANGLEY HIRST . . IV.-Camphorylcarbamates and their Physiological Action. By HANS EDUARD FIERZ-DAVID and WALTER MULLER V.-The Determination of Surface Tension from the Marrimurn Pressure in Bubbles.Part 11. By SANOEL SUGDEN . V1.-The Variation of Surface Tension with Temperature and some Related Functions. VII.-Stereoisomerkm and Local Anaesthetic Action in the p-Eucaine Group. Resolufion of p- and iso-fLEucaine. B~&ROLD&NG . VIII.-The Rapid Admixture of Hot Combustible Gases with Air. By PRANK MAURICE CUY and WILLIAM EDWARD GARNER . =.-The Dissociation Constant of Boric Acid. By EDMUHD BRYDGES RUDHALL PRIDEAUX and ALERED THOASAS X.-The Reaction between Copper and Nitrogen Peroxide. By JAMES RITCHIE PARK and JAMES RIDDICK PARTINGTON =.-The Influence of Catalysts on the Production of Potass-ium Perchlorate by the Action of Heat on Potassium Chlorate.By WALTER FARMER and Jams BRIERLEP FIRTH . XII.-The Additive Formation of Four-membered Rings, Past 111. The Nomenclature of Four-membered fIetero-cyclic Rings and the Formation and Properties of some Derivatives of Methylene-1 2 4-oxadi-imine. By Ckms-TOPHER KELK INGOLD . By SAWEL SUGDEN . WARD . PAGE 1 10 15 26 27 32 41 57 69 72 82 87 X1II.-The Chlorohydrins of p-Pinene. By GEORGE GERBLI) HENDERSON and CARL A ~ o ~ s m s KERR . . 10 iv CONTENTS. X1V.-Some Oxidation Products of p-Pinene. By GEORGE GERALD HENDERSON and DONALD CHISHOLM . XV.-Preparation of 2 4 2' 4'-Tetrahydroxybenzophenone. By JOHN BALDWIN SHOESMITH and JOHN HALDANE . XV1.-The Decomposition of Substituted Carbamyl Chlorides by Hydroxy-compounds.Part I. The Reaction between Phenylmethylcarbamyl Chloride and Ethyl Alcohol at Different Temperatures. By TUDOR WILLLAMS PRICE XVI1.-Piperitone. Part VII. The Constitution of Piper-itone. By JOHN READ HENRY GEORGE SMITH and REGINALD SLATER HUGHESDON . XVII1.-The System Antimonious OxideHydrochloric Acid-Water. By CHARLES LEA and JOHN KERFOOT WOOD . X1X.T-Bromophenyltrimethylammonium Perhalides By THOMAS HAROLD READE . XX .-p- Iodophenyltrimethylammonium Perhalides . By THOMAS HAROLD READE and STUART ANDERSON SIM . XX1.-The Dependence of Polarisation-overvoltage on Hydroxyl- and Hydrogen-ion Concentration. Part I. Polarisation-overvoltage of an Antimony Cathode in Aqueous Alkaline Solution. By HENRY JULIUS SALOMON SAND and EDWARD JOSEPH WEEKS XXI1.-The Additive Formation of Four-membered Rings.Part IV. The Influence of Temperature on the Tendency Towards Self-addition of the Nitroso-group. By CHRIS-TOPHER KELK INCOLD and HENRY ALE'RED PIQGOTT . XXII1.-The Constitution of Disulphoxides. Part I. By SAMUEL SMILES and DAVID TEMPLETON GIBSON . XX1V.-Tetrachloroioddes of Organic Bases. By FREDERICK DANIEL CHATTAWAY and FRANK LESLIE GARTON XXV.-A Synthesis of Pyrylium Salts of Anthocyanidin Type. Part 111. A New Synthesis of Pelargonidin Chloride. By DAVID DOIG PRATT and ROBERT ROBINSON . XXV1.-A Synthesis of Pyrylium Salts of Anthocyanidin Type. Part IV. Flavylium Salts Related to Chrysin Apigenin, and Luteolin. By DAVID DOIG PRATT ROBERT ROBINSON and PERCY NOEL WILLIAMS . XXVI1.-Some Derivatives of Benzopyrylium.By ROBERT EOBINSON and (in part) HERBERT GRACE CRABTREE, CHINYANN KUWA DAS W~LFRID LAWSON ROBERT WINSTANLEY LUNT BERNARD HOLTOM ROBERTS and PERCY NOEL WILLIAMS . XXVIII.-Some Benzopyrylium Salts. By LESLIE RANDAL RIDGWAY and ROBERT ROBINSON . . PAGE 107 113 115 129 137 148 157 160 168 176 183 188 199 207 21 CONTENTS. V PAGE XX1X.-A Quantitative Study of the Interaction of Glucose and Phenylhydrazine. By EDMUND KNECHT and I!RANK PEBERDY THOMPSON . XxX.-Synthesis of the Higher Monoalkylmalonic Acids. By (MRS.) GERTRUDE MAUD ROBINSON -1.-Reduction Products of the Hydroxyanthraquinones. Part IV. By JOHN WALTER ECBOYD HALLER and AJFZHUR GEORGE PER= . XXXI1.-Estimation of Ferrocyanides.By WILLIAN M m -XXXIII.4hloronitrobenzenes and Thiocarbamides. By XXXIV.-Intermittent Current Electrolysis. Part 111. . DOCH CUMNING. JOHN TAYLOR and AUCUSTUS EDWARD DIXON The Measurement of Overvoltage. By SAMUEL GLASSTONE XXXV.-Transference Numbers and Ionic Complexity of Hycirofluoric Acid Solutions. By CECIL WHITEIELD DAVIES and LAWSON JOHN HUDLESTON XXXV1.-Ring-chain Tautomerism. Part IX. The Muta-rotation of the Sugars. By JOHN WXLIAM BAKER, CHRISTOPHER KELK INGOLD and JOCELYN XIELD THORPE XXXVI1.-The Isomerism of the Oximes. Part XV. The Alleged Fourth Benzildioxime. By OSCAR LISLE BRADY and FREDERICK PERCY DUNN . By KENNETH GUY BLAIKIE and WILLIAM HENRY PERKIN, jun. XXX1X.-Dyes Derived from Acenaphthenequinone. By ANUKUL CHANDRA SIRCAR and SISIR K u ~ t s ~ GUHA .XL.-The Interaction of Ethyl Acetoacetate with o-Hydroxy-styryl Ketones. By THOMAS ALFRED PORSTER and ISIDOR MORRIS HEILBRON . XL1.-The Relation between the Glow of Phosphorus and the Formation of Ozone. By WII~LISM ERIC DOWNEY . XLI1.-The Chemistry of Lignin. Part I. Flax Lignin and some Derivatives. By WALTER JAMES BOWELL and HENRY WHITTAKER . Part VII. The Reciprocal Salt Pair Ammonium Nitrate and Sodium Sulphate. By EDGAR PHILIP PERMAN and WILSON REGINALD H~RRISON. By W. E. GARNER and I?. C. RANDALL . . XXXVII1.-The Methoxyindoles and their Derivatives. XLII1.-The Properties of Ammonium Nitrate. XL1V.-The Rhythmic Crystallisation of Undecoic Acid. . 222 226 231 240 243 250 260 268 291 296 335 340 347 357 364 36 vi CONTENTS.PAW XLV.-Researches on Residnal AfEnity and &-ordination. Part XVII. Stannic Derivatives of fI-Diketones. By GILBERT T. MORGAN and HARRY DUUALD KEITH DREW . Parts I-IV. By FRANCIS FRANCIS and (in part) WALTER FREDERICK M~ILARD C m HENLY RUTT CYRn; MERCER W A ~ S REGINALD WILFRED WALLINUTON, and CHARLES PERCY GARNER . . 381 XLVII.-The Unimolecular Decomposition of Phosphine. By CYRIL NORMAN HINSHELWOOD and BRYAN TOPLEY . 393 XLVIIL-The Absorption Spectra of some Derivatives of Phenol and other Substances. By JOHN EDWARD PURVIS . . 406 XLIX.-Studies in Pluorescence Spectra. Part 11. Phenol and Phenolic Ether Vapours. By JOSEPH KENNETH MhSE . . 418 L.-The Dissociation Constants of Phosphoric Acid.By EDMTND BRYDGES RUDHALL PRIDEAUX and ALFRED THOMASWARD . . 423 L1.-Calculations on the Neutralisation of Mixtures of Acids, and a Universal Buffer Mixture. By EDWD BRYDGES RUDELALL PRIDEAUX and ALFRED THOMAS WARD . 426 LII.4tudies on the Dolomite System. By HANS L. J. BACKSTROM . . 430 LII1.-The Correlation of Additive Reactions with Tauto-me& Change. Part 11. Reversibility in Relation to the Stability of Carbon Chains. By EDITH H ~ D A L1V.-Electrolysis of Potassium Oleate. By GEORGE WILLIAM FRASER H O ~ O Y D and JAMES ERIC WYNFIELD RHODES . . 438 LV.-Preparation and Reactions of the Dihalogenodinitro-methanes. By REGINALD ARTHUR GOTTS and Loms HUNTER . . 442 LW.-Substitution Derivatives of Aurin. By CLAUDE HYMm SPIERS . . 450 NOTEs.-fievention of “ Bumping ” during Vacuum &I-372 XLV1.-The Velocity of Oxidation of P a r a f i Wax.INGOLD (USHXRWOOD) . . 435 tillation. By H. G. BECKER . . 460 Device for Gas-heated Thermostats. By WALTER MURRBY 461 Action of Ozonised Oxygen on Mercury. By VICTOR OLIVER JOHN HODGSON . . 462 Alkaline Reduction of the Carbon Tetrahalides and of Potassium mi-Nitroform. By RICECARD OWEN Glxumrr~ and LOUIS HUNTER . . . 46 CONTENTS. vii PAQE LVI1.-Action of Diacetyltartaric Anhydride and Chloro-fumaryl Chloride upon Aromatic Amine3 and Hydrazines. By FREDERICK DANIEL CHATTAWAY and GEORGE DAVTD PARKES . LVIII .-Reduction Products of the Hydroxyanthraquinones. Part V. By FREDERICK LEATHLEY G-OODALL and ARTHUR GEORGE PERKIN . LIX-Electro-osmotic Experiments on the Reversal of the Electrical Charge of Colloids and Precipitates and the Preparation of Stable Sols with a Charge opposite in sign to that commonly obtained.By JNANENDRA NATH MUKHERJEE and BANKIM CHANDRA ROY LX.-The Sorption of Iodine by Carbons prepared from Paraffin Hydrocarbons Carbon Dioxide Aromatic Hydro-carbons and Derivatives and from the Products of Oxidation of Wood Charcoal with Fuming Nitric Acid. By JAMES BRIERLEY FIRTH WALTER FARIMER and JOHN HIGSON . LXI.-The Solubility of Anilinesulphonic Acids. By JAMES CHARLES PHILIP and ROBERT STANLEY COLBORNE . LXII.-Rmctions at the Interface of Two Immiscible Liquids and the Part Played by the Vapour of Each. The Reaction between Water and Benzyl Chloride. By GEORGE HARKER . LXII1.-The Life Period of the Overvoltage Compounds.By EDGAR NEWBERY . LX1V.-The Volumetric Estimation of Titanium. By ARTHUR MII;NEs MORLEY and JOHN KERFOOT WOOD . LXV.-Constitutional Studies in the Monocarboxylic Acids Derived from Sugars. Part 11. The Methylation of Tetramethyl Gluconic Acid. By JOHN PRYDE . LXV1.-The Solubility of the Aminophenols. By NEVIL VINCENT SIDGWICK and ROBERT KENNETH CALLOW . LXVI1.-Abnormal Benzene Derivatives. By NEVIL VIN-CENT SIDGWICK and ROBERT KENNETH CALLOW. LXVII1.-Properties of Neighbouring Hydroxy-groups attached to a Benzene Nucleus. By RUPCILBND LILARAM ALIMCHABNDANI . Part IV. Anilinoflavindulines and Phenanthraquinoneazo-dyes. By ANUKUL CHANDRA SIRCAR and DHIRENDRA CHANDRA ROY . LXIX.-Dyes Derived from Phenanthraquinone.464 470 476 488 492 500 511 518 520 522 527 539 54 viii CONTENTS. LXX.-The Isomerism of the Oximes. Part XVI. The Action of Ultra-violet Light on Aldoximes and their Derivatives. By OSCAR LISLE BRADY and GERALD PATRICK MCHUGH . LXX1.-Action of Sodium Sulphite on Coumarins. By B ~ N BIHARI DEY and KARNAD KRISHNA Row . LXXI1.-Studies on Hypophosphorous Acid. Part VI. Its Reaction with Chromic Acid. By ALEC DUNCAN ~ T C H E L L . LXXII1.-The Constitution of Kojic Acid a y-Pyrone Derivative formed by Aspergillus o r y m from Carbo hydrates. By TEIJIRO YABUTA . LXX1V.-The Oxime of Mesoxamide (isoNitrosomalonamide) and some Allied Compounds. Part V. Structural and Stereo-isomerism in the Methyl Ethers of the p-Tolyl Derivatives By ARTHUR PLOWMAN and MARTHA ANNIE WHITELEY LXXV.-The Periodic Dissolution of Metals in certain Reagents.By ERNEST SYDNEY HEDGES and JAMES ECKERSLEY MYERS . LXXV1.-Harmine and Harmaline. Part VII. A Synthesis of apoHarmine and of certain Carboline and Copyrine Derivatives. By WILFRID LAWSON WILLIAM HENRY PERKIN jun. and ROBERT ROBINSON LXXVI1.-Harmine and Harmaline. Part VIII. The Con-stitution of certain Harmaline Derivatives. By HIDE-JIRO NISHIKAWA WILLIAM HENRY PERKIN jun. and ROBERT ROBINSON . LXXVII1.-The Action of Nitrogen Peroxide on Cuprous Oxide. By JAMES RIDDICK PARTINGTON . LXX1X.-Use of Amalgamated Zinc in the Evolution Method for the Estimation of Sulphur in Iron and Steel. By TERUO ASHIDA . By HILDYARD JOHN EGLINGTON DOBSON and IRVINE MASSON LXXX.-The Activity of Water in Hydrochloric Acid, LXXX1.-The Vapour Pressure of Hydrochloric Acid.By JOHN STANLEY DUNN and ERIC KEIGHTLEY RIDEAL . LXXXII .-The Promoting Action of Palladium on Copper. Part I. Catalytic Combustion. By WILLIAM WALTER HURST and ERIC KEICIHTLEY RIDEAL LXXXII1.-The Promoting Action of Palladium on Copper. Part 11. The Adsorption of Hydrogen and Carbon Mon-oxide. By WILLIAM WALTER HWT and ERIC KEIBHT-LEY RIDEAL . PAGE 547 554 564 575 587 604 626 657 663 665 668 676 685 69 CONTENTS. is PAGE LXXXIV.-The Mutarotation of the Sugars. By ROBERT GILMOUR . LXXXV.-The Oxidation of 2-Thiol-4 5-diphenylglyoxaline. By IVAN DOUGLAS ~ M B and FRANK LEE PYW . LXXXV1.-Quantitative Reduction by Hydriodic Acid of Halogenated Malonyl Derivatives.Part 111. A Study of the Mechanism of tlhe Reaction. By RALPH WINTON WEST . LXXXVI1.-1 2 8-Trimethoxy-6-methylanthraquinone and 1 2 8-Trimethoxy-7-methylanthraquinone. By JOHN LIONEL SIMONSEN . LXXXVIIL-The Density and Viscosity of Acetone a t Low Temperatures. By EBEN HENRY ARCHIBALD and W~LIAM URE . LXXX1X.-Interaction of Tellurium Tetrachloride and the Higher p-Diketones. Part I. By GILBERT T. MORGAN and HARRY DUGALD KEITH DREW [with C . R. PORTER and I. AcKERMAN] . XC.-Interaction of Tellurium Tetrachloride and the Higher P-Diketones. Part 11. By GILBERT T. MORGAN and REUBEN WILLIAM THOMASON . XC1.-Interaction of Tellurium Tetrachloride and the Higher p-Diketones. Part 111.By GILBERT T. MORGAN and EUSEBIUS HOLMES . NoTES.-The Oxidation of Sabinene with Chromyl Chloride. A Correction. By G. G. HENDERSON and J. M. ROBERTSON The Freezing-point Curves for the System Aceto-2-chloro-anilide and Aceto-4-chIoroanilide. By KENNEDY JOSEPH PREVITE ORTON and GLYN OWEN Preparation of 3 3’-Dinitrobenzophenone. By EDWARD DE BARRY BARNETT and MARCUS ATTRELIUS MATTHEWS Action of Hydrogen Chloride on a Dry Solution of a Chloro-amine. By FREDERICK GEORGE SOPER . XCII.-Properties of Mixtures of Aniline Water and Some Fatty Acids. By JAMES ROBERT POUND and REUBEN SUSSEX RUSSELL . XCIII.-Catalytic Effects of the Oxides of Cerium and Thorium and their Bearing on the Theory of the Wels-bach Mantle. By RICITARD LESLIE SWAN . XC1V.-Kinetics of the Process of Coagulation of Colloids in the Light of Smoluchowski’s Theory.By JNANENDRA NATH MUKHERJEE and SUBODH KUMAR MAJUMDAR . . * 705 706 710 721 726 731 754 760 765 766 767 768 769 780 78 X CONTENTS. XCV.-The Infiuence of Anions on the Coagulation of Negatively Charged Suspensoids. By JNANENDRA NATH MUKHERJEE and SUBODH GOBINDA CHAUDHURI . XCVL-Dyes derived from Carbazole and Thiodiphenyl-amine. By SIKHIBHUSHAN DUTT . XCVII.-Preparation of 2- and 4-Nitro-1 -naphthols. By HERBERT HENRY HODGSON and ERNEST ICILNER . XCVIII.-Studies in Nitration Part 11. Mononitration of Phenol. By FRANCIS ARNALL . XC1X.-Germanium. Part I. The Mineral Germanite and the Extraction of Germanium and Gallium Therefrom. By JOHN SMEATH THOMAS and WILLIAM PUGH .C.-The Mechanism of E. Fischer’s Synthesis of Indoles. Application of the Method to the Preparation of a Pyrindole Derivative. By (Mrs.) GERTRUDE MAUD ROBINSON and ROBERT ROBINSON . C1.-Stereoisomeric Semicarbazones. By FORSYTH J m s WILSON and ROBERT MILROY MACAULAY CII.-Migration of Groups in Derivatives of Benzoin and Desylamine. By ALEX. MCKENZIE and ROBERT ROGER CII1.-Organo-derivatives of Bismuth. Part VII. Iodo-and Nitro-derivatives of Triphenylbismuthine. By JOHN FREDERICK WILEINSON and FREDERICK CHALLENGER . CIV.-The Action of Inorganic Halides on Organometallic Compounds. By FREDERICK CHALLENQER and FREDA PILITCHARD [with JAMES RIG- ASHWORTH JINKS] . CV.-Derivatives of 3-0xy( 1)thionaphthen. By LESLIE RALPH HART and SAMUEL SMILES CVI.-Alternation in the Heats of Crystallisation of the Normal Monobasic Patty Acids.Part I. By W. E. GARNER and F. C. RANDALL The Radioactivity of the Rocks. Hugo Miiller Lecture, Delivered before the Chemical Society on February 28th, 1924. By JOHN JOLY D.Sc. F.R.S. . CVI1.-Dyes of the Aurin Type. Part 11. By HARRY BAINES and JOHN EDMDND DRIVER . CVII1.-The Dimorphism of Diphenylarsenious Chloride (Diphenylchloroarsine). By CHARLES STANLEY GIBSON and (the late) DUDLEY CLOETE Vmma C1X.-The Optically Active Sulphilimines. By E~EDERICK GEORGE and (Sm) W n m ~ JAUKSON POPE . CX.-The Sulphonation of Glyoxalines. Part II. By ROBERT FoRsmH JOSEPH ALBERT MOORE and FRANK LEE PYMAN . . . . . . PAGE 794 802 807 811 81 6 827 841 844 854 864 876 881 897 907 909 911 91 CONTENTS.xi PAGE CX1.-Optically Active p - Pht halimino- p -phenylpropiophen-ones. By ALEX. MCKENZIE and THOMAS MARTIN AIT~EN TUDHOPE . . 923 CXI1.-Researches on Phellandrenes. Part 11. By HENRY GEORGE SMITH PETER GEORGE CARTER and JOHN READ 930 CXII1.-Nitration of p-Bromoacetanilide. By ROLAND HALL GRIFPITH . 940 CX1V.-The Constitution of Polysaccharides. Part VIII. The Molecular Structure of P-Hexa-amylose. By JAMES COLQUHOUN IRMNE HANS PRINGSHEIM and JOHN MACDONALD . . 942 CXV.-The Reaction between Lime and Nitrogen Peroxide. By JAMES RIDDICK PARTINGTON and FRANK ARCHER WIIJJAMS. . 847 By GEORGE MACDONALD BENNETT . . 958 The Purification of Acetic Acid. By KENNEDY JOSEPH PREVITE ORTON and ALAN EDWIN BRADFIELD .. 960 Action of Potassium Hydroxide on Nitric Oxide. By GUY BARR . . 961 The Ultra-violet Absorption Spectrum of Eugenol. By GARTHA THO~SON . . 962 Action of Hydrogen Chloride on Methyl Alcohol. By S. R. CARTER and J. A. V. BUTLER . . 963 A Simple Method for Determining the Approximate Index of Refraction of Liquids with a Common Microscope. By CLAUDE CLAYTON JXIPLINGER . . 963 ANNUAL GENERAL MEETING . . 966 OBITUARY NOTICES . . 984 Some Aspects of Russia’g Contribution to Chemistry. NOTES.-InterpretatiOn of Surface Energy Data. Pre-sidential Address. Delivered at the Annual General Meeting March 27th 1924. By WILLIAM PALMER CXV1.-The Reaction between Phosphorous Acid and Mercuric Chloride. By ALEC DUNCAN MITCHELL .1013 CXVI1.-The Activity of Hydrogen-ion in Aqueous Solu-tions of Hydrogen Fluoride. By WILLIAM FR~-CIS KENRICK WYNNE-JONES and LAWSON JOHN HUDLESTON CXVII1.-The Formation of Quaternary Ammonium Salts. Part 11. By EDWARD DE BARRY BARNETT JAMES WILFRED COOK and WILLIAM CEARLES PECK . . 1035 CX1X.-The Correction of the Density of Liquids for the Buoyancy of Air. By GUY BARR . . 1040 WYNNE D.Sc. F.R.S. . . 997 103 Xii CONTENTS. CXX.-The Application of Weerman’s Reaction to a Methylated Sugar. By JAMES COLQUHOUN IRMNE and JOHN PRYDE . CXX1.-Mercuration of Nitrohydroxybenzaldehydes. By THOMAS ANDERSON HENRY and THOMAS MARVEL SHARP CXXI1.-The Isomerism of the Oximes. Part XVII. Some Bromo- and Nitro-substituted Mono- and Di-methoxy-benzaldoximes.By OSCAR LISLE BRADY and LINGAIAH BASAVALINGIAH MANJUNATH . CXXII1.-Influence of Intensive Drying on Inner Equilibria. By AXDREASMITS . CXX1V.-The Isomorphism of the Amides and Substituted Amides of Dichloro- and Chloroiodo-acetic Acids and of Chlorobromo- and Chloroiodo-acetic Acids. By PHYLLIS V. MCKIE CXXV.-Studies in the Anthracene Series. Part VIII. By EDWARD DE BARRY BARNETT and MARCUS AURELIUS MATTHEWS . CXXV1.-Studies in the Anthracene Series. Part IX. By EDWARD DE BARRY BARNETT and JAMES WILFRED COOK CXXVIL-The Isomerism of the Oximes. Part XVIII. The Action of 2 4-Dinitrochlorobenzene on some Isomeric Aldoximes. By OSCAR LISLE BRADY and RICHARD TRUSZKOWSKI . CXXVII1.-The Chlorination of Ethyl Alcohol. By FREDERICK DANIEL CHATTAW-AY and OTTO GUIDO BACEEBERG .CXX1X.-The Effect of Complex Formation on Oxidation Potentials. The Influence of the Cyanide-ion on the Ferrocyanide-Ferricyanide Potential. By J. A. V. BUTLER and GEORGE PARKER DAVIES CXXX.-The Hydroferrocyanides and Hydroferricyanides of the Organic Bases. Part 111. By WILLIAM MURDOCH CUMMING CXXX1.-Reduction of Nitronaphthalenes. Part 11. Re-duction of p-Nitronaphthalene. By WILLIAM MURDOCH CUMMING and GEORGE STRATON FERRIER . CXXXII .-The Hydrogen Overvoltage of Zinc. By GEORGE NEREDYTH WESTRIP CXXXII1.-Optical Activity and the Polarity of Groups Attached to the Asymmetric Atom. Part I. By HAROLD GORDON RULE . CXXXIV.-Colour and Molecular Geometry. By JAMES Mom . . PAGE 1045 1049 1060 1068 1075 1079 1084 1087 1097 1101 1106 1108 1112 1121 113 CONTENTS.xiii PAGE CXXXV.-Synthesis of Cyclic Polysulphides. Part I. Condensation of Dithioethylene Glycol with Benzylidene Chloride. By SIR PRAFULLA CHANDRA RAY . CXXXVI .-Formation of 3-Halogenocarbazoles from Carb-azole-3-diazonium Halides. By STANLEY HORWOOD TUCKER . CXXXVI1.-Application of Thallium Compounds in Organic Chemistry. Part I. Thallous Hydroxide. By ROBERT CHARLES MENZIES and EDWARD MANWARING 'n71~ms CXXXVII1.-Derivatives of Semioxamazide. Part 11. By FORSYTH JAMES WILSON and ERIC CHARLES PICKERING CXXX1X.-An Examination of the Binary System Sodium Sulphite-Wa ter by Extrapolation from the Ternary System Sulphite-Sulphate-Water . By NEIL BANNA-TYNE LEWIS and ALBERT CHERBURY DAVID RIVETT .CXL.-Miscibility of Anhydrous Sulphite and Sulphate of Sodium. By NEIL BANNATYNE LEWIS and ALBERT CHERBURY DAVID RIVETT CXL1.-The Influence of the Orientation of Surface Mole-cules on the Surface Tension of Pure Liquids. By SAMUEL SUGDEN . CXLI1.-A Relation between Surface Tension Density and Chemical Composit.ion. By SAMUEL SUGDEN . CXLII1.-Conductivity and Ionisation of Solutions of Potassium Iodide in Nitromethane. By JAMES C. PHILIP and HENRY B. OAKLEY CXL1V.-Nitrogen Chlorides derived from Nitro-substituted Acetanilides. By FREDERJCK DANIEL CHATTAWAY and HENRY JAMES DOWDEN . CXLV.-Investigations on the Dependence of *Rotatory Power on Chemical Constitution. Part XXI. The Chemical Significance of Rotatory Dispersion. By HAROLD HUNTER .. CXLV1.-Polymorphic Nitrobenzaldehydehydrazones. By FREDERICK DANIEL CHATTAWAY and ARTHUR JOHN WALKER . CXLVI1.-A New Method for the Preparation of Thiocarbo-hydrazide Mono- and Di-thio-p-urazine. By PRAPH-ULLA CHANDRA GUHA and SATISH CHANDRA DE CXLVIIL-Rate of Photochemical Change in Solids. By EDMUND JOHN BOWEN HAROLD HARTLEY WILLIAM DONALD SCOTT and HAROLD GARFIT WATTS CXL1X.-Investigations on the Supposed Existence of Copper Carbonyl. By EMILE MOND and CHRISTIAN HEBERLEIN . . 1141 1144 1148 1152 1156 1162 1167 l177 1189 1195 1198 1207 1215 1218 122 xiv CONTENTS. CL.-Sugar Ca'rbonates and their Derivatives. Part I. By CHARLES PREDERICK ALLPRESS and WALTER NORMAN HAWORTH . By EDMTJND J o m BOWEN . Part VIII.Analysis of Crystalline Deposits from Solution in Fused Ammonium Nitrate. By EDGAR PHILIP PERMAN and DAVID RICHARDAWKINS . CLII1.-Influence of Colloids on the Rate of Reactions Involv-ing Gases. Part 11 Decomposition of Hydrogen Peroxide and of Nitrosotriacetonamine. By ALEXANDER FINDLAY and D'ILLIAM THOMAS CLIV.-Researches on Residual Affinity and Co-ordination. Part XVIII. Interactions of Zirconium Salts and p-Diketones. By GILBERT T. MORGAX and hmmt RILEY BOWEN CLV.-Researches on Residual Affinity and Co-ordination. Part XIX. Interactioiis of Germanium Tetrahalides and p-Diketones. By GILBERT T. MORGAN and HARRY DUGALD KEITH DREW CLV1.-Action of Selenium Tetrachloride on Di- and Tri-ketones. Selenium Phenylacetyl- and p-Phenylpro-pionyl-acetones.By GILBERT T. MORGAN and CHARLES RAYMOND PORTER . CLVI1.-The Action between Bromine and Malonic Acid in Aqueous Solution. By RALPH WINTON WEST . CLVII1.-The Periodic Catalytic Decomposition of Hydrogen Peroxide. By ERKEST SYDNEY HEDGES and JAMES ECKERSLEYOMYERS . CLIX.-The Heat of Adsorption of Oxygen by Charcoal. By ERNEST ALFRED BLENCH and WILLIAM EDWARD GARNER . CLX.-The Bromine Compounds of Phenanthrene. Part 111. By HERBERT HENSTOCK . CLXI.-Sulphonation of m-Cresol and its Methyl Ether. By ROBERT DOWNS HAWORTH and ARTHUR LAPWORTEI . CLXIL-The Dissociation Pressures of Hydrated Double Sulphates. Part 11. Various Double Sulphates of the Type M**S0,,M2S04,6H20. By ROBERT MARTIN CAVEN and JOIIN FERGUSON . CLXII1.-Polarity Effects in Aromatic Halogen Compounds.By JOHN BALDWIN SHOESMITH ARTHUR CLEIKENT HETHERIXGTON and ROBERT HENRY SLATER CLI.-The Photochemistry of the Halogen Hydrides. CLI1.-The Properties of Ammonium Nitrate. . PAGE 1223 1233 1239 1244 1252 1261 1269 1277 1282 1288 1296 1299 I307 131 CONTENTS. xv PAQE CLX1V.-The Correlation of Additive Reactions with Tauto-meric Change. Part 111. The Cyano-imino Additive Process. By EDITH HILDA INGOLD . CLXV.-The Chemistry of Posidonia Fibre. Part 11. The Cellulose. By JOHN CAMPBELL EARL . CLXV1.-Tautomerism of the Mesoxalic Acid and Pyruvic Acid Phenylhydrazones. Evidence for the Hydrazone Structure of the Tautomerides. By HAROLD ROBERTS STEVENS and FRED WILBERT WARD CLXVI1.-Researches on Chromammines .Part I. Salts of Nitro- and Other Dyes. By HERBERT JOSEPH SEYBIOUR KING . CLXVIII.-Synthesis of Amygdalin. By RAY CAMPBELL and WALTER NORMAN HAWORTH . CLX1X.-Derivatives of a New Form of Mannose. By JAMES COLQUHO~ IRVINE and PITILLLAM BURT. CLXX.-The Synthesis of an Azocyanine. By FRANCES MARY HAMER CLXX1.-The Hydrolysis of Potassium Ferricyarzide and Potassium Cobalticyanide by Sulphuric Acid. By HENRY BASSETT and ALEXANDER STEVEN CORBET . CLXXI1.-The Potassium Salts of Phenolphthalein. By HENRY BASSETT and DOUGLAS JAMES TALBOT BAGNALL CLXXII1.-Physostigmine (Eserine). Part 11. The Syn-thesis of Physostigmol Ethyl Ether. By EDGAR STEDBEAN CLXXIV.-The Orienting Influence of the Thiocyano-group in Aromatic Compounds. By FREDERICK CHALLENGER and ALFRED DREW Coums .CLXXV.-Induced Alternate Polarities in a Carbon Chain on the Basis of Bohr’s Theory. By KRISTIAN H~JEN-CLXXV1.-Investigations on the Dependence of Rotatory Power on Chemical Constitution. Part XXII. Some Compounds containing the Secondary Octyl Radical Linked to Oxygen. CLXXVI1.-Investigations on the Dependence of Rotatory Power on Chemical Constitution. Part XXIII. The Normal Aliphatic Ethers of d-7-Nonanol. By JOSEPH KENYON and THOMAS WALDEN BARXES NOTES.-~ Intense Lithium Flame for Polarimetric Use. By E ~ R O L D HUNTER . Sulphonation of m-Dinitrobenzene. By ROLAND HALL GRIFFITH DAHL . By HAROLD HUNTER . . 1319 1322 1324 1329 1337 1343 1348 1358 1366 1373 1371 1381 1389 1395 1401 140 xvi CONTENTS.Tellurium Monoxide. By J. J. DOOLAN and J. R. PARTINGTON . Atomism in Modern Physics. Faraday Lecture. Delivered before the Fellows of the Chemical Society in the Theatre of the Royal Institution on June 12th 1924. By R. A. MILLIKAN CLXXVIIL-The Isomerism of the Oximes. Part XIX. Substituted Cinnamaldoximes. By 0. L. BRADY and H. J. GRAYSON . CLXX1X.-Some Binary Systems Composed of Acetic Acid and the Homologues of Aniline. By EDMUND ARTHUR O'CONNOR . CLXXX.-Equilibrium in the Systems Cupric Sulphate-Potassium Sdphate-Water and Cupric Sulphate-Ammonium Sulphate-Water at 25" 51" and 61". By ROBERT MARTIN CAVEN and THOMAS CORLETT MITCHELL CLXXX1.-The Tautomerism of Amidines. Part IV. The Methylation of 4(or 5)-Nitroglyoxaline and 4( or 6)-Phenylglyoxaline.By CHARLES EDGAR HAZELDINE, FRANK LEE PYMAN and (the late) JOHN WINCHESTER. CLXXXI1.-The Relation between the Crystal Structure and the Constitution of Carbon Compounds. Part 11. Crystallography of further Simple Substitution Products of Methane. By ISABEL ELLIE KNAGGS . CLXXXIIL-Quebrachamine. By ELLEN FIELD . CLXXX1V.-The Action of Thionyl Chloride on Hydroxy-anthraquinones. Part I. Thionylalizarin. By ALBERT GREEN . CLXXXV.-The Solubility of Sodium Fluoride in Hydro-fluoric Acid. By DAVID BRET JEHU and LAWSON JOHN HUDLESTON . CLXXXV1.-The Additive Formation of Four-membered Rings. Part V. The Formation of Stable Dimethylene-1 2-oxaimines from Ethylenes and Nitroso-compoimds, with Special Reference to the Direction of the Addition.By CHRISTOPHER KELK INGOLD and STANLEY DOUGLAS WEAVER CLXXXVIL-Action of Diazo-salts on Methanesulphon-amide. By PAVITRA KUMAR DUTT . . . PAW 1402 1405 1418 1422 1425 1431 1441 1444 1450 1451 1456 1463 CLXXXVII1.-The Rotatory Dispersive Power of Organic Compounds. Part XI. The Molecular Weight of Ethyl Tartrate and the Origin of Anomalous Rotatory Dispersion in Tartaric Acid and its Derivatives. By THOMAS MARTIN LOWRY and JOHN OUTRAM CUTTER . 146 CONTENTS. xvii PAQE CLXXXIX.-Sedimentation of Bentonite By HUBERT FRANK COWARD . CXC.-Studies in Optical Superposition. Part V. d-sec.-Octyl &Tartrate. By T. S. PATTERSON and CH;BRLEs BUCIIANAN . CXCI.-The Formation of Triphenylmethylphosphinic Acid from Triphenylmethoxyphosphorus Dichloride.By DAVID RUNCIMAN BOYD and FREDERICK JAMES SMITH CXCIL-Halogenation of 8.-Dipotassium Tetranitroethane. By LOUIS HUNTER . CXCII1.-Studies in Mutual Solubility. Part 111. The Mutua’l Solubility of Glycerol and Amino- and Hydroxy-compounds. By RAM Rso PARVATIKER and BASIL CHARLES MCEWEN . CXC1V.-Studies in the Configuration of uz’-Dibromo-dibasic Acids. Part 11. Derivatives of Adipic Acid. By ALLAN WILLY BERNTON HARRY RAYMOND h a , and WILLIAM HENRY PERKIN jun. . CXCV.-1 2 3 4 5 6 7 8-Octahydrocarbazole and its Derivatives. By WILLIAM HENRY PERKIN jun. and SYDNEY GLENN PRESTON PLANT . CXCV1.-Glycogen. Part I. Partial Methylation and the Isolation of Methylated Glucoses. By ALEXANDEB KILLEN MACBETH and JOHN MACKAY . CXCVIL-The First Law of Photochemistry.By MURIEL CATHARINE CANNING CHAPMAN. CXCVII1.-The Decomposition of Ethylene Bromide by Potassium Iodide and Sodium Iodide Solutions. By T. S. PATTERSON and JOHN ROBERTSON . CXC1X.-Tautomerism of Dyads. Part 11. Acetylene and its Halogen Derivatives. By EDITH HILDA INGOLD (USHERWOOD) . CC.-Titanous Salts as Reducing Agents. By EDXUND KNECHT [with (Miss) E. HIBBERT] NoTEs.-Device for Maintaining a Constant Level in a Water-bath. By RICHARD BROOKS . A Simple Non-splash Ring for Use with Scheibler’s Desic-cator. By S. C. BRADFORD . 4-Nitro - 2 - sulphophenyldehydrothio - p - toluidinesulphonic Acid. By DAVID HENRY PEACOCK . CC1.-Colour and Molecular Geometry. Part 11. Explan-ation of the Results of Chattaway and Clemo.By JAMES Mom . . 1470 1476 1477 1480 1484 11492 1503 1513 1521 1526 1528 1537 1546 1546 2847 154 XViii CONTENTS. PAQE CCII.-Balogen-substituted Aryl Thiocarbimides. By FREDERICK DANIEL CELATTAWAY RICHARD KENNETH HARDY and HEDLEY GEORGE WATTS . . 1552 CCII1.-Application of the Grignard Reaction to some Acetylenic Compounds. Part 11. By FORSYTH JAMES WILSON and WILLIAM MCNINCH HYSLOP . . 1556 CCIV.-A Criticism of the Distillation Method of Measuring Vapour Pressure. By LAWSON Jom HUDLESTON . 1558 CCV.-Electrical Conductivities of Rlixtures of Aniline, Acetic Acid and Water. By JAMES ROBERT POUND . 1560 CCT-’I.-The Bromo-derivatives of 1 -Methylglyoxa,lie and the Constitution of ‘‘ Chloroxalmethylin.” By ISIDORE ELKANAH BALABAN and PRANE LEE PYMAN .. 1564 C1CVII.-The Electrometric Titration of Chromic Acid using (a) the Hydrogen Electrode and ( b ) the Oxygen Electrode. By HUBERT THOMAS STANLEY BRITTON . 1572 CCV1II.-Catalytic Racemisation of the Diastereoisomeric I-Menthyl Phenylbromoacetates. By ALEX. MCKENZIE and ISOBEL AGNES SMITH . 1552 CCIX.-The Rotatory Dispersive Power of Organic Com-pounds. Part XII. Octyl Alcohol and Octyl Oxalate. By THOMAS MARTIN LOWRY and EVAN MATTHEW RICHARDS . 1593 CCX .-ortho-Chlorodinitro toluenes. Part V . 2-Chloro-3 6-dinitrotoluene. By GILBERT T. MORGAN and THOMAS GLOVER . . 1597 CCXI.-cycZoTelluropentanediones and cycbTelluripentane-dione Dihalides. By GILBERT T. MORGAN and HARRY DUGALD KEITH DREW . . 1601 CCXI1.-Synthesis of 4-Tetrahydroquinolone and a new Synthesis of 4-Methoxyquinoline By GEORGE ROGER CLEMO and WILLIAM HENRY PERKIN junr.. . 1608 CCXIIL-Condensation of Aryldiazonium Salts and of MkyI Nitrites with certain Derivatives of Cyanoacetic Acid. By THOMAS KENNEDY WALKER . . 1622 CCXIV.-The Behaviour of Titanic Acid towards Hydro-chloric Acid. By ARTRUR MILNES MORLEY and JOHN KERFOOT WOOD . . . 1626 Part 111. The Effect of the Addition of Oxygen on the Production of Hydrocyanic Acid. By WILLIAM EDWARD GARNER and SIDNEY WALTER SAUNDERS . . 1634 CCXVI.-The Ternary Alloy System AIurninium-Cadmium-Zinc. By NORMAN FREDERICK BUDGEN . . 1642 CCXV.-The Explosion of Acetylene and Nitrogen CONTENTS. xix PAGE CCXVI1.-A Phase Rule Study of the Cupro- Argento-, Auro- and Thallo-cyanides of Potassium.By HENRY BASSETT and ALEXANDER STEVEN CORBET CCx~II.-~-e~iBerberine. By JOHANNES SYBRANDT BUCK and WILLIAM HENRY PERKIN junr. . CCX1X.-+-Berberine. By ROBERT DOWNS HAWORTH, WILLIAM HENRY BERKIX junr. and JOHN RANKM . CCXX.-The Reactions of Thiocarbonyl Chloride. Part I. React ion with Aromet ic Primary Amino -compounds. By GEORGE MALCOLM DYSON and HERBERT JOHN GEOI~GE . Part IX. The Reciprocal Salt Pair Ammonium Nitrate and Lithium Chloride. By EDGsR PHILIP PERMAN and WILSON REGINALD HARRISON . CCXXII .-Electrolytic Formation of Alloys and Amalgams of Manganese. By ALAN NEWTON CAMPBELL . CCXXII1.-Electrometric Studies on Azo- and Hydrazo-compounds. By EINAR BIILMANN and JAKOB H. BLOM CCXXIV.-Researches on Residual AEnity and Co-ordina-tion.Part XX. Chromic and Cobaltic Lakes of Mordant Azo-dyes. By GILBERT T. MORGAN and J. D. CCXXV.-Studies in the Resolution of Racemic Acids by Optically Active Alcohols. Part 111. The Resolution of r-Tartaric and r-Dimefhoxysuccinic Acids by I-Menthol. By HENRY WREN and (MISS) KATHLEEN H. HUGHES . CCXXV1.-Tesla-luminescence Spectra. Part IV. Some Hydrocarbons containing a Single Benzene Nucleus. By WILLIAM HAMILTON MCVICKER JOSEPH KENNETH MARSH and ALFRED WALTER STEWART CCXXVI1.-Strychnine and Brucine. Part 11. By GEORGE ROGER CLEIHO WILLIAM HENRY PERRM jun. and ROBERT ROBLNSON . CCXXVII1.-Vinyl Derivatives especially of Carbazole and Tetrahydrocarbazole and their Behaviour with Acids. By GEORGE ROGER CLEMO and WILLIAM HENRY PERKIN jun.. CCXXIX.-Studies in the Configuration of otor’-Dibromo-dibasic Acids. Part 111. The ad-Dibromo-succinic Acids. By HARRY RAYMOND ING and WILLIAM HENRY PE- jun . CCXXX.-Ring-chain Tautomerism. Part X. Inhibited Tautomerism. By ZRAXK DICKENS LAURENCE HORTON, and JOCELYN EIELD THORPE . CCXX1.-The Properties of Ammonium Nitrate. MAINSlVIITH . . 1660 1675 1686 1702 1709 1713 1719 1731 1739 1743 1751 1804 1814 183 xx CONTENTS. CCXXX1.-The Thermal Decomposition of Chlorine Monoxide. Part 11. Relation to the General Theory of Bimolecular Reactions. By CYRIL NORMAN HINSHEL-WOOD and JOSEPH HUGHES . CCXXXIL-Conversion of Hydroaromatic into Aromatic Compounds. Part I. Action of Chlorine on 6-Clhloro-1 l-dimethyl-A4-cycZohexen-3-one.By LEONARD ERIC HINKEL. CCXXXII1.-Direct Sulphuration of Aniline. By HERBERT HENRY HODGSON . CCXXXIV.-The Ignition of Gases. Part 111. Ignition by the Impulsive Electrical Discharge. Mixtures of the P a r a h s with Air. By RICHARD VERXON WHEELER CCXXXV.-The Ignition of Gases. Part IV. Ignition by a Heated Surface. Mixtures of the Paraffins with Air. By WALTER MASON and RICHARD VERNON WHEELER . CCXXXVI.-Investigations of the Chromates of Thorium and the Rare Earths. Part 11. The Chromates of Lanthanum Praseodymium Neodymium and Samarium. By HUBERT THOMAS STANLEY BRITTON . CCXXXVI1.-Oxidation Potentials of Ferrous and Ferric Salts in Concentrated Hydrochloric Acid and Phosphoric Acid. By SYDNEY RAYMOND CARTER and FRANCIS HERBERT CLEWS .CCXXXVIIL-The Composition and Properties of Clay. By ALFRED FRaNcrs JOSEPH and JOHN STANLEY HANCOCK. CCXXX1X.-Studies on the Dependence of Optical Rotatory Power on Chemical Constitution Part V. Rotatory Dispersions of d- Camp horimide d- Camp horbenz ylimide , Benzyl-d-camphoramic Acid and their Derivatives. By BAWA KARTAR SINGH and ATUL CHANDRA BISWAS . CCXL.-The Hydrolysis of the p-Toluenesulphonchloro-amides in Water. By FREDERICK GEORGE SOPER . CCXLI.-Compounds of Tervalent Molybdenum. Part I. A New Oxysulphate. By WILLIAM WARDLAW FRANK HAROLD NICHOLLS and NORMAN DARBY SYLVESTER. CCXLI1.-The Cyanine Dyes. Part VIII. Synthesis of a 2 4’-Carbocyaaine. Constitution of the Dicyanines. By WILLIAM HOBSON MILLS and RONALD CHARLES ODAMS . CCXLII1.-Studies of Valency.Part IV. Absorption Spectra of Camphor Benzylidenecamphor and Camphor-quinone. Optical Evidence of Two Types of Con-jugation. By THOMAS MARTIN LOWRY and HELEN SOMERSBY FRENCH . PAGB 1841 1847 1855 1858 1869 1875 1880 1888 1895 1899 1910 1913 192 CONTENTS. xxi PAGE CCXL1V.-The Chemistry of the Glutaconic Acids. Part XVI. Three-carbon Tautomerism in the cyclo-Propane Series. Part 111. Refractometric Evidence. By FRANK ROBERT Goss CHRISTOPHER KELK INGOLD and JOCELYN FIELD THORPE . CCXLV.-Pission of the Pyridine Nucleus During Reduction. By BRIAN D m c m SHAW . CCXLV1.-Studies in the Phenylsuccinic Acid Series. Part VIII. The Resolution of r-Diphenylsuccinalic and r-Diphenylsuccino-p-toluidic Acids into their Optical Antipodes.By HENRY WREN and RICHARD ELLIS BURROWS CCXLVI1.-The Volumetric Estimation of Total Carbonic Acid in Dilute Solutions of Calcium Hydrogen Carbonate or in Hard Tap-waters. By EDWARD MORTIMER CROWTHER and WALLACE STANLEY MARTIN CCXLVII1.-The Rotatory Dispersion of Derivatives of Tartaric Acid. Part I. Methylene Derivatives. By PERCY CORLETT AUSTIN and VICTOR ALEXANDER CAR-CCXLIX.-A New Method of Micro-gas Analysis. By LEWIS REEVE . CCL.-The Temperature Coefficient of the Quinhydrone Electrode. By EINAR BIILMANN and INGER KBARUP . CCL1.-The Influence of Nitrogen Dilution on the Speed of Flame. Part I. By COLIN CAMPBELL and OLIVER COLIGNY DE CHAMTFLEOR ELLIS . CCLI1.-The Influence of Nitrogen Dilution on the Speed of Flame.Part 11. By OLIVER COLIGNY DE CHAMPFLEUR ELLIS and SYDNEY ROBERT STUBBS . CCLII1.-Researches on Residual Affinity and Co-ordination. Part XXI. Boron P-Diketone Difluorides. By GILBERT T. MORGAN and RICHARD BRIAN TUNSTALL NoTES.-conversion of Nickel Carbonyl into Carbonate in Toluene Solution. By PERCY CYRIL LESLEY THORNE . An Apparatus for Collecting a Gas at a Constant Pressure. By HILDYARD JOHN EGLINTON DOBSON Solid Phases of Invariable Composition. By THOMAS WESTON JOHNS TAYLOR . CCL1V.-A Modified Dichromate Method for the Estimation of Glycerol. The Hydration of Curd Fibres of Sodium Palmitate. By HAROLD BENSON BENNETT . CCLV.-The Velocity of Benzylation of certain Amines. By DAVID HENRY PEACOCK . . PEXTER . . . 1927 1930 1934 1937 1939 1946 1954 1957 1960 1963 1967 1968 1969 1971 197 sxii CONTENTS.CCLV1.-Diazonium Tetrachloroiodides and Plumbichlorides. By FREDEREK DANIEL CHATTAWAY FRANK LESLIE GARTON and GEORGE DAVID PARKES CCLVIL-The Chemistry of Cadinene. Part I. By GEORGE GERALD HENDERSON and ALEXANDER ROBERTSON . CCLVII1.-Researches on Residual Affinity and Co-ordina-tion. Part XXII. Optically Active Salicylatocobalt Diethylenediammines. By GILBERT T. MORGAX and J.D. MAIN SMITH . CCL1X.-Metallic Hydroxy-acid Complexes. Part 111. The Constitution of Cuprimalates and Aiinlogous Corn-pounds. By IAN WILLIAM WARK . CCLX.-A Direct Method for the Estimation of Glucose and Other Carbohydrates. By EDMUND KKECHT and EVA HIBBERT . CCLX1.-Resolu tion of trans-cycZoBu tane- 1 2-dicarbonylic Acid.By LEONARD JAMES GOLDSWORTHY . CCLXI1.-Derivatives of Methylstannonic Acid. Part 11. By HERBERT LAMBOURNE CCLXII1.-The Apparent Concentration of the Hydrogen-ion in Solutions Containing Sucrose. By THOMAS WESTON JOHNS TAYLOR and RAYMOND FRANCIS BOM-CCLXIV.-The Explosion of Ammonia with Electrolytic Gas and Oxygen. By JABXES RIDDICK PARTINGTON and ALFRED JOHN PRINCE . CCLXV.-Organic Compounds of Arsenic. Part I. Deriv-atives of o-Benzarsinic Acid. By JOHN ALFRED AESCHL~MANN and NIAL PATRICK MCCLELAND CCLXV1.-The Viscosity and Surface Tension of Solutions of Iodine and Potassium Iodide. By ERNEST AUGUSTOS DANCASTER . CCLXVI1.-Chloro-Perbromide Equilibria. By ERNEST AUGUSTUS DANCASTER . CCLXVII1.-The Dependence on Pressure of the Adiabatic Cooling of Some Organic Substances.By NICOLAI ANTONOVICH PUSHIN and ELIJAH VASILJEVICH GREBEN-CCLX1X.-The Mutarotation Lag in Sucrose Inversion. By STUART WORTLEP PENNYCUICE. CCLXX.-The Interaction of Acetoacetic Ester and o-Hydroxydistyryl Ketones. By ISIDOR MORG~IS H~ILBRON and THOMAS ALFRED FORSTER . . FORD . . SHCHIKOV PAGE 1980 1992 1996 2004 2009 2012 2013 2016 2018 2025 2036 2038 2043 2049 206 CONTENTS. xxiii PAGE CCLXX1.-Selective Solvent Action by the Constituents of Aqueous Alcohol. Part 111. The Effect of some Water-soluble Semi-solutes. By ROBERT WRIGHT . CCLXXI1.-The Conditions of Reaction of Hydrogen with Sulphur. Part V. Photochemical Union. By RONALD GEORGE WREYFORD NORRISH and ERIC KEIGRTLEY RIDEAL .CCLXXII1.-Studies of Dynamic Isomerism. Part XVI. Form-The By HENRY BURGESS The Mutarotation of Beryllium Benzoylcamphor. ation of an Additive Compound with Chloroform. Optical Activity of Beryllium. and THOMAS MARTIN LOWRY . CCLXXIV.-An Apparatus for the Viscosimetric Deter-mination of Transition Points. By NORMAN HOLT €€ARTSHORNE . CCLXXV.-The Isomerism of the Styryl Alkyl Ketones. Part I. The Isomerism of 2-Hydroxystyryl Methyl Ketone. By ALEXANDER MCGOOKIN and ISIDOR MORRIS HEILBRON . CCLXXV1.-Elimination of the Amino-group of Tertiary Amino-alcohols. Part 11. The Semipinacolinic De-amina t ion of p - Hydr ox y - 01 p - dipheny 1 - p -nap h t h yle thyl-amine. By ALEX. MCKENZIE and WALTER SAMUEL DENNLER .CCLXXVI1.-The Colorimetric Dissociation Constants of the Mono- and Di-nitroquinols. By EDMUND BRYDGES RODHALL PRIDEAUX and GLENCOE RONALD NUNN . CCLXXVII1.-Derivatives of 1 8-Naphthalic Acid. Part I. The Preparation and Properties of 1 8-Naphthalyl Chloride. By PREDERICK ALFRED MASON CCLXX1X.-Derivatives of 1 8-Naphthalic Acid. Part 11. The Preparation and Properties of 1-Benzoyl-naphthalene-8-carboxylic Acid and its Derivatives. By FREDERICK ALFRED MASON . CCLXXX.-Studies in Fluorescence Spectra. Part 111. By THOMAS HENRY NUNAN Aromatic Amine Vapours. and JOSEPH KENNETH MARSH . CCLXXX1.-The Chemistry of the Glutaconic Acids. Part XVII. The Tendency towards Reversion t o Type. By CHRISTOPHER KELK INGOLD JAMES HEREERT OLIVER, and JOCELYN FIELD THORPE .. 5068 2070 3081 2096 2099 2105 2110 2116 2119 2123 2 12 xxiv CONTENTS. CCLXXXII.4tudies on the Walden Inversion. Part VIII. The Influence of the Solvent on the Sign of the Product in the Conversion of p-Hydroxy- p-phenylpropionic Acids into P-Bromo- p-phenylpropionic Acids. By GEORGE SENTER and ALLEN MILES WARD CCLXXXII1.-The Action of Hydrazines on Semicarbazones. Part I. By MARGARET MILLEN JEFFS SUTHERLAND and FORSYTH JAMES WILSON . CCLXXX1V.-The Dehydration of the Optically Active Methyl- and Ethyl-hydrobenzoins. Rv ALEX. MCKENZIE and ROBERT ROGER CCLXXXV.-Influence of Substituents on Chemical and Physical Properties the Velocity of Reaction between Substituted Benzoic Anhydrides and an Aliphatic Alcohol. By HAROLD GORDON RULE and THOMAS RAMSAY PATERSON .CCLXXXV1.-A Synthesis of $-Pelletierine. By ROBERT CHARLES MENZIES and ROBERT ROBINSON . CCLXXXVII.-5-Carboline and some Derivatives. By ROBERT ROBINSON and SIDNEY THORNLEY . CCLXXXVII1.-Oxidation of Substituted 1 -13enzyI-3 4-dihydroisoquinolines and a Synthesis of Papaveraldine . By JOHANNES SYBRANDT BUCK ROBERT DOWNS HAWORTH and WILLIA4M HENRY PERELIN jun. CCLXXX1X.-The Influence of Substituents on the Form-ation of Derivatives of 1-Hydrindone from @-Phenyl-propionic Acids. By ERIC ALFRED SPEIGHT ARNOLD STEVENSON and JOCELYN FIELD THORPE . CCXC.-An Accessible Derivative of Chromonol. By JAMES ALLAN and ROBERT ROBINSON. xoTEs.-Mononitration of p-Chlorotoluene. By HERBERT HENRY HODGSON and PETER ANDERSON The Photochemical Action of Iodine on Moist p-Chloro-toluene.By OSWALD SILBERRAD . A Combined Fractionating Column and Condenser. By W. J. GOODERHAM . CCXC1.-Studies with the Microbalance. Part I. The Photochemical Decomposition of Silver Bromide. By ERNEST JOEUNNES HARTUNG . Part V. The Monosulphide and Disulphide of Lithium. By JOHN SMEATH THOM~S and JOHN HENRY JONES . . . CCXCI1.-The Polysulphides of the Alkali Metals. PAGE 2137 2145 2148 2155 2163 2169 2176 2185 2 192 2195 2196 2197 2198 220 CONTENTS. xxv PAQB CCXCII1.-Studies in the Organic Polysulphides. Part 11. The Action of Anhydrous Potassium Pentasulphide on Ally1 Iodide and on some Aromatic Halogen Compounds. By JOHN SMEATH THOMAS and RICHARD WILLIAM RIDING .CCXC1V.-Cryoscopic Measurements with Nitrobenzene. Part 11. The Variation of the Molecular Depression with Water Content. By FREDERICK STANLEY BROWN and CHARLES R. BURY . CCXCV,-The Ionisation Constant of Hypochlorous Acid. By FREDERICK GEORGE SOPER CCXCVL-Some Electrochemical Aspects of the Oxidising Properties of Sulphur Dioxide. By SYDNEY R,AYMOND CARTER and FRANK JAMES . CCXCVI1.-A New Route to the 3-Hydroxybenzopyrylium Salts. By LESLIE RANDAL RIDGWAY and ROBERT ROBINSON . CCXCVII1.-The Dissolution of Substances in Mixed Liquids with Special Reference t o Colloids. By ERNEST WALTER JOHN MARDLES . CCXCIX.-The Carbonates of Ethylene Glycol and Related Compounds. By CHARLES FREDERICK ALLPRESS and WILLIAM Miw CCC.-Condensation of Acetylene and Hydrogen Sulphide in Presence of Catalysts.By MARGARET GROSVENOR TOMKINSON . CCC1.-The Action of Sodium on the *4cetates of 0- and p-Cresol. By RICHARD ISAAC EDWARD HALL . CCCI1.-The Measurement of the Vapour Pressures of Aqueous Salt Solutions by the Depression of the Freezing Point of Nitrobenzene. By NEVIL VINCENT SIDGWICK and ELINOR KATHERINE EWBANK CCCII1.-The Hydration of Salts and their Effect on the Vapour Pressure of Water. By N e v r ~ VINCENT SIDG-WICK and ELINOR KATHERINE EWBANE CCC1V.-A Convenient Method for the Preparation of Arsinic Acids from the Corresponding Chloroarsines. By HAROLD BURTON and CHARLES STANLEY GIBSON , CCCV.-Polarity Effects in the Isomeric o-Bromoxylenes and Isomeric Iodotoluenes. By JOHN BALDWIN SHOE-SMITH and ROBERT HENRY SLATER .CCCV1.-The Solvent Action of Trialkyl Trimethylenetri-amines on Uric Acid. By JOHN GRAYMORE . CCCVIL-Syntheses in the Indole Series. Part I. By WILLIAM OQILVY KERMACK . . . 2214 2219 2227 2231 2240 2244 2259 2264 2266 2268 2273 2275 2278 2283 228 XXVi CONTEXTS. CCCVII1.-Organic Derivatives of Silicon. Part XXX. Complex Silicohydrocarbons [ SiPh,],. By FREDERICK STABLEY KIPPING . CCCIX.-The Isomerism of the Oximes. Part XX. The Isomeric p-Nitrobenzophenoneoximes and their Four Methyl Ethers. . CCCX.-Resolution of a-Terpineol. By ALBERT THOMAS FULLER and JOSEPH KENYON . CCCXI.-Equilibrium across a Parchment Membrane in the Case of Sodium Chloride in Presence of Sodium Caseinate. By PERCY ARCHIBALD SPORING .CCCXI1.-Studies in Electro-endosmosis. Part I. By FRED FAIRBROTHER and HAROLD MASTIN. By 0. L. BRADY and R. P. MEHTA CCCXII1.-7-Hydroxystearic Acid. By PERCIVAL WALTER CLUTTERBUCK . CCCX1V.-Reduction Products of Arylidenecyanoacetic Acids. By WILSON BAKER and ARTHUR LAPWORTH . CCCXV.-The Interaction between Ethyl Ethylidene-malonate and Anilinophenylacetonitrile. By LUCY HIGGINBOTHAD/I ARTHUR LAPWORTH and CHARLES SIMPSON . CCCXV1.-The Influence of Catalysts on Carbonisation. By RUDOLF LESSING and MAURICE ALFRED LISTER BANKS . CCCXVli1.-Nitration of 2 3-Dimethoxybenzaldehyde. By WILLIAM HENRY PERXIN jun. ROBERT ROBINSON and FRAXCIS WILBERT STOYLE . CCCXVII1.-Derivatives of Aniline Disulphoxide. By CHARLES MONTAGUE BERE and SAMUEL SMILES CCCX1X.-2 6-Distyrylpyridine and its Derivatives.By BRIAN DUNCAN SHAW . CCCXX.-Pyridofluorene and some of its Derivatives. By WILLIAM HOBSON MILLS WILLIAM HAROLD PBLMER, MA MARGARET G. TOMKINSON . Part 11. Molybdenyl Monochloride. By WILLIAM WARDLAW and ROBERT LOUIS WORMELL . CCCXXII.-The Density of the Oxides of Zirconium and Hafnium. By GEORGE HEVESY and V~aao BERGLUND CCCXXI.-Compounds of Tervalent Molybdenum. PAQB 2291 2297 2304 2316 2319 2330 2333 2339 2344 2355 2359 2363 2365 2370 237 CONTENTS. xxvii CCCXXII1.-New Halogen Derivatives of Camphor. Part IV. Action of Hydroxylamine on a- and ar'-Chloro-camphor and Bromocamphor. Part V. Action of Sodium Methoxide and Ethoxide on ap-Dibromo-camphor. Formation of Esters of a-Rromocampho-lenicAcid.By HENRY BIJWESS . CCCXX1V.-The System Sodium Carbonate-Sodium Sdph-ate-Water. By WILLLAM AUGUSTUS CASPARI . CCCXXV.-Limits €or the Propagation of Flame in Inflam-mable Gas-Air Mixtures. Part I. Mixtures of Air and One Gas at the Ordinary Temperature and Pressure. By ALBERT GREVILLE WHITE . CCCXXV1.-The Resolution of dE-Diphenylpropylenedi-amine and dl-1 4-Diphenyl-2-methylpiperazine. By FREDERIC BARRY KIPPING and WILLIAM JACKSON CCCXXVIL-The Reactions of the Unsymmetrical Trinitro-By 0. L. BRADY S. W. HEWETSON and CCCXXVII1.-Condensation of Diphenylformamidine with Phenols. Part 11. The General Nature of the Reaction. By JOHN BALDWIX SHOESMITH and JOHN HALDANE . CCCXX1X.-Blue Adsorption Compounds of Iodine. Part CCCXXX.-Studies of Electrolytic Polarisation.Part I. The Cathodic Overvoltage of Lead. By SAMUEL GLASSTONE . CCCXXX1.-Halogen-substituted 1- Arylpyrazolones. By FREDERICK DANIEL CHATTAWAY and CHARLES RICHARD NOEL STROUTS CCCXXXI1.-The Oxidation of Acetomesitylene with Per-manganate. By WILLJAM HENRY PERKIN jun. and RICHARD ARTHUR BEATER TAPLEY . CCCXXX1II.-Tetrahydroacridine Octahydroacridine and their Derivatives. By WILLIAM HENRY PERKIN jun., and WILLIAM GREENWELL SEDGWICK CCCXXX1V.-Derivatives of Acridone and Tetrahydrocarb-azole. By WILFRED HERBERT LIXNELL and W~LLIAM HENRY PERKIN jun. . Part 111. The Action of the Disulphides of the Alkali Metals and of Sodium Tetrasulphide on some Organic Halogen Compounds. By JOHN SMEATH THOMAS and POPE .toluenes. L. KLEIN Iv. By GEORGE BARGER and FREDERICE J O H N EATON CCCXXXV.-Studies in the Organic Polysulphides. RICHARD WILLIAM RIDING . . PAQB 2375 2381 2387 2396 2400 2405 2407 2414 2423 2428 2437 245 1 246 xxviii CONTENTS. CCCXXXVL-Amylene- and Butylene-oxidic Forms of Tetramethyl Galactose. By WALTER NORMAN EAWORTH DAVID ARTHUR RUELL and GEORGE CRONE WESTGARTH . CCCXXXVI1.-Aluminium Amalgam as a Reducing Agent in the Sugar Series. By DINSHAW RATTONJI NANJI and FREDERIC JAMES PATON . Part 11. By HELEN WINIFRED CARNELLEY and PAVITRA KUMAR DUTT . CCCXXX1X.-Behaviour of Nitrophenols with p-Toluene-sulphonyl Chloride. By SHRIRANG M. S A N ~ and SHUM SUNDER JOSECI . CCCXL.-Substitution in the Benzene Nucleus on Nitration of 2-Phenylglyoxaline and its Carboxylic Acids.By FRANK LEE PYMAN and EDMUND STANLEY CCCXL1.-Extraction of the Isomeric Xylenes from Crude Xylol. By T. S. PATTERSON ANDREW M C ~ L A N and ROBERT SOMERVILLE CCCXLII .-A Spectroscopic Study of the Luminescent Oxidation of Phosphorus. By HARRY JULIUS EMEL~US and WELU ERIC DOWNEY . CCCXLII1.-Studies in Electro-endosmosis. Part 11. By FRED FAIRBROTHER. CCCXL1V.-A New Method for the Preparation of 9-Alkyl-carbazoles. By HAROLD BURTON and CHARLES STANLEY GIBSON . CCCXLV.-The a- and p-Naphthalenesulphonylalanines. By WZLU MORRIS COLLES and CHARLES STANLEY Gmso~ . CCCXLV1.-The Rotatory Dispersive Power of Organic Compounds. Part XIII. The Significance of Simple Rotatory Dispersion. Rotatory Dispersion of Camphor-quinone and of Sucrose.By THOMAS MBRm LOWRY and EVAN MATTHEW RICHARDS CCCXLVI1.-Ring-chain Tautomerism. Part XI. The Fluoresceins and Rhodamines. By SIKHIBHUSHAN DUTT and JOCELYN FIELD THORPE . CCCXLVIII .-The System Zinc SulphateWater. By CHARLES R. BURY . CCCXLIX.-The Hydrof erroc yanides and Hydroferri-cyanides of the Organic Bases. Part IV. By WILLIAM CC.CXXXVIII.-2 5-Iminodihydro-1 2 3-triazole. . MURDOCH CUMMING . PAGE 2468 2474 2476 2481 2484 2488 2491 2495 2501 2505 251 1 2524 2538 254 CONTENTS. xxix PAGE CCCL.-Tautomerism Depending on the Mobility of a Hydroxyl Group. Part I . Open-chain Triad Systems. By MAURICE DUNCAN PARROW and CHRISTOPHER KELK INGOLD CCCL1.-The Complexity of the Solid State. Part I . The Behaviour of Pure Sulphur Trioxide. Part I. By ANDREASMITS and PIETER SCHOENMAKER CCCLI1.-The Complexity of the Solid State. Part 11. The Behaviour of Phosphorus Pentoxide. Part I. By ANDREASMITS and AREND JOAN RUTGERS CCCLIII.4tudies in Optical Superposition. Part VI. The Methyl-n-hexylcarbinyl Dimethoxysuccinates. By T. S. PATTERSON and CHARLES BUCHANAN . CCCL1V.-The Velocity of Reaction in Mixed Solvents. Part VPI. The Influence of the Base on the Velocity of Saponification of Esters in Methyl Alcohol-Water Mixtures. By WALTER IDRIS JONES HAMILTON MCCOMBIE and HAROLD ARCHIBALD SCARBOROUGH . CCCLV.-Trypanocidal Action and Chemical Constitution. Part I. Arylamides of p-Aminophenylarsinic Acid. By HAROLD KING and WILLIAM OWEN MURCH CCCLV1.-Isomeric Benzoyl Derivatives from Vinyldi-acetonamine. By FREDERIC STANLEY KIPPING and TOM GREASLEY Part XXXI. Action of Mercuric Oxide on Diaryldichlorosilicanes. By LEONARD REGINALD VYLE and FREDERIC STANLEY KIPPING . CCCLV1II.-An X-Ray Investigation of the Lower Members of the Fatty Acid Series. By REGINALD EDMUND GIBBS . CCCL1X.-Substituted Carbonates derived from p-Cresol. By ROLAND HALL GRIFFITH . CCCEX.-Influence of Pressure on the Freezing Point of p-Nitrotoluene m-Dinitrobenzene and Guaiacol. By NICOU ANTONOVICH PUSHIN . CCCLX1.-The Rotatory Dispersion of certain Normal Alkyl Hexahydromandelates. By CHARLES EDMUND WOOD and MERVYN ARTHUR COMLEY. Part 11. The Cathodic Overvoltage of Mercury. By SAMUEL GLASSTONE . By GEORGE DEAN . . CCCLVI1.-Organic Derivatives of Silicon. CCCLXII.-Studies of Electrolytic Polarisation. CCCEXII1.-The Atomic Weights of Carbon and Silver. 2543 2554 2573 2579 2590 2595 2611 2616 2622 2625 2628 2630 2646 265 xxx CONTENTS. PAGE NOTES .-The Behaviour of the Simple Halides with Water. By NEVIL VJXCENT SIDGWICK . . 2672 The Influence of Nitrogen Dilution on the Speed of Flame. By OLIVER COLIGNY DE CHAMPFLEUR ELLIS . . 2674 A Trustworthy Shaking Machine. By ARTHUR GEORGE MILLICAN . 2674 The Orientation of Derivatives of Triphenylphosphine Oxide. By FREDERICK CHALLENUER and JOHN FREDERICK WIL~NSON . . 2675 Spontaneous Combustion of Ethylene during the Prepar-ation of Ethylene Dichloride. By RAM KRISHEN SHARMA . . 2676 OBITUARY NOTICES . 267

ISSN:0368-1645    

DOI:10.1039/CT92425FP001

出版商:RSC    

年代:1924

数据来源: RSC

摘要:

10 IRVINE AND GILCHRIST: 11.-The Condensation of Nannitol with Olive Oil. By JAMES COLQUHOUN IRVINE and HELEN SIMPSON GILCHRIST. THE results described in the preceding paper have been applied to the investigation of the '' mannitol fat " prepared by the inter-action of mannitol and olive oil in the presence of sodium ethoxide (Lapworth and Pearson Biochem. J . 1919 13 296). On the evidence of analysis this synthetic fat contains mannitan dioleate and isomannide dioleate but the exact composition of the mixture and the structure of the constituents remained uncertain. It will be recalled that in the preparation of a " methylglucoside fat " by parallel methods the first compound formed is methyl-glucoside mono-oleate which on heating a t 200"/10 mm. loses a molecule of water and is converted into anhydro-methylglucoside mono-oleate.This behaviour suggests that the analytical samples of mannitol fat in the condition in which they were used did not represent precisely the composition of the original material. The specimens were dried for several hours a t 200-220" under diminishe TRE CONDENSATION OF MANNITOL WITH OLIVE OIL. 11 pressure before being submitted to analysis and in our experience, this treatment results in molecular dehydration. It would therefore appear that the isomannide dioleate detected by Lapworth and Pearson in mannitol fat originated principally during the drying process. Accordingly in repeating the reaction between mannitol and olive oil we removed the liberated glycerol by distillation in steam and limited the drying of the product to heating a t 100°/10 mm.Under these conditions the essential compound formed is mannitan dioleate contaminated with a trace of isomannide together with a small quantity of mannitol which lowered the carbon and hydrogen values ; no isomannide dioleate was present. The persistence with which unchanged mannitol remains dissolved in the synthetic fat is remarkable as this impurity resists the effect of boiling water and is not removed even by washing a dilute ethereal solution. Examination of the products of numerous preparations leads to the opinion that the first reaction in the condensation of mannitol with olive oil is the formation of mannitol dioleatc. This in turn is readily dehydrated to give maimitail dioleate and under more drastic conditions a second molecule of water is lost and isomannide dioleate is produced.Simultaneously any free mannitol left dissolved in the fat is ultimately converted into isomannide. There is no sharp line of demarcation between these consecutive reactions, although under conditions described in the experimental part a mannitol fat can be obtained which contains 90 per cent. of mannitan dioleate. Information bearing on the constitution of this compound was obtained by subjecting the fat to methylation a process which yielded monomethyl mannitan dioleate together with a trace of monomethyl isomannide. The latter was removed by distillation and the residual methylated fat was thereafter decomposed to give ethyl oleate and monomethyl mannitan. This in turn was con-verted into trimethyl mannitan and as the alkylation remained completely suspended a t this stage it was evident that one of the terminal hydroxyl groups of the hexitol chain remained intact (Irvine and Paterson T.1914,105 916). Obviously the strubture of the original mannitol fat can be deduced if the constitution of the above trimethyl mannitan is known. Preserving the condition that a terminal hydroxyl group is unsub-stituted the compound may be formulated in ten different ways, and although our experiments do not serve to discriminate between these possibilities the combined results of the research lead to a consistent structural formula for mannitan dioleate. In the original condensation the ease of formation of the anhydro-ring points to the fact that after the oleyl residues had entered the hexitol chain, R* 12 IRVINE AND GILCHRIST : the usual positions for anhydro-ring formation were still unsub-stituted.If the stereochemical formula for mannitol be written as H H OH OH I I I I G 5 4 3 2 1 it is evident that the anhydro-ring may couple any two of the hydroxyl groups with the exception of 6. Previous researches on mannitol have shown that these groups display a tendency to form five-membered rings possessing a cis-linking (Irvine and Paterson, T. 1914 105 898). The above conditions are satisfied only if the oxygen atom of the ring connects positions 1 and 4 so that the most probable formula for trimethyl mannitan is H H OMe OMe I I I 1 I I I HO*CH,-C -C -C--C -CH, OMel H H I L O - _ I On this basis the oleyl residues in the mannitol fat must occupy two of the three positions 2,3 and 5 but as substitution in position 5 of the mannitol chain is difficult the location of the acyl residues is practically restricted to 2 and 3.Taking all these factors into consideration and so far as the present experimental evidence leads the formula for " mannitol fat " may be stated as OXOXH H (X = CO*[CH,],*CH:CH*[CH,],.CH,) E X P E R I M E N T A L. Mannitan Dioleate. The preparation of a mixture of mannitan and isomannide dioleates has been described by Lapworth and Pearson (loc. cit.). As under the conditions outlined there is no guarantee that all the glycerol has been removed from the system a further purification was considered necessary and the synthetic fat after having been acidified with acetic acid was subjected to distillation in steam THE CONDENSATION OF MANNITOL WITH OLIVE OIL.13 The undistilled residue was dissolved in ether washed repeatedly with water and the solution dried over magnesium sulphate. On distilling the solvent a t first under ordinary pressure and later under diminished pressure the product was obtained as a pale yellow, very viscous oil which became practically solid a t the ordinary temperature. Analysis showed that the main constituent of the fat was mannitan dioleate but as the figures obtained were not in complete agreement with the calculated values some impurity was evidently present [Found C = 70.03 69.93; H = 10.32 10.44. Mannitan dioleate (C42H7607) requires C = 72.83; H = 10.98 per cent,.].The low value obtained for both carbon and hydrogen led to the conclusion that the impurity was mannitol or one of its dehydration products. As mannitol (C6H1406) requires C = 39.56 ; H = 7.69 per cent. it is evident that a small percentage of this compound would seriously affect the combustion values of the synthetic fat. Moreover it was found that mannitol is soluble in mannitan dioleate on heating and does not separate out on cooling the solution. Moncmsthyl Mannitan Dioleate. The quantities of reagents employed were calculated on the assumption that in mannitan dioleate two hydroxyl groups of the molecule are free for methylation. Thirty grams of mannitan dioleate (1 mol.) were dissolved in 49.3 grams of methyl iodide (8 mols.) and methylated by the addition of 40-2 grams of silver oxide (4 mols.).The reaction which was spontaneous proceeded normally and was completed by heating for eight hours on a water-bath. The methylated product isolated in the usual manner, proved to be essentially monomethyl mannitan dioleate [Found : OMe = 6.1. Monomethyl mannitan dioleate (C,3H7,0,) requires OMe = 4.5 per cent.]. As only one methyl group had entered the chain it was deemed advisable to carry out a futher methylation to ascertain if the remaining free hydroxyl group could be sub-stituted. It was found however that no increase took place in the methoxyl content (Found OMe = 5.9 per cent.). This result adds another example to the cases of steric hindrance encountered in the mannitol series.It will be seen that the value of the methoxyl content is slightly high which is consistent with the idea that a small proportion of mannitol had escaped condensation and had subsequently under-gone methylation. The methylated fat was accordingly heated a t 200°/10 mm. and as the temperature rose from 100" to 160° a few drops of a volatile compound distilled (n 1.4506). Estimation of the methoxyl content of this distillate gave the notably high value o 14 THE CONDENSATION OF MANNITOL WITH OLIVE OIL. (1) 20.67 ; (2) 18.10. Monomethyl isomannide (C,H,,O,) requires OMe = 19.38 per cent. Although it was difficult to carry out accurate analysis on such a small scale it is quite evident that the original fat contains some impurity in all probability a dehydration derivative of mannitol which on methylation gives a compound having a much greater methoxyl content then the normal product.This accounts adequately for the analytical result previously reported for monomethyl mannitan dioleate. Hydrolysis of Monomethyl Mannitan Dioleate and Simultaneous Condensation of the Acid Product with Ethyl Alcohol. A 4 per cent. solution of the methylated mannitol fat in ethyl alcohol containing 0.5 per cent. of hydrogen chloride was heated according to the method adopted by Irvine and Rose (T. 1906 89, 814). A small quantity of charcoal was added to tihe solution, which was boiled under a reflux condenser for eighty hours. The liquid was then neutralised with barium carbonate the filtrate being evaporated to dryness under diminished pressure after which the residue was extracted with absolute alcohol the solution filtered and the solvent distilled.On extracting the product with cold ether and evaporation of the solvent a colourless highly refractive liquid remained (b. p. 125-130"/0~02 mm. n 1.4544) [Found OEt = 15.35. Ethyl oleate (C,,H,,O,) requires OEt = 14.52 per cent.]. Monomethyl Mannitan. The material left unextracted with cold ether in the above prepar-ation was dissolved in acetone containing a little alcohol and gave, on subsequent evaporation of the solvents a very viscous syrup. This was purified by extraction with ethyl acetate a t the boiling point and proved to be monomethyl mannitan [Found (7 = 46.98 ; H = 8.00; OMe = 15.74. Monomethyl mannitan (C7Hl4O5) re-quires C = 47.19; H = 7.92; OMe = 17.41 per cent.].Trimethyl Mannitan. Monomethyl mannitan obtained as above was subjected to the silver oxide reaction. The reaction mixture consisted of 1.5 grams of monomethyl mannitan (1 mol. containing three free hydroxyl groups) 11.7 grams of silver oxide (6 mols.) and 14.4 grams of methyl iodide (12 mols.) a little methyl alcohol being added to aid solution. The product on isolation was subjected to a second methylation in which no extraneous solvent was required, aa the partly methylated syrup was freely soluble in methyl iodide. This second reaction yielded a clear syrup (n 1.4528) and after a third treatment the refractive index was unaltered showing tha THE CONSTITUTION OF POLYSACCHARIDES. PART VII. 15 no further methylation had taken place. On distillation under diminished pressure (b. p. 115-~20"~0~18 mm.) the product was isolated as a clear mobile syrup (n 1.4518). Analysis showed t'hat the terminal hydroxyl group in the chain had resisted methyl-ation thereby proving that the anhydro-linking in the original fat must occur between two other groups of the alcohol chain [Found : C = 52.72; H = 8.56. Trimethyl maniiitan (C,H,,O,) requires C = 52.42 ; H = 8.73 per cent.]. The thanks of the authors are due to the Food Investigation CHENICAL RESEARCII LABORATORY, UXIVEBSITY OF ST. ANDREWS. Board under whose auspices the work was conducted. UNITED COLLEGE OF ST. SALTATOR AND ST. LEONARD, [Receiaed November 7th 1923.

ISSN:0368-1645    

DOI:10.1039/CT9242500010

出版商:RSC    

年代:1924

数据来源: RSC

摘要:

THE CONSTITUTION OF POLYSACCHARIDES. PART VII. 15 111. -The Constitution of Polysacchurides. Part VII. Esparto C'ellulosc. By JAMES COLQUHOUN IRVINE and EDMUND LANGLEY IIIRST. IT is now recognised that the expression " cellulose " is applied in a general sense and is made to include a number of closely-related substances which whilst they display many physical and chemical features in common are so divergent in their properties that they must be regarded as different chemical individuals. This point has not been overlooked in our investigations on mole-cular structure and accordingly our earlier work in this field was carried out on cotton cellulose which is regarded as the standard example of a normal cellulose. The cellulosic constituents of many other fibre-bearing plants show variations from this standard and the question is raised as to whether such substances are mixtures, containing cotton cellulose as one constituent or are composed essentially of an isomeric variety of the polysaccharide.This does not exhaust the alternatives and theoretically it is possible that polysaccharides of many different types may exist. For example these compounds may in some cases consist of large molecules or they may be polymerides of simple molecules con-taining identical or different hexose units. Finally they may consist of polymerised units in which hexose residues are con-densed with either higher or lower members of the sugar group. It is evident that even the elemcntary study of different varieties of cellulose is complicated if consideration is given to all the theoretical possibilities involved 16 IRVINE AXD HIRST THE CONSTITUTION OF We have selected esparto cellulose for inclusion in our research programme partly in view of its technical importance but principally on account of its comparative simplicity and close relationship to cotton cellulose.As is well known approximately one-half of the weight of dried esparto grass can be extracted on boiling with sodium hydroxide (preferably under pressure) and the residue constitutes an important paper-making material. Esparto cellulose is not however identical with cotton cellulose. The distinction is more than physical as apart from variations in property which are attributable to the condition of the fibres and are thus apparent in mechanical working this variety of cellulose is characterised by a number of special reactions.Amongst these is the formation of furfural on heating with acids a result which indicates the presence of a pentose constituent. Prolonged diges-tion with sodium hydroxide gradually eliminates this component, and the extract is found to contain a " pentosan " which may be precipitated. It follows in consequence t.hat the esparto cellulose of the paper-maker will always contain a variable amount of one component capable of yielding furfural and the proportion of this constituent will depend on the conditions adopted in the pre-liminary treatment with alkali. In general about 80 per cent. of esparto cellulose is composed of authentic cellulose possessing the formula (C,H,,05)Z and convertible quantitatively into a hexose on hydrolysis.Taking these factors into consideration esparto cellulose may consist of (1) a mixture of polysaccharides derived respectively from hexose and pentose units or (2) a mixed polysaccharide in which the hexose and pentose residues are condensed together. It was with the object of discriminating between these alternatives and of definitely identifying the parent hexose and pentose sugars that the present research was undertaken. The process of disrupting a cellulose by the action of highly concentrated acid offers little prospect of success in this particular case as the liberation of furfural introduces serious complications. This method of attack has already been explored by Cunningham (T.1918 113 173) and in the course of a separate inyestigation (Hirst and Robertson forthcoming paper) the limitations attached to the process have been defined. We have accordingly utilised the series of reactions originally designed to ascertain the com-position of cotton cellulose and have converted esparto cellulose into the fully substituted acetate (in this case a mixture) from which the corresponding methylhexoside and methylpentoside were prepared. The esparto cellulose employed was obtained from Spanis POLYSACCHARIDES. PART VII. ESPARTO CELLULOSE. 17 Grass which was subjected to the usual boil with alkali and the residue thereafter treated with moist chlorine to remove colouring matter and residual lignin. Although the white fibrous mass was apparently uniform it yielded 12 per cent.of its weight of furfural on distillation with acid; the result corresponds to the presence of 18.5 per cent. of a pentosan and this constituent was completely removed by prolonged extraction with boiling sodium hydroxide solution. The materials requiring separate examination were thus : (a) Esparto cellulose free from lignin. ( b ) Pentosan constituent extracted from (a). ( c ) Esparto cellulose free from pentosan. Description will be facilitated by stating that the product ( b ) proved to be a xylan which was identified by conversion into crystalline xylose and also into the characteristic trimethyl p-methyl xyloside. In addition product (c) was transformed by standard methods into cellobiose and also into 2 3 6-trimethyl glucose, so that in essential chemical character this constituent is mole-cularly akin to if not actually identical with the cellulose of cotton.Special attention was therefore directed to esparto cellulose in the original form in which the xylosan component is still present. On acetylation the cellulose yielded a fully substituted acetate and as the loss of pentosan in this reaction was negligible the pro-duct contained both a hexosan triacetate and a pentosan diacetate. On the basis of analysis the total yield of acetate was 97.2 per cent. of the theoretical amount a result which may be taken as quantitative in view of the experimental difficulties involved. Thereafter by heating with methyl alcohol containing hydrogen chloride the esparto cellulose acetate was converted into a crystalline mixture of methylglucoside and methylxyloside.This modification of the usual.method of hydrolysing a carbohydrate complex proved of material service in preserving the quantitative aspect of the work as the xylose on liberation was continuously transformed into methylxyloside and was thus protected from the destructive action of the hydrochloric acid. By means of control experiments, conducted with artificial mixtures of glucose and xylose con-ditions were established which diminished the loss of pentose in the reaction to a minimum (3 per cent.). The joint weight of methylglucoside and methylxyloside thus obtained corresponded to 91.9 per cent. of the theoretical quantity and a sample of the total product when hydrolysed with dilute aqueous acid gave a mixture of glucose (84 per cent.) and xylose (16 per cent.) 18 Ir \ a- & B-~~ethylglucosides.a- & B-Methylxylosidos. .i. Xylose IRVINE AND HIRST THE CO1U’STITUTION OF Discussion of Results. To facilitate reference the complete series of transformations involved in the research may be represented by the scheme :-Esparto Grass Esparto Cellulose (Xylan content = 18.5 per cent ) 4 Cellulose + Xylan I 1 Esparto Cellulose Acetate consisting of cellulose triacetate and xylan diacetate (xylan content = 18.5%) / \ Series A has no quantitat’ive significance but furnishes evidence as to the constitution of the two main components. On the other hand series B represents a sequence of quantitative operations and the over-all yields of pure crystalline products show that as a minimum the esparto cellulose employed was converted to the extent of 89.4 per cent.into glucose and xylose. The experi-mental loss is almost entirely due to the formation of traces of furfural and as this factor was controlled a t each stage by analysis, it is possible to recalculate the results. On introducing the neces-sary correction the combined glucose and xylose obtainable from esparto cellulose is 92.0 per cent. of the amount theoretically possible according to the equation I n the particular samples of esparto cellulose employed the ratio nx my was 4.04 1 but although typical this is a variable and is entirely dependent on the conditions of the preliminary boiling process. A sample of esparto cellulose may in fact contain any proportion of xylan from about 20 per cent.downwards. Unless the unlikely assumption is made that the action of alkali is prefer-ential and whilst leaving hexose units largely unattacked detaches and dissolves combined pentose units from a polysaccharide it follows that esparto cellulose is not a chemical individual but is a mixture. This was supported by the fact that when esparto cellulose was subjected to acetolysis under varied conditions no trace of any disaccharide containing a xylsse residue was detected POLYSACCHARIDES. PART BII. ESPARTO CELLULOSE. 19 On the other hand cellobiose was obtained by the acetolysis of the hexose cellulose which remained after complete removal of the xylose cellulose by the action of alkali.Inspection of the experimental details gives an indication of the relative molecular complexity of the two components present in esparto cellulose. The ready solution of the xylan constituent in alkali and the fact that after precipitation it may be dissolved in hot water point to a comparatively low molecular weight. On the other hand the extreme resistance to attack by reagents dis-played by the hexose cellulose is even more pronounced than in the case of cotton. Up to the present our experiments do not serve to show if the xylan is mechanically mixed with the hexose cellulose or if the two constituents form a solid solution. Micro-scopic examination of esparto fibre and of the acetates to which it gives rise supports the latter view and this aspect of the general inquiry is being included in an extension of the research.Summary. 1. Esparto cellulose in the condition in which the material is used for paper-making is a mixture (or more probably a solid solution) of a genuine hexose cellulose (81.5 per cent.) and a pentosan (1 8-5 per cent .) . 2 . The hexose cellulose is composed entirely of glucose residues, is convertible into cellobiose and also into 2 3 6-trimethyl glucose In these respects and also in its high molecular complexity the compound resembles the cellulose of cotton. 3. The pentosan component is a polymerised anhydro-xylose and may be isolated as a definite xylan which yields xylose on hydrolysis. 4. Esparto cellulose yields on acetylation the triacetate of the glucose cellulose together with the diacetate of the xylan.Yield 97.2 per cent. 5 . The product of acetylation has been converted into mixtures of a- and p-methylglucoside with a- and (3-methylxyloside. Yield 91.9 per cent. 6. No sugars other than glucose and xylose have been detected in the hydrolysis products obtained from esparto cellulose. 7. A method of preparing xylose from esparto cellulose is described. E X P E R I M E N T A L. The “ boiled esparto grass ” used in the present investigation was supplied by Messrs. Tullis Russell & Co. of Markinch. It had been subjected to the usual extraction with 6 per cent. aqueous alkali under 45 lb. steam pressure but was still unbleached and showed in places portions of unchanged lignin. With the object o 20 IRVINE AND HIRSTI THE CONSTITUTION OF obtaining a starting material which would be as far as possible a normal esparto cellulose the colouring matter and the residual lignins were removed by treatment with moist chlorine.After thorough washing with warm water and drying in air the esparto cellulose presented the appearance of a white fibrous mass con-taining moisture 10-5 and ash 1.07 per cent. Distillation with 12 per cent. aqueous hydrochloric acid gave an amount of furfural, estimated as the phloroglucide compound (Kruger and Tollens, 2. angew. Chem. 1896 2 33) corresponding to 18.5 per cent. of xylan (Krober J. Landw. 1900 48 379). I n view of the later experiments which indicated the absence of other pentoses the figures quoted refer to pentosans in the form of xylan.Acetylation of Esparto Cellulose. Acetylation of esparto cellulose by Barnett's method did not proceed so readily as in the case of cotton cellulose (Irvine and Hirst T. 1922 121 1585) but the difficulties appeared to be chiefly mechanical and to be due to the failure of the acetylating reagents to penet>rate the hard compact surface of the dry material. I n preliminary experiments efforts were made to disintegrate the esparto cellulose by rapid mechanical agitation in boiling water, but these proved to be unsuccessful owing to the very extensive " ricing " which took place. Acetylation could be accelerated by raising the temperature of the reaction but this promoted the destruction of the pentose constituent. The most satisfactory results were obtained by the method now described by means of which more than 200 grams of esparto cellulose acetate were prepared.Fourteen grams of air-dried finely-shredded esparto cellulose were incorporated with 60 C.C. of glacial acetic acid, through which a stream of dry chlorine had been passed for thirty seconds and 60 C.C. of acetic anhydride were thereafter added. After efficient stirring of the mixture sulphur dioxide gas was bubbled through the mass for one minute and the whole then continuously stirred for a period of several hours. The spon-taneous rise of temperature was small and after two hours the esparto cellulose gelatinised and dissolved slowly. The later sta.ges were hastened by warming the mixture at 40" and a t the end of twenty-four hours a clear almost colourless solution was obtained which was treated with chloroform and water in the manner already described for cotton cellulose acetate (Irvine and Hirst loc.cit.). The acetate when dried a t 100" weighed 21.06 grams. Calculating for the triacetate of a C,H,,05 unit and a diacetate of a C,H,O, unit present in the proportions of 82 per cent. and 18 per cent., respectively and allowing for the moisture and ash content thi POLYSACCHARIDES. PART VII. ESPARTO CELLULOSE. 21 yield corresponds to 97.2 per cent. of the theoretical value. The a,queous portion gave a slight trace of reduction with Fehling's solution and consequently the whole of the filtrate and the wash-ings were distilled in steam to remove acetic acid boiled with 4 per cent. hydrochloric acid for nine hours to hydrolyse any acetate, and thereafter evaporated to a small bulk.This solution showed no optical activity ; the residue left after neutralisation and evapor-ation to dryness had practically no action on Fehling's solution, thus proving that the weight of water-soluble material formed during acetylation was negligible. Esparto Cellulose Acetate.-The esparto cellulose acetate was white in colour and differed from cotton cellulose acetate prepared in the same manner by being softer in texture and more sensitive to high temperatures. Decomposition of the majority of speci-mens began a t 120° but this was variable and appeared to depend largely on the efficiency of the washing process in eliminating every trace of acid. The acetate was soluble in chloroform and acetone, but insoluble in alcohol.The specific rotation of a chloroform solution was of the order - 20" (c = 1*2) but owing to the cloudi-ness of the solution this value is only approximate [Pound Mois-ture = 1.5; ash = 0.29; C = 49.8; H = 5-46; CH,*CO = 44.9; furfural = 6.9. Calc. (for a mixture containing 18.5 per cent. of xylan before acetylation) C = 50.0 ; H =.5.55 ; CH,*CO = 43-6 ; furfural = 6.8 per cent.]. No loss of pentosan had therefore occurred during the acetylation. Conversion of Esparto Cellulose Acetate into Methylglucoside and Met hylxyloside. As in the case of cotton cellulose acetate it was found that on treatment at 120-130" with methyl alcohol containing a small proportion of hydrogen chloride esparto cellulose acetate gradually dissolved with elimination of the acetyl groups together with hydrolysis of the polysaccharide and condensation of the products of hydrolysis wit'h methyl alcohol.Under parallel experimental conditions it was invariably the case that esparto cellulose acet-ate was more resistant to the action of these reagents than cotton cellulose acetate. On account of this difficulty higher temperatures an& longer periods of treatment were required and this involved slight loss of material owing to traces of decomposition. Careful temperature control was thus required and even under the best experimental conditions partial destruction of the pentose residues took place. Control experiments on the action of acid methyl alcohol on xylose at 120-130" proved that the decomposition of the pentose with formation of furfural was unavoidable.Th 22 IRVINE AND KIRST THE CONSTITUTION OF yields quoted below which have becn confirmed on several occasions, must therefore be taken only as minima. It was found convenient to use 4 grams of esparto acetate in each experiment the material being heated with 60 C.C. of methyl alcohol containing 1.5 per cent. of hydrogen chloride a t 130" for 120 hours. The solid remaining undiSsolved weighed 0.12 gram and consisted partly of ash (silica) and partly of regenerated cellulose. After one treatment with animal charcoal the solution was only slightly coloured and by the usual procedure gave 2.490 grams of syrup precautions being taken to ensure the complete dryness of the product.The cal-culated quantity of mixed glucoside and xyloside obtainable from 4 grams of an acetate giving 6.9 per cent. of furfural is 2.710 grams, and the yield was therefore 91.9 per cent. of the theoretical amount. The syrup crystallised spontaneously (m. p. 105-150" ; [a]= +!Woo for c = 1.200 in acid methyl alcohol). This optical value was permanent no change being recorded after further t'reatment in a sealed tube a t 100". Analysis of the crystalline product showed that a loss of 3 per cent. of pentose had occurred and this corresponds to approximately 16 per cent. of the total pentose present [Found C = 43.3; H = 7.25; OMe = 15.6; xylose = 15.7. Calc. for a mixture of C6H1,0 (84 per cent.) and C,H,,O, (16 per cent.) C = 43.4 ; H = 7.23 ; OMe = 16.4 per cent.].On recrystallisation from ethyl alcohol pure cc-methylglucoside was obtained (m. p. 164") and a polarimetric study of the hydrolysis of the mixed hexoside and pentoside from the sealed tubes showed that the material consisted of cc- and p-methylglucosides together with cc- and (3-methylxylosides. 0.4140 Gram dissolved in 25 C.C. of 3 per cent. aqueous hydrochloric acid and heated at 100" with-the addition of a small quantity of charcoal gave the following readings (C = 1.656) : Time .................. 0 min. 45 mins. 90 mins. 240 mins. [ a ] D ..................... +90" 59.1' 46.2" * 45.6" * (constant) * Concentration calculated on weight. of sugar formed during hydrolysis. The equilibrium value of the specific rotation of a mixture of glucose (84 per cent.) and xylose (16 per cent.) is + 46-6".Further evidence was obtained by estimation of the sugar present after hydrolysis by Allihn's method. Ten C.C. of the solution after completion of hydrolysis gave (after neutralisation) on treatment with Fehling's solution 288.8 mg. of copper (calculated 294 mg.). Behuviour of Artijicial Mixtures of Xylose and Glucosc. The identification of the pentose constituent as xylose was confirmed by comparing the behaviour of an artificial mixtur POLYSACCHARIDES. PART VII. ESPARTO CELLULOSE. 23 of glucose (84 per cent.) and xylose (16 per cent.) with that of the material isolated from the sealed-tube experiments. 5.0 Grams of such a mixture were treated with acid methyl alcohol at 100" for twenty-f our hours and the mixture of methylxylosides and methyl-glucosides was isolated in the usual manner.Yield 5.3 grams or 97.5 per cent. of the theoretical amount. This mixture crystallised spontaneously (M. p. 105-140") and showed [.ID +90.6" in acid methyl alcohol for c = 1.445 (Found C = 43.3 ; H = 7.07 ; OMe = 16.1 ; xylose = 15.4. Calc. C = 43.25; H = 7.24 ; OMe = 16-4 ; xylose = 16.0 per cent,). On hydrolysis under the same conditions as before 0.527 gram dissolved in 25 C.C. of 3.5 per cent. aqueous hydrochloric acid gave the following figures on heating a t 100" (c = 2.108) : Time ............ 0 min. 45 mins. 180 mins. 270 mins. 300 mins. [U]D ............... $90" 58" 45.6" 46.1" * 4&1° * * Concentra,tion recalculated on weight of free sugar formed. The calculated value for the end-point is + 46.6".When treated with Fehling's solution 3-2 C.C. of the fully hydrolysed solution gave 123 mg. of copper (calc. 121 mg.). Control Experiments. The above evidence as to the identity of the pentose constituent is based on polarimetric readings and is valid only if xylose is stable under the conditions of hydrolysis. In view of the marked action of dilute mineral acids on pentoses it was necessary to study the action of 3 per cent. aqueous hydrochloric acid on xylose. With exactly the same experimental conditions as those described above, the following observations were recorded which prove the stability of xylose in so far as the present series of experiments is concerned. Time .......................................... 0 min 90 mins.240 mins. [ a ] ~ ............................................. +20*6' 2 0 . 2 O 19.2' Unchanged xyiose per cent. ............ 100 99 92 Slight traces of furfural were observed after 150 minutes. The amount of xylose remaining after 250 minutes was confirmed (after steam distillation to remove any furfural) by a copper estimation. Reactions of Esparto Cellulose free f r m Xylan. As stated in the introduction esparto cellulose which has been extracted with alkali until all xylan has been removed displays the essential chemical properties of cotton cellulose. The conversion into cellobiose octa-acetate was carried out with small quantitie 24 IRVINE AND HIRST THE CONSTITUTION OF of material in order' to secure efficient temperature control and the following is an account of a typical experiment.Two grams of extracted esparto cellulose were treated a t 15" with a mixture of 30 C.C. of acetic anhydride and 3 C.C. of con-centrated sulphuric acid. The temperature was then suddenly raised to 110" and maintained at this point until the solution became nearly black. On pouring into excess of cold water cello-biose octa-acetate was precipitated and this after washing with water and recrystallisation from ethyl alcohol weighed 0-35 gram. Under exactly parallel conditions control experiments with 2 -gram lots of cotton cellulose gave 0.38 gram of the octa-acetate. Similarly when exhausted esparto cellulose was methylated by methyl sulphate and alkali alkylation proceeded as in the case of cotton cellulose and a trimethyl derivative was formed.This was converted by standard processes into the corresponding trimethyl methylglucoside which was finally hydrolysed to give the parent substituted glucose. As a result of these operations 2 3 6-tri-methyl glucose was obtained displaying the physical constants characteristic of this compound. These reactions point to the chemical identity of cotton cellulose with extracted esparto cellulose but it is worthy of mention that in no case was cellobiose octa-acetate obtained from material which had not been fully exhausted with alkali. Preparation of Xylose from Esparto Cellulose. This was accomplished in two stages in the first of which xylan was isolated and this was afterwards hydrolysed to give crystalline xylose. One hundred parts of esparto cellulose were boiled gently with frequent stirring for ten to twelve hours with a solution of 120 parts of sodium hydroxide in 1,000 parts of water.The residual solid was filtered (using a porcelain Buchner funnel without filter-paper) and well pressed. This residue still contained about 143 per cent. of pentosan which was removed completely by a second treatment with the alkali. On cooling the dark brown filtrate to 50" and adding an equal bulk of 90 per cent. alcohol a white, flocculent precipitate formed and after standing for twelve hours, the supernatant liquid was poured away. The crude xylan was then filtered rapidly and while still moist was triturated with aqueous acetic acid to remove alkali after which the material was washed with water alcohol and ether in succession.Unless the xylan was dried slowly and a t a low temperature the material became discoloured and formed a hard horny mass. Yield 15-16 parts. In this condition the xylan contained 3 - 4 per cent. o POLYSACCHARIDES. PART vn. ESPARTO CELLULOSE. 25 mineral matter and gave a yield of furfural corresponding with a xylan content of 91 per cent. Hydrolysis was effected by dissolving in 2 per cent. aqueous sulphuric acid and heating at go" when the rotation altered to dextrorotatory and rempined constant after six to eight hours' treatment. Judging from the optical value the amount of xylose then present was about 75 per cent. of the theoretical weight the loss being due to the formation of furfural. After neutralisation with barium hydroxide the filtered solution was evaporated under diminished pressure when the syrup thus obtained crystallised spontaneously.The average yield was of the order 3 5 - 4 0 per cent. of the theoretical amount but occasionally yields of more than 50 per cent. were obtained. No pentoses other than xylose were detected in any of the experiments and this was confirmed by preparing the characteristic xylose phenylosazone from (a) the recrystallised sugar (b) the original crude syrup and (c) the mother-liquors accumulated during recrystallisations. In each case the osazones were identical under the microscope and melted at 152-160" with decomposition. The recrystallised xylose showed the correct mutarotation and permanent specific rotation ([a];" + 19') and melted at 143-144". The figures quoted in the literature vary from 140" to 145" and a mixed melting point with an authentic specimen showed no depression. Final confirmation of the identity of the pentose was obtained by the methylation process which gave the same trimethyl @-methyl-xyloside as had previously been obtained from xylose (Carruthers and Hirst T. 1922 121 2299). The investigation of the subjects dealt with in the present paper is being continued and we desire to reserve the application to cellulose of methods developed in this laboratory. We also take the opportunity to express our thanks to Messrs. Tullis Russell and Co. for valuable help in the provision of material and to the Carnegie Trust for a Fellowship which enabled one of us to take part in the work. CHEMICAL RESEARCH LABORATORY, UNIVERSITY OF ST. ANDREWS. UNITED COLLEGE OF ST. SXLVATOR AND ST. LEONhRD, [Received Nocernber 6th 1923.

ISSN:0368-1645    

DOI:10.1039/CT9242500015

出版商:RSC    

年代:1924

数据来源: RSC

摘要:

26 CAMPHORYLCARBAMATES AND THEIR PHYSIOLOGICAL ACTION. IV. -Camphorylcarbamates and their Physiological Action. By HANS EDUARD FIEBZ-DAVID and WALTER MULLER. FORSTER and FIERZ (T. 1905 87 110) prepared methyl and etlhyl camphorylcarbamates by the interaction of camphorylcarbimide with the corresponding alcohols but the method and also the yields were unsatisfactory. A very simple method of preparation consists in the interaction of aminocamphor and alkyl chloro-formates the urethanes being obtained in almost quantitative yield : Thirty-seven grams of isonitrosocamphor dissolved in 150 C.C. of 30 per cent. sodium hydroxide were reduced with 37-40 grams of zinc dust the base was removed with ether and extracted therefrom with 40 per cent. hydrochloric acid. The aqueous solution was twice extracted with 50 C.C.of ether and the dissolved ether removed by a current of air a t 80". The solution of aminocamphor hydro-chloride mixed with 100 C.C. of 30 per cent. sodium hydroxide was heated at 60' and stirred mechanically while the chloroformic ester (110 per cent. of the theoretical quantity) was added slowly. The urethane which separated as a viscous mass was distilled under diminished pressure. isoAmyl and allyl camphorylcarbamateg are viscous oily liquids ; the others mentioned in the table crystallise in long lustrous needles. Camphorylcarbamate. M. p. B. p. [a]= in CHCI,. Methyl . . . . . . . . . . . . 110" 169" (11 mm.) + 39.4" Ethyl . . . . . . . . . . . . . . 85 178 (13 mm.) + 35-1 i80Pl'Opyl . . . . . . . . . . 73 170 (10 mm.) + 35.3 isoButyl .. . . . . . . . . . . 83 184 (11 mm.) + 33.9 isoAmyl . . . . . . . . . . . . liquid 199 (11 mm.) + 34.2 Ally1 9 9 186 (10 mm.) + 34.3 .............. The analytical data are recorded in Dr. W. Miiller's thesis (Zurich, 1923). Ally2 Curbonate.-The oil obtained by the action of carbonyl chloride upon allyl alcohol is mixed with water when two oily layers separate. The heavy oil is allyl chloroformate which boils a t l l O o not 180" as stated by Thiele and Dent (Annulen 1880, 205 227; 1898 302 269). The light oil on distillation yields uZZyE carbonate b. p. 166'1730 mm. as a mobile liquid of unpleasant odour (Found C = 59.03 ; H = 7-28. C,HloO requires C = 59.15 ; H = 7.04 per cent.). The physiological action of these camphorylcarbaiaates was examined with the hope that they would produce the combine DETERMINATION OF SURFACE TENSION ETC. PART 11. 27 effects of camphor and the urethanes. The investigation was undertaken by Prof. Loewy in the laboratories of the Aktiengesell-schaft fur Anilinfabrikation Berlin. He reported that their pro-nounced poisonous action renders these compounds unsuitable for practical application. Administered to dogs in doses of 0.3 gram per kilogram of body-weight they had no marked action on the heart but induced slow respiration and sleep suddenly interrupted by strong convulsions. THE Sw-ISS TECHNICAL HIGIK SCHOOL, ZURICH. [Received November Znd 1923.

ISSN:0368-1645    

DOI:10.1039/CT9242500026

出版商:RSC    

年代:1924

数据来源: RSC

摘要:

DETERMINATION OF SURFACE TENSION ETC. PART 11. 27 V.-The Determination of Surface Tension from the By SAMUEL SUGDEN. SOME time ago (T. 1022,121 858) the author discussed the theory of the method of maximum bubble pressure and described a simple apparatus by means of which determinations of the surface tension of water and benzene had been made. Measurements of the surface tension of some twenty different substances a t temperatures up to 300" have now been carried out by this method. The results of these experiments will be discussed in subsequent papers; the present communication describes an improved form of apparatus which has been evolved during this investigation and outlines a much simpler method of calculating the surface tension from the observed data. 1.Description of Apparatus.-The apparatus consists essentially of three parts the vessel holding the liquid under examination (referred to below as the bubbler) a pressure gauge and a small mercury aspirator. The improved form of bubbler is shown in Fig. 1. The side tube A is connected to the gauge and aspirator. Air (dried if necessary) enters the tube B and passes through the capillary if tap C is closed but through the wide tube if C is open. The ground joint at D and the tap C must fit well as no lubricant can be used except the substance under investigation and in many cases when this is solid a t the ordinary temperature one has to rely on the unlubricated joint. Fortunately the pressure differences concerned are slight and a small leak can be neutralised by a rather more rapid flow of mercury in the aspirator.The apparatus as supplied by the makers * is fitted with the Maximum Pressure in Bubbles. Part 11. * The bubblers and gauge wcre supplicd by Scientific Supplies Ltd. 52, Hatton Garden E.C.1 28 SUGDEN THE DETERMINATION OF SURFACE TENSION two inner tubes protruding about an inch below the stopper. A suitable length of tube of 3 to 4 mm. diameter is cut with the lower end of sharp cross-section normal to the axis of the tube and is sealed on to the limb bearing the stopcock. A length of 2 mm. tube is then sealed on to the other limb and is drawn out into a suitable capillary which is cut off level with the end of the wide tube. After a little practice the size of capillary needed can be FIG. 1. estimated by the eye.The best test is to set up the apparatus and take a rough reading with the aid of benzene. A gauge containing absolute alcohol being used, the capillary is satisfactory if bubbles are formed with a gauge reading of not less than 4 cm. and not more than 10 cm. The upper limit corresponds to tubes with a diameter of 0-005 cm.; smaller tubes are difficult to work with as they are too readily blocked by particles of dust. The water gauge used in the earlier experiments was very troublesome and required continual cleaning to give trust-worthy readings. Absolute alcohol tinted with magenta was therefore substituted for the water and the gauge was enclosed in a water-jacket. The density of the sample of alcohol used was determined a t loo Z O O and 30° and a table con-structed to convert gauge readings a t any temperature within these limits into dynes /cm .2. The mercury aspirator described in the previous paper has been found satis-factory. For smooth working it is im-portant t o see that there is an unbroken column of mercury between the tap and the end of the capillary. that 2 . Method of Calculation.-It was shown in the previous paper P y = ~l-?-jpq . . . . . . mliere y is the surface tension in dynes/cm. and P is the difference between the pressures required to liberate bubbles from the tw FROM THE MAXIMUM PRESSURE IN BUBBLES. PART II. 29 tubes measured in dynes/cm.2. X and X are functions of a2 and rl and r where (22 = g ( D - d ) 2y- . . * . . . . . Here g = acceleration due to gravity = 981 cm./sec.2 D and d are the densities of the liquid and vapour respectively and rl and r2 are the radii of the two tubes.In the paper referred to above, equation (1) was solved by a method of successive approximations using a table giving the ratio X / r for a number of values of rla. Now (I) may be written y = A . P .f(r1 r2 a ) . . . . . . (3) As a increases and r decreases f (r, r2 a ) tends to unity and for the sizes of tubes used and for most organic liquids a t tem-peratures up to the boiling point it is never greater than 1.04. Further since rl is small X varies very little from liquid to liquid, so that we can regard the factor multiplying AP as a function of r2 and a or as a function of r2 and the quantity gDIP which is nearly proportional to a2.It has been found that within the limits specified below equation (1) can be replaced by y = A . P when r2 is measured in crn. The limits within which this formula holds were tested by cal-culating a number of values by (4) and by the general method given in the previous paper. In Table I the column headed Surface Tension (1) gives the values calculated by equation (4). In these calculations D = 1. TABLE I. Surface tension. rl r2 P a2 g D (1) (2) em. cm. dyn./cm.2. mm.2 1+0*69r2? * dyn./cm. dyn./cm. Diff. 0.005 0.100 6540 3.546 1.0104 17.39 17.39 0 0.005 0-200 6540 3.493 1.0207 17-14 17.12 0.02 0.010 0.100 3270 3.774 1.0207 18-51 18.53 0.02 0.010 0.200 3270 3.658 1.0414 17.94 17.93 0.02 0.005 0.100 19620 10.56 1.0035 51.80 51.78 0-02 0.010 0.200 9810 11.185 1.0138 54.85 54.86 0.01 For organic liquids at the boiling point a2 is rarely much less than 4 mm.2.Hence from the first four lines of Table I it is seen that formula 4 holds with an accuracy of 1 part in 1000 when rl is less than 0.010 em. and rz is not greater than 0-20 cm. These limits are determined by practical considerations. If rl is greater than 0.010 cm. the readings on the gauge are too small t~ giv 30 SUGDEN THE DETERMINATION OF SURFACE TENSION accurate values for the surface tension; on the other hand tubes smaller than 0.005 cm. are very easily blocked by particles of dust. 3. Culibrutim and CuEcuZutions.-The direct measurement of the radius of the capillary as described in the previous paper is some-what tedious and is scarcely practicable in a series of measure-ments as the capillaries may be broken when the apparatus is being cleaned.The surface tension of benzene a t 20" is now known with accuracy and may be taken as 28.88 dynes/cm. (Richards and Carver J . Amer. Chem. Soc. 1921,43 827 ; Harkins and Brown ibid. 1919 41 499). This value has been confirmed by the author by two methods that of capillary rise (T. 1921, 119 1483) and by the method of maximum bubble pressure (Zoc. cit.). Hence benzene may be used as a convenient reference liquid. It has also been found that traces of common impurities such as thiophen have no appreciable effect on its surface tension and a suitable specimen may be prepared by freezing " crystallisable " benzene once rejecting about one-third as the more fusible fraction, fractionally distilling the remainder through a column of glass beads and collecting the fraction boiling from 80" to 80.5".The purified benzene has (usually) been dried and stored over sodium, but this has been found unnecessary. To test this point an experi-ment was made using benzene which had been dried over sodium for ten weeks. The surface tension of the dry liquid was first determined a drop of water added and the measurements were repeated; a further set of readings was made after the benzene and water had been in contact for forty-eight hours. As the figures below show moisture has no appreciable effect on the surface tension as measured by the met,hod of maximum bubble pressure. Surface tension in dynes/cm.Temp. Dry. Water added. After 48 hours. 21" 28.81 28.74 28-78 39 26.33 26.38 26.36 61 23.65 33.65 23-54 Table I1 gives the surface tension of benzene a t every degree It is calculated by the formula from 10" to 30". y=.70-26(1 -A) 1'20 . . . . which as will be shown in a subsequent paper reproduces the experimental data on this substance with accuracy from the freezing point to the critical point. This table enables benzene to be used as standard liquid a t the laboratory temperature FROM THE MAXIMUM PRESSURE IN BUBBLES. PBRT 11. 31 TABLE 11. Temp. ...... 10" 11" 12" 13" 14" 15" 16" y dyneslcm. 30.19 30-05 29.92 29-79 29.66 29.53 29-40 Temp. ...... 17" 18" 19" 20" 21" 22" 23" y dyneslcm. 29-27 29.14 29-01 28.88 28-76 28.62 28.49 Temp. ......21" 25" 26" 27" 28" 29" 30" y dynes/cm. 28.36 28.23 28.10 27.97 37.84 27.71 27.58 As an example of the method of calculation a few figures for benzene are given below in detail. Apparatus 3 . r2 = 0.159 cm. At Z O O with benzene H = 10.90 cm. H is the observed difference in gauge readings for the wide and narrow tubes. Gauge temperature 14"; at this temperature the factor t,o convert gauge readings into dyneslcm.2 is 780.5, whence P = 8508 dynes/cm.2. If (b represents the correction factor so that D + = 1 + 0*69r,$ . . . . . then since D = 0.877 + = 1.0111 and from (4) A = 0.003358, the required constant for this particular instrument. With this value of A observations on benzene a t other temperatures are calculated below. fl Gauge Gauge P D Y. Temp. em. temp. factor. dyncs/cm.2. gm. jc.c. 9. dyneslcm. 13.5" 11*20 12-5" 781.7 9757 0-885 1.011 29.72 34.5 10.18 14 780.5 7943 0.862 1.012 26.98 72 8-34 14 780.5 6510 0.819 1.0135 22.15 P is obtained by multiplying H by the gauge factor + is then calculated by (6) and the surface tension by (4) the value found above for the constant A being used. The author is indebted to the Research Fund Committee of this Society for a grant which has largely defrayed the cost of this investigation. BIRKBECP COLLEGE, UNIVERSITY OF LONDON. [Received October 23rd 1923.

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DOI:10.1039/CT9242500027

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J O U R N A L €1. R. BAKER C.B.E. D.Sc. P.R.S. E. C. C. BALY C.B.E. F.R.S. 0. L. BRADY DSc. A. W. CROSSLEY C.M.G. D.Sc., H. R. DUDLEY O.B.E. M.Sc. Ph.1). U. R. EVANS M.A. J. J. Fox O.B.E. D.Sc. C. S. GIBSON O.B.E. 111.6. W. N. HAWORTH D.Sc. Ph.D. I. M. HEILBRON D.S. O. D.Sc. T. A. HENRY D.Sc. H. BASSETT D.Sc. Ph.D. F.R.S. OF T. M. LOWRY C.B.E. D.Sc. F.R.S. J. W. MCBAIN Ph.D. F.R.S. J. I. 0. MASSON M.B.E. D.Sc. W. H. MILLS Sc.D. F.R.S. T. S. MOORE M.A. B.Sc. G. T. MORGAN O.B.E. D.Sc. F.R.S. J. C. PHILIP O.B.E. D.Sc. F.R.S. R. H. PICKARD D.Sc. F.R.S. T. S. PRICE O.B.E. D.Sc. F.R.S. F. L. PYMAN D.Sc. F.R.S. J . F . THORPE C.B.E. D.Sc. F.R.S. W. P. WYNNE D.Sc. F.R.S. H. MCCOMBIE D.S.O. M.C. D.Sc. THE CHEMICAL SOCIETY. 6;bifor : CLdRENCE SMITH D.SC. $abexes : MABCARET LE PLA B.Sc. 1924. Vol. CXXV. Part II. pp. 1405-end. LONDON: GURNEY k JACKSON 33 PATERNOSTER ROW E.C. 4. 1924 PRINTED IN GXICAT BRITAIH BY HICHARD GLAY & SONS LIX~TICD, BUNGAY SUlWOLB

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32 SUGDEN THE VARIATION OF SURFACE TENSION VI.-The Variation of Surface Tension with Tern-perature and ~ome Belated Functions. By SAMUEL SUGDEN. IT is well known that a linear relationship between surface tension and temperature can only be used over small ranges of temperature. In 1894 van der Waals (2. physikal. Chem. 13 716) gave two formuh connecting surface tension and temperature which involve the critical constants. . . . . . . y = K,O,V,-S(l - m)B (1) = K28&p,3(1 - m)B (2) . . . . . . Here O, V, and p are the critical temperature volume and pressure m is the reduced temperature and K, K, and B are universal const ants. Ferguson (Phil. Hag. 1916 [vi] 31,37) has suggested the formula . . . . . . . . y = yo(l - bt)’& (3) where n varies from substance to substance.This variation is not large the values of n for non-associated liquids ranging from 1-192 to 1.248 and Ferguson states that the mean value 1-21 gives satisfactory results in most cases. More recently Macleod (Tram. Faraday Soc. 1923 19 38) has shown that where C is a constant for a given liquid over a large range of tem-perature. Here D is the density of the liquid and d that of the vapour. In a paper recently read before the Faraday Society (2nd July 1923) Fekguson has shown by eliminating 1 - m between (3) and Katayama’s modification of the Ramsay-Shields equation namely, . . . . . . . . . y = C(D - 4 4 (4) . . . . . . . y(&&Jt= A8,(1- m) ( 5 ) (Sci. Rep. Tohoku Imp. Univ. 1916,4 373) that Macleod’s relation results if n = 1-20.Hence if Macleod’s relation holds Ferguson’s equation reduces to that of van der Waals and the universal constant B has the value 1.20. This leads us to inquire whether it is necessary to have a variable exponent to reproduce the experimental figures with sufficient accuracy or whether a formula of the van der Waals type is adequate. We may rewrite (1) . . . . . . . . y = y,(l - m)’’‘20 where yo = K10cVc-3 = K,B,Jp,% (6) ( 7 ) . . . . WITH TEMPERATURE AND SOME RELATED FUNCTIONS. 33 By applying (ti) to the experimental data we can test the constancy of B and then from the values of yo and the critical constants see if K l and K are universal constants. The most important measurements of surface tension up to the neighbourhood of the critical temperature are those contained in the classical paper of Ramsay and Shields (Phil.Trans. 1893, 184 647). It is however now certain that the surface tensions obtained by these workers are too low because of an inadequate correction for the capillary rise in the wider tube. Fortunately, sufficient experimental data are recorded in this paper to enable one to calculate the necessary correction. Details of the calculation of this correction are given in an appendix to the present paper but the method employed may be described briefly here. In the first place measurements were made of the surface tension of benzene and chlorobenzene up to the boiling point by the method of maximum bubble pressure (this volume p. 27). To these figures a formula of type (6) was fitted and the surface tensions a t temperatures a few degrees above the boiling point were obtained by extrapolation.From these and the capillary rise observed by Ramsay and Shields the radius of the wide tube was calculated using the theory of the method of capillary rise worked out by the author two years ago (T. 1921, 119 1483). Once this radius is determined the corrected values of the surface tension can be calculated. To save labour the corrected surface tensions have been calculated at 30" intervals instead of the 10" intervals given by Ramsay and Shields. Further it should be noted that these corrected surface tensions are calculated from the observed values of the capillary rise whilst Ramsay and Shields's figures are deduced from a smoothed value. It seemed preferable to allow the figures to be burdened with the experimental error rather than to use an arbitrarily smoothed curve since the main object of the work was to test whether formula (6) was capable of representing the experimental figures with sufficient accuracy.A further check on the values for benzene chlorobenzene and carbon tetrachloride was obtained from the observations of Walden and Swinne (2. physikul. Chem. 1912 79 700). These workers employed the method of capillary rise and constructed an apparatus with one tube of large diameter (2-3 cm.) so that the correction for capillary rise in this tube was very small and could be calculated accurately. They deduced the radius of the capillary from observ-ations on benzene using Ramsay and Shields's figures for the surface tension of this substance and found a radius of 0.1930 mm.If this figure is recalculated using accurate values for the surface VOL. cxxv. 34 SUGDEN THE VARIATION OF SURFACE TENSION tension of benzene a much higher value is obtained as is shown below. The radius of the capillary is given by the equation Benzene. h D-d Y . r Temp. cm . gm./c.c. dynes/cm. mm. 20" 3.374 0.8787 28-88 0-1985 30 3.237 0.8680 27.59 0*2000 40 3.134 0.8569 26.31 0-1996 50 3.015 0.8455 25-03 0.1999 Similarly from the accurate values of Richards and Carver (J. Amer. Chem. Soc. 1921 43 827) for the surface tension of toluene and carbon tetrachloride two more values of r can be obtained, namely toluene r = 0.1991 mm. carbon tetrachloride r = 0.1995 mm.Taking the mean figure 0.1994 cm. the figures of Walden and Swinne can be corrected by multiplying by 0.1994/0.1930 = 1.0335. This simple method of correction can be adopted in this case because the correction for the wide tube is so small and mould not be altered appreciably if one employed the corrected surface tension instead of the old figure to determine the magnitude of the capillary rise in this tube. It is interesting to note that Walden and Swinne made a direct determination of the radius of the ca,pillary by means of a mercury thread. They found a value of 0.1978 mm. which however they disregarded adopting the figure 0.1930 in all their calculations. Having obtained the corrected figures for the surface tension, the next step was to test equation (6) This was done by plotting ryi against the temperature when as is seen in Fig.1 the points for any one liquid were found to lie on a straight line. From the intercepts of this line on the axes of the graph t.he constants of (6) were calculated and the formula was then used to predict the surf ace tensions. As will be seen from the table on pages 37,38 the observed figures are reproduced with considerable accuracy in the case of the six normal liquids benzene chlorobenzene diethyl ether carbon tetra-chloride methyl formate and ethyl acetate. The greatest differ-ences between observed and calculated figures are found with chlorobenzene but these dserences are irregularly distributed and could not be eliminated by giving to n another value than 1-20.In the column headed "observer," R. & S. stands for Ramsay and Shields W. & S. for Walden and Swinne R. & C. for Richards and Carver and S. for Sugden. The three associated liquids do not obey this law as can b WITH TEMPERATURE AND SOME RELATED FUNCTIONS. 35 seen in Fig. 1 where methyl and ethyl alcohols and acetic acid give lines of marked curvature. The next test is to compare the values of the critical temperature deduced from the surface tension measurements with the figures obtained by direct observation. These are shown in the table below ; the critical temperatures are those given by Young (Proc. Roy. SOC. Dublin 1910 12 374). FIG. 1. -+t 100 200 300 10 5 + t I. Benzene. II. Chlorobenzene. 111. Diethyl ether. IV. Carbon tetrachloride.V. Methyl formute. VI. Ethyl acetate. VII. Methyl alcohol +. VIII. Ethyt alcohol 0. IX. Acetic acid. Critical temperature. Substance. Calc. Obs. Diff. Benzene ..................... 257" 288.5" - 1.5" Chlorobenzene ............... 358 359.2 - 1.2 Diethyl ether ............... 193 193.8 - 0.8 Methyl formate ............ 212 214 -2 Ethyl acetate ............... 249 250.1 - 1.1 Carbon tetrachloride ...... 2 80 253.1 - 3.1 It will be seen that the predicted critical temperatures are usually a degree or two below the observed value but in general there is 0 36 SUGDEN THE VARIATION OF SURFACE TENSION good agreement although not so good as that obtained by Ferguson (Zoc. cit.). This however is only to be expected as his formula allows n to be varied slightly and should give a closer fit.The next point which arises is the relationship between the critical constants and yo which van der Waals deduced from the theory of oorresponding states. In the table below the critical data are due to Young (Zoc. c k ) and K and K are the constants in equations (1) and (2). Van der Waals's Constants. Substance. yo. 8,. atm. gm./c.c. C.C. K1. K,. Benzene ... ..... ...... 70-26 561-5 47.89 0.3405 256.1 5.047 0-646 Chlorobenzene . . . . . . $0.33 673.2 44-64 0.3654 307.8 4-763 0-638 Diethyl ether . . ... . . . . 55-96 466.8 35.61 0-2625 281.9 5.155 0.667 Carbon tetrachloride 66.27 556.2 44-98 0.5576 276.1 5.171 0.637 Methyl formate . . . . . . 75.85 487 59.25 0.3489 172.0 4.818 0.635 Ethyl acetate ...... 65-24 523.1 38.00 0.3077 286.0 5.414 0.716 It will be seen that K and K are roughly constant for these six substances but vary by several units per cent.from one sub-stance to another. Finally there remains for consideration the relation between surface tension and density discovered by Macleod (Zoc. cit.). The last column in the table on pages 37,38 gives the value of $/(D - d). This quantity in the case of the six normal liquids is remarkably constant up to within about 40" of the critical temperature where the surface tensions and densities are difficult to determine with accuracy. For the three associated liquids this function increases slowly with increasing temperature. Pe de v, E x P E R I M E N T A L. Details of the measurements on benzene have been given in the preceding communication (this vol.p. 27). Measurements of the surface tension of chlorobenzeiie were made by the same methods and details of these measurements are given below. PuriJication.-A good commercial specimen was fractionally distilled and the specimen used boiled steadily at 131" (corr.) a t 750 mm. Apparatus.-Two instruments were used No. 1 for which r2 = 0.163 em. and A = 0-003736 and No. 3 for which r = 0.159 em. and A = 0.003333. Densities are due to Young (Zoc. cit.). Temp. dynes/cm.2. gm. /c.c. 9. dyncs/cm. 12" 9070 1.115 1.014 34-36 80 7860 1-073 1-016 29.83 App. 1 93 6573 1-025 1.018 24.99 81 7 708 1.039 1.01 6 26.10 App. 3 123 6377 0.991 1.018 21-63 P D-d WITH TEMPERBTURJZ AND SOME RELATED FUNCTIONS. 37 Summary. (1) The surface tension measurements of Ramsay and Shields and of Walden and Swinne have been corrected.(2) For six non-associated liquids it has been shown that the variation of surface tension with temperature is represented accur-ately by the formula y = yo(l - rn)l'ao where m is the reduced temperature and yo a constant. (3) The relations between yo and the critical constants predicted by van der Waals have been shown to hold approximately. (4) Macleod's relationship between surface tension and density is found to hold accurately for non-associated liquids up to about 40" below the critical t,emperature. Temp. 13.5' 20 20-5 21 32-5 34.5 39 41.5 54.8 61 72 90 130 150 1 so 210 340 2 70 280 12 18-7 24.1 41 50 52.2 62.1 81 93 123 150 180 210 2 40 2 i 0 300 320 333 0 bservor.S. R. & C. TV & s. S. w. & s. S. S. w. a s. w. & s. S. S. R. & S. Y9 9 ) ? ? ? 9 9 9 37 S. w. 82 s. 9 9 ?? S. w. & s. S. 9 9 7 9 It. % 8. 9 9 9 ? ? ? ? ? ? ¶ ? ? 2 ) y obs. 29-72 28-88 28.91 28-74 27-30 26.98 26.36 26.08 24-28 23.61 22-1 5 20.13 16.42 13.01 9.56 6.46 3-47 1-05 0-36 11. 34.36 33-35 32-55 30.78 29.83 29.38 28-20 26-10 24.99 21-63 18.56 1540 12.16 9.30 6-43 4-05 2-39 1.63 TABLE. y cnlc. Diff. I. Benzene. 29.74 +0.02 28.88 +O.OO 28.75 +0*01 27-11 3-0.13 26.44 +0.08 26-12 +0*04 24.43 +0*15 23.65 fO.04 22-26 +0*11 20.06 -0.08 16.45 +Om03 12.97 -0.04 9.64 f-0.08 6.48 +Om03 3.59 4-0.12 1.06 +0-01 0-37 +O.Ol 28.82 -0.09 27.27 -0.03 Chlorobsnzene.34.41 -0.15 33-42 f0.13 32.78 -0.07 30.79 3-0.01 29.75 -0.08 29.49 +0*11 28-36 f0.14 26.19 +0*09 24.83 -0.16 21.50 -0.13 18.57 +0.02 15-40 &O*OO 12-35 +0*19 9.41 +0*11 6.61 +0.18 4.01 -0*04 2-25. -0.14 1.4G -0.17 U - d . 0.8857 0.8787 0.8782 0.8777 0.8653 0.8631 0.8581 0.8553 0-5400 0-8330 0.5207 0.8006 0.7616 0.7166 0.6657 0.601 1 0-5137 0.3696 0.2305 1.115 1.108 1.102 1.083 1.073 1.070 1.059 1.039 1.025 0.991 0.9545 0.9122 0-8622 0.8054 0.7341 0,6442 0.5628 0*4'314 Yt D y d ' 2.637 2.638 2.641 2-638 2.642 2.641 2-641 2.642 2.642 2.647 2-643 2.646 2.643 2-650 2-641 2.651 2.657 2.739 3.352 2.166 2.173 2.172 2.174 2.178 2.176 2.176 2-1 76 2.182 2.1 76 2.174 2.172 2-166 2.168 2.169 2.202 2.210 2.29 38 Temp.20 50 80 110 140 170 185 20 21.1 33-0 45.0 90 120 150 180 210 240 2 70 50 80 110 140 170 200 90 120 150 180 210 240 20 70 100 130 160 190 220 230 20 80 110 140 170 200 230 130 160 190 220 260 280 SUGDEN THE VARJATION OF SURFACE TENSION Observer. R. & c. R. & S. Y 9 Y 9 Y 7 7 9 7 9 R. & C. w. & s. R. % S. 9 ) 7 ) 9 7 Y Y 9 ) I ¶ 9 ) R. 8% s. Y Y ? Y 9 9 Y Y Y Y R.& S. Y 9 9 ) Y Y Y Y Y Y R. & C. R. & S. 9 Y Y Y 9 ) 7 ) 9 ) Y Y R. & C. R. & S. I t Y > Y Y Y Y ? 9 R. 8z S. 9 ) Y 9 Y 9 Y 9 9 9 111. Diethyl ether. yobs. ycalc. Diff. 17.01 17-04 +Ow03 13.69 13.56 -0.13 10.25 10.23 -0.02 7-00 7.06 +Om06 4-00 4-12 3-0.12 1-42 1.51 +0-09 0.40 0.43 +0.03 IV. Carbon tetrachloride. 36.95 26.80 -0.15 26.71 26.66 -0.05 25.22 25.20 -0.02 23.63 23.63 ,tO.OO 18.5 1 18.40 -0.11 14.95 14-96 +O.Ol 11-46 11.66 +0*20 8-50 8.51 +O.Ol 5.67 5.55 -0.12 2-64 2.83 +Om19 0.49 0-55 +0*06 V. Methyl formate. 20.48 20.35 -0.13 1545 15.92 -0.03 11.77 11.66 -0.11 7.63 7.69 +0*06 3-98 4.03 +Om07 0.92 0.90 -0.02 VI. Ethyl acetate.15-74 15.67 -0.07 12.08 12.19 +Om11 8-85 8.87 +0.02 5-70 5-75 +0.05 2-94 2.90 -0.04 0.50 0.50 &O*OO VII. Methyl alcohol. 22.61 18.50 15-73 12.66 9.34 5-56 1.95 0.77 22.27 17-97 14.49 11-34 7.85 4.26 0.95 VIII. Ethyl alcohol. IX. Scctic acid. 17-05 14.21 11.45 8-71 5-70 2-83 D -d. 0.7109 0.6713 0.6286 0.5707 0.4936 0-3785 0.2698 1.593 1.591 1.567 1.540 1.4475 1.3740 1.2914 1-1945 1.0687 0.8980 0.5955 0.9251 0.8698 0-8048 0-7156 0-6081 0.4131 0.8065 0.7580 0-7005 0.6265 0-5232 0.3278 0-7910 0.7445 0-7100 0.6676 0-6141 0.5369 0.4036 0.3223 0.7888 0.7360 0.7008 0.6516 0.5920 0-5050 0.3415 0-9190 0.8729 0.8245 0.7643 0.6841 0.5685 Ya-D-d' 2.857 2.865 2.850 2-865 2.865 2.947 1429 1.428 1.429 1.432 1.433 1.431 1.425 1.429 1.444 1.419 1.405 2.300 2-297 2.301 2-322 2.319 2-37 2.884 2.470 2.450 2-462 2-467 2-50 2-56 2.757 2.787 2,804 2.826 2.846 2.866 2.928 2-905 2.755 2-797 2.785 2.817 2.828 2.845 2.891 2.211 2.224 2.231 2.248 2.258 2,28 WITH TEMPERATURE AND SOME RELATED FUNCTIONS.39 Appendix. Correction of Ramsay and Shields's Data. The apparatus used by Ramsay and Shields consisted of a capillary tube mounted concentrically in a wider tube. It is very difficult to deal witsh this case mathematically but a complete solution of the analogous problem of two communicating tubes has been given by the author (T.1921 119 1483). Since the correction to be calculated is small (about 5 per cent.) it would seem that the quantity required might be calculated in the following manner. Using accurate data for some standard liquid and the observed capillary rise recorded by Ramsay and Shields one can cal-culate the radius of an equivalent wide tube which if it were placed in communication with the capillary and not around it would have the same effect as R'amsay and Shields's concentric tube. Then by the aid of the tables in the paper referred to above the observ-ations of these workers can be recalculated as the radii of both tubes have been determined. The assumption made here is that an external tube which has the same effect as a concentric tube a t one particular surface tension has the same effect as the concentric tube at all surface tensions This assumption whilst perhaps not rigidly true must be so to a first approximation and since the total correction for the capillary rise in the wide tube is about 10 per cent at the lower temperatures and diminishes to zero a t the critical temperature it does not seem likely that any large error will result if this method is adopted.What may be termed " internal evidence " for the truth of this hypothesis may be found in the table on pages 37,38 where it will be seen that the corrected data obtained in this manner are in harmony with the values found by other observers. The standard liquids chosen for the determination of the radius of the wide tube were benzene and chlorobenzene.From a series of measurements by the method of maximum bubble pressure it was found that the surface tensions of these liquids could be repre-sented by the formulae Benzene y = 70.26 ( 1 -&y2 . . . Chlorobenzene y = 70-33 1 - ( &)'? . . . where 6 is the absolute temperature. for benzene at 90" y = 20-05 dynesjcm. D - d = 0.8006 whence a2 = 5.105 mm.2. with two communicating tubes From (9) it is found tha,t At this temperature, Now for an apparatua l / b - l / b 2 = H/a2 40 THE VARIATION OF SURFACE TENSION WITH TEMPERATURE ETC. where b and b are the radii of curvature at the lowest points of the liquid surface in the capillary and wide tubes respectively. To calculate l/bl we proceed as follows. In Ramsay and Shields's apparatus rl = 0-012935 cm.hence rJa = 0-05275. From the table in the a,uthor's paper referred to above this corresponds to r,/b = 0.9989 whence l / b = 77.22. The capillary rise for benzene found by Ramsay and Shields a t this temperature was H = 3.460 em. from which H/a2 = G7.78 and l/b2 = 9-44. By the aid of the table connecting r/a and rjb it was found that for this value of a2 1,'b = 9.50 when r2 = 0.099 cm. and l / b = 9-39 when r2 = O-lCO cm. whence by interpolation r2 = 0.0996 cm. Similar calculations were made for benzene a t 120" and for chlorobenzene a t 150" and 180" with the following results. Temp. ......... 90" 120" 150' 180" r2 crn ............. 0.100 0.096 0.096 0.097 Mean 0-097 cm. Using this value of r2 any of the observations of Ramsay and Shields may be recalculated by the method of successive approxim-ations detailed in the author's 1921 paper (Eoc.cit.). This would involve a very laborious series of calculations which can be avoided in the following manner. Benzene. Chlorobonzene. Since (12) (13) 2 H a2 = -Y -g(D - d ) - l / b l - l/&i * * ' we can write where . . . . . . . . y = H(D - d)+ Kow # is a function of rl r2 and a2 and for a given apparatus, where rl and r2 are fixed is a function of H only. Hence if + is calculat'ed for a few values of H intermediate values can be obtained by interpolation. The table below gives corresponding values of # and H for the range required. H ...... 0.10 0.15 0.20 0.40 0.70 1 -00 d ...... 6.828 6.839 6.881 6.881 7.108 7.158 ...... 4.0 5.0 OD ...... 7.280 7.321 H 1.50 2.00 3-0 Q) 7.208 7-233 7.259 1 . ~ 7 1 From these values a curve was drawn to give intermediate values of Q and the correct'ed surface tensions mere calculated by equation (13). Liquid. Temp. II. D-d. 9. y corr. y R. & S. Benzene ......... 90" 3.460 0-8006 7.365 20.13 19.16 ......... 240 0.945 0.5137 i-155 3.47 3.41 Chlorobenzene ... 150 2.68 0.9546 7-251 18-55 17.67 9 . ... 320 0.60 0.5638 7.084 2.39 5-35 - 0 A few examples are given below. ? STEREOISOMERISM AND LOCAL ANZSTHETIC ACTION ETC. 41 The last columii in the table gives the surface tension calculated by Ramsay and Shields. It will be seen that the corrected figures are about 1 dynelcm. higher at the lower temperatures the difference diminishing as the temperature rises. The authbr is indebted to the Research Fund Committee of the Chemical Society for a grant which has largely defrayed the cost of this investigation. BIRRBECK COLLEGE, UNIVERSITY OF LONDON. [Received October 23rd 1923.

ISSN:0368-1645    

DOI:10.1039/CT9242500032

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年代:1924

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摘要:

STEREOISOMERISM AND LOCAL ANZSTHETIC ACTION ETC. 41 VII.-Stereoisomerisin and Local Anmsthetic Action Resolution of p- and in the P-Eucaine Group. iso-B-Eumine. By HAROLD KING. WHEN the work detailed below was begun there was no case known where the dextro- and lzevo-modifications of any of the local anesthetics had been examined for their relative anzesthetic properties. In the meantime however Gottlieb has described (Arch. Exp. Path. Pharm. 1923 97 113) the relative anzesthetic effect of dI- and I-cocaine and of d- and I-$-cocaine which have recently become available. The present author chose p-eucaine a i d stovaine as representatives of synthetic local armsthetics suitable for resolution. So far no crystalline salts have been obtained from stovaine mith optically active acids but p-eucaine forms a series of such salts which crystallise extremely well.Vinyldiacetonamine (2 2 6-trimethyl-4-piperidone) (I) on re-duction with sodium ain,zlga,ni gives two racemic alcohols a- and p-vinyldiacetoiialkamines (4-hydroxy-2 2 6-trimethylpiperidinne) (I1 and 111) (Harries Amulen 1897 294 336), each of which on benzoylation gives a mono-0-benzoyl derivative. The conditions necessary for the- preparation of N-bestzoyl- p-~innyldi-c 42 KING STEREOISOMERISM AND LOCAL acetonallcarnine ON-dibenxoyl-p-vinyldiacetonal~mamine and ON-di-benzoyl-a-vinyldiacetonalkamine are described in the experimental portion of this paper. The constitution of N-benzoyl- p-vinyldi-acetonalkamine which was only obtained in small quantity follows because it is different from the product of benzoylation of O-benzoyl-p-vinyldiacetonalkamine.0-Benzoyl-a-vinyldiacetonalkamine is known as p-eucaine whilst for convenience of reference O-benzoyl-p-vinyldiacetoiialkamine will be called hereinafter iso- p-eucaine. This latter base is unrecorded in Beilstein's "Handbuch" or Richter's " Lexicon,'' but a brief description of it may be found in D.R.-P. 95620 and in a paper by Vinci (Pfuger's Archiv 1897, 149,220). Each of these bases has been resolved and a comparison made of their physiological properties. I n this way it has not only been possible to effect a comparison of two diastereoisomerides, p-eucaine and iso-p-eucaine but also of two pairs of enantiomorphs, d- and I-p-eucaine and d- and I-iso-p-eucaine.The resolution of p-eucaine and of iso-p-eucaine both present somewhat novel features. The normal salts of p-eucaine with d-camphoric d-tartaric and I-rnalic acid are partial racemates. With d-camphor-10-sulphonic acid the stable salt over the range between room temperature and below zero is also a partial racemate, dl- p-eucaine d- camphor- 1 0-sulphonaie crys tallising in massive tablets containing a molecule of alcohol of crystallisation but it has been found possible to resolve this salt by means of the more soluble active forms which are unstable in respect of the partial racemate. Ladenburg found (Ber. 1894 27 75) that when he evaporated solutions of p-pipecoline tartrate a t water-bath temperatures the salt which separated was the partial racemate but when the solu-tions were evaporated a t the ordinary temperature he obtained the salt containing a preponderance of I-pipecoline.I n a later paper (Ber. 1898 31 527) he added a postscript showing that crystallis-ation of quinine methylsuccinate between 0" and 30" yielded the partial racemate but above 70" an acid was obtained having a rotation of + 0.1" in 10 per cent. solution. The present case differs from these in that resolution has been effected within the transition interval where the partial racemate is the most stable form. A reference to the accompanying isothermal solubility diagram, which is purely qualitative will render the phenomena observed easier of interpretation. A and B are the solubilities respectively, of d- p-eucaine d-camphorsulphonate and I - p-eucaine d-camphor-sulphonate at room temperature in a constant amount of the solvent alcohol in this case.The curve joining these points being continuous expresses the solubility of the continuous series of mixe BNABTHE!MC ACTION IN THE f3-EOCmE GROUP. 43 crystals which are formed by these salts. The solubility curve of the partial racemate dl- p-eucaine d-camphorsulphonate which is much less soluble is represented by DF. A supersaturated solution of the partial racemate point x kept a t temperatures between - 5" and + 30" will in general deposit the partial raeemate point E as being the least soluble form. Owing however to the inter-vention of Ostwald's rule of the prior formation of less stable forms the solid deposited may not be the partial racemate but mixed crystals of the two optically active salts not represented by the point C but by some point in the region between C and B (not necessarily on BC as the composition of the mixed crystals cannot be represented adequately on this type of diagram).If however, the partial racemate makes its appearance at any time as fre-quently happens especially on keeping the solutions over-night, it is followed by rapid solution of the mixed crystals. Owing to the relatively sparing solu-bility of the partial racemate, even solutions which contain a preponderance of the I - p -eucaine d- cam phorsulp hona t e and in which the process of resolution by fractional crystal-lisation has proceeded a con-siderable way towards com-pletion will deposit the partial racemate and thus negative the quantitative progress to-FIG.1. wards resolution. Beyond the point where EF and CB intersect the stability conditions are reversed. The relative stability of the various forms a t higher temperatures has not been examined. The fact however that the partial racemate crystallises with 1 mol. of alcohol which is readily lost would suggest that at higher temperatures this form of the partial racemate would be unstable. By fractional crystallisation of the unstable forms it has been possible to isolate 54 per cent. of E-p-eucaine d-camphor-sulphonate. Owing to the formation of a continuous series of mixed crystals between the two active salts it was not found possible to isolate the more soluble salt d- p-eucaine d-camphorsulphonate.By the use however of I-camphor-10-sulphonic acid kindly lent to the author by Professor C. S. Gibson of Guy's Hospital the isolation of d-p-eucaine I-camphorsulphonate became an easy matter. c* 44 KING STLREOISOMERISM AND LOCAL The chemical results with p-eucaine are tabulated below : 2-8 -Eucainc. d-8 -Eucaine. Base : Appearance Columns Columns M. p. ......... 57-58' cow. 57-58' corr. Hydrochloride : Appearance Rectangular plates Rectangular plates M. p. ......... 244-248" corr. 244-245" corr. [a]= ......... - 13.0" + 13d0 Picrate : Appearance Prisms -ill. p. ......... 198-199' corr. -_ r-B -Eucaine. Plates or tablets 70-71" corr. Small tablets 277-279" corr. -Short rods 231-5-232-5" corr. A point which calls for remark is the melting point of r-p-eucaine base.A great variety of values is recorded in the literature. In D.R.-P. 97672 the value 78" is given Vinci (loc. cit.) gives the two values 87" and 75" on the same page whilst Parsons ( J . Amer. Chem. Xoc. 1901 23 885) gives the figure 91". r-p-Eucaine pre-pared from its pure optically active components has m. p. 70-71" (corr.) the same as that of the commercial base and it seems likely that Parson's value 91" is a misprint for 71". iso- p-Eucaine forms an uncrystallisable salt with camphor-10-sulphonic acid but its resolution is effected without great difliculty by means of &-a-bromo-wcamphorsulphonic acid. Here again, the behaviour is somewhat unusual. The first time the author fractionated this salt from absolute alcohol the successive products of crystallisation showed steadily increasing rotations and eventually d-iso- 8-eucuine d- bromocamphorsulphonade mas isolated almost pure.When however a larger batch of material was submitted quite independently to the same process the rotations fell and 1-iso-p-eucaine d-bromocamphorsulphonate was isolated as the apparently least soluble salt. The matter is further complicated by the fact tJhat d-iso-p-eucaine cl-bromocamphorsulphonate crystallises with a molecule or less of water of crystallisation from alcoholic solutions. At first it was thought that this was the determining factor but it seems that the anomalous behaviour is due to the approximately equal solubilities of the two salts and to the fact that they do not show any great tendency to form a difficultly separable series of mixed crystals.It was found in working up the mother-liquors of the larger batch that the successive crops of pure material isolated by repeated fractional crystallisation were almost alternatively dextro and laevo ANXSTHETIC ACTION IN THE b-EUCAINE GROUP. 45 The chemical results with iso- p-eucaine .are tabulated below : Z- iso-fi -Eucaine . d-iso- 8- Eucaine dl-iso- B- Eucaine . Base : Appearance SFUP Syrup Syrup Hydrochloride : Appearance Bold needles Bold needles Dirnorphous, M. p. ......... 271-273" cow. 271-273" corr. 269-271" corr. needles and plates - 16.3" + 17.0" - ...... Picratc : Appearance Needles - Rectangular leaflets M. p. ......... 280' cori.. - 256-258" corr.Tutin (T. 1910 97 1797) has directed attention to the unusual fact for a picrate that benzoyl-d-oscine picrate melts a t 211-213" without decomposition. A still more striking example is furnished by dl-iso-p-eucaine picrate which melts at 256-258" without decomposition and if the melting point tube be removed from the bath its contents resolidify and will melt again at the original temperature. As p-vinyldiacetonalkamine is according to Harries converted quantitatively into a-vinyldiacetonalkamine by boiling with sodium amyloxide the behaviour of the optically active forms to the same reagent was deemed worthy of investigation. Accordingly, l-iso- p-eucaine was hydrolysed giving d-p-vinyldiacetonalkamine, which on boiling with sodium amyloxide for thirty-two hours gave a 77 per cent.yield of d- u-vinyldiacetonalkamine h,ydrochloride having [a16461 -/- 17.6" whereas the pure salt has [a15461 + 18.5". The racemising influence of the sodium amyloxide is thus confined to the >CH*OH group and does not involve the other asymmetric centre, The vinyldiacetonalkamines rmemic and active have been fully characterised as bases and by preparation of their hydrochlorides and picrates. The circuit of reactions detailed in this communica-tion is summarised by the following diagram : Vinyldiacetonamine a. Vinyldiace tonalkaminc 4 .1 Benzo yl-a-vinyldiacetonalkamiiie (8-Eucaine) I J. d -fl -Eucaine d-a - Vinyldiacetonalkamine /3 -Vinyldiacctonalkani ne .1 J, Benzoyl-B-vinyldiace toxialkamine (iso-jI-Eticaine) I J.E- is0 - 13 - Eucaine f- d- p -Vinyldiace tonal kamin 46 KING STEREOISOMERJSM AND LOCAL The author is much indebted to Dr. J. H. Burn of these labora-tories for a determination of the relative anaesthetic action of p-eucaine Sso-p-eucaine and their optically active forms. On the rabbit’s cornea p-eucaine iso- 8-eucaine and their optically active components have approximately equal local anmthetic action the limiting concentration for complete anzsthesia lying between 0-25 and 0.5 per cent. On the sciatic nerve of the frog however, p-eucaine is a more potent anzsthetic than iso-p-eucaine; d- and Z-p-eucaines in 5 per cent. solution completely block the impulses produced by electrical stimuli applied to the nerve in fifteen to fwenty minutes their effectiveness being approximately equal ; but d- and Z-iso-p-eucaines in 5 per cent solution have little effect in blocking the impulses even after twenty minutes.How do these results fall in with the general trend of observations on the relation between physiological action and chemical con-stitution ? Although the fundamental chemical mechanism of the action of drugs is not known with any certainty the present position may be very broadly summarised by the statement that the physiological action which results from the application of a drug is mainly a matter of its distribution in the tissues. The classic work of Dale and Barger on the adrenaline-like action of derivatives of ethylamine shows that a great number of substances of this type exist which have a similar action but differ in the quantitative aspect.It seems that the same physiological receptor or receptors are concerned in each case but the amount of drug which arrives at the seat of action differs in each case. Similarity of chemical build thus determines similarity of localisation and resultant physiological action. The reason however for the difference in the quantitative aspect of the phenomena is suggested by the recent remarkable observations of Porter and Ihrig ( J . Amer. Chem. SOC., 1923,45,1990> who showed that wool treated with racemic m-azo-p-naphtholmandelic acid has a selective affinity for the dextro-form, the unused dye being almost a pure Zceuo-form. It seems likely that two substances of similar build on penetrating tissues will therefore in general arrive a t the seat of action in different amounts through selective adsorption en route.As the mammalian body is largely an asymmetric environment the destro- and laevo-forms of a drug will usually show a quantitative difference in their distribution although their action will be of a similar type because they are similarly built. Hyoscine (IV) and atropine (V) furnish an interesting example o ANBSTHETIC ACTION IN THE P-EUCAINE GROUP. 47 such relationship. Their similarity in build is plain and part of the physiological picture of the action of hyoscine is made up of atropine-like effects. Working with the d- and Z-hyoscines prepared by the author (T. 1919 115 476) Cushny found ( J . Pharm. Exp. Ther., 1921 17 41) that Z-hyoscine is 15 to 18 times as powerful as d-hyoscinein its specific atropine effects but on nerve endings in striated muscle on unstriated muscle and on the central nervous system their action is identical.The relative anaesthetic actions of p- and iso-p-eucaines may be interpreted in analogous terms. p- and iso-p-Eucaines and their optically active forms are all equally anaesthetic on the cornea; they are similarly built and similarly localised and any quantitative difTerence in their intensity of action is not measurable by present methods. On the sciatic nerve of the frog p-eucaine is more potent than iso-p-eucaine and the action of d- and 1-p-eucaine is equal; here again the action of p- and iso-p-eucaines is of the same type but there is a quantitative difference indicating a difference of pene-trating power.The toxicity of these bases was determined on mice by subcutan-eous injection and is expressed in milligrams per gram of mouse : r-8-Eucaine ......... 0.8-0-9 r-iso-B -Eucaine ............ 0.5 d-B-Eucaine ......... 1.5 d-iso-B-Eucaine ............ 0.5 Z-8-Eucaino ......... 0.6-0.7 Z-is0-B -Eucaine ............ 0.5 As d- and Z-p-eucaines are equally anaesthetic and Z-p- is about twice as toxic as d-p-eucaine if other factors were equal the use of d-P-eucaine would be indicated in preference to Z- or r-p-eucaine. E x P E R I ni E N T A L. Preparation of a- and P- Vinyldiacetonalkamines. For the preparation of these bases Harries's method (AnnuZen, 1897 294 336) was in the main followed. The separation of the two hydrochlorides by reason of the sparing solubility of the a-vinyl-diacetonalkamine hydrochloride in a mixture of equal volumes of alcohol and ether is not quantitative and the addition of the ether can be omitted without disadvantage.After isolation of as much a- and p-bases as possible by a repetition of the above process on the contents of the mother-liquors there always remains an un-crystallisable residue in the benzene mother-liquors of the p-base. This was fractionated by distillation under reduced pressure at 20 mm. Between 120" and 130" (external bath temperature) a limpid oil distilled over and consisted of unreduced vinyldiaceton-amine. Between 140" and 150" a mixture of a- and p-vinyldi-acetonalkamines came over and rapidly solidified and finally between 180" and 200" a viscous liquid distilled the latter portion 48 KING STEREOISOMERISM AND LOCAL of which readily crystallised.This high-boiling fraction is in all probability the pinacol formed by fusion of the two nuclei. As it was a mixture and probably consisted of six possible forms two meso and four racemic it was not further investigated. It appears to be formed to the extent of between 5 and 10 per cent. during the ordinary process of reduction by sodium amalgam. a- Vin yldiacetonalkamine picrate prepared from the free base, is very readily soluble in water and crystallises in well-formed, orange prisms m. p. 238-239" (corr.). p- Vinyldiacetonalkamine picrate is even more soluble than the picrate of the a-base. For its preparation the free base must be used and excess of picric acid avoided.It crystallises from water in laminae formed by the fusion of needles m. p. 171-172" (corr.). Vinyldiacetonamine picrate prepared from its components is soluble to the extent of 1 part in 57 parts of boiling water and crystallises in clusters of prisms m. p. 198-199" (corr.; clecomp.). p-Eucaine and Optically Active Acids.* Camphoric Acid.-p-Eucaine (1.0 gram) was mixed with a one-half molecular proportion (0.4 gram) of d-camphoric acid and dis-solved in boiling methyl ethyl ketone. The crystalline 8-eucaine camphorate was recrystallised thrice from methyl ethyl ketone. The melting point was unchanged throughout and p-eucaine regenerated from the final salt was devoid of optical activity. dl- p-Eucaine d-camphorate crystallises from methyl ethyl ketone in very compact clusters of plates m.p. 211-212" (corr.). It is readily soluble in t'he boiling solvent but sparingly soluble in the cold (Found C = 68.9; H = 84. C,,H,,0,,2C,SH,,0,N requires C = 69-1; H = 8.4 per cent.). l-Malic Acid.-p-Eucaine (4.94 grams) was mixed with one molecular proportion (2.68 grams) of 1-malic acid in aqueous solu-tion but the salt which separated was the normal salt (3.45 grams), having [aID - 2.6" in water. It was recrystallised twice more from water yielding 1-85 grams of salt with properties unchanged. A quantity (1.4 grams) was decomposed with dilute ammonia and the recovered p-eucaine proved to be optically inactive in hydro-chloric acid solution. dl- 8-Eucaine l-malate crystallises readily from water.It is anhydrous and melts a t 212-213O (corr.) (Found C = 64.8; * A sample of 8-eucaine of unknown origin crystallised with bromocam-phorsulphonic acid from alcohol gave an extremely insoluble salt m. p. 283-284" (corr.) (Found C = 54-1; H = 6.6. Calc. C = 53.7; H = 6-5 per cent.). It gave a syrupy base and a laevorotatory crystalline hydro-chloride not identical however with I-B-eucaine or Z-iso-8-eucaine ANBSTHETIC ACTION M THE P-EUCAINE GROUP. 49 H = 7.6. M = 7.7 per cent.). The specific rotation was determined in water c = 1-06; ,? = 2 dcm. ; a - 0.06" ; [.ID - 2.6" whence [fM]D for the normal malate-ion is -16.3". This is of the same order as the value - 17.2" obtained by extrapolation from Schneider's values (Annalen, 1881 207 271) for sodium malate.d-Tartaric A cid.-Equimolecular proport ions of p - eucaine (4.9 grams) and d-tartaric acid (3.0 grams) were dissolved in water. The salt which separated was however the normal salt (yield 2.2 grams) reacting neutral to litmus. On addition of a second mole-cular proportion of p-eucaine to the mother-liquors a large crop (5.9 grams) of the normal salt was obtained having [a]* + 9.6". The rotations after two more crystallisations were + 11-2" and 10.1", respectively. There was 110 evidence of resolution. dl- p-Eucuine d-tartrate crystdlises from water without solvent of crystallisation in large tablets which melt m d decompose a t 257' (corr.) (Found C = 63.4; H = 7.5. C,H,0,,2C,5H2,02N requires C = 63.3; H = 7.5 per cent.).The specific rotation was determined in water G = 0.53; I = 2 dcm.; aD + 0.11"; [.ID + 10.1". C,H,05,2C15H2102N requires C = 64.9; p-Eucaine and d-Camphor-10-sulphonic Acid. Crystallisation without Resolution.4.9 Grams of p-eucaine were combined in alcoholic solution with one equivalent (5.2 grams) of d-camphor-10-sulphonic acid. On keeping a t room temperature or at zero dl-p-eucaine d-camphor-10-sulphonate separated in massive tablets. The yield was 7.5 grams and the specific rotation [.ID + 10.7". On recrystallisation it separated in two forms, needles and tablets but on keeping over-night the needles had disappeared leaving the more stable form of tablets. The sequence of rotation for the successive crystallisations of the stable tablet form was [&ID + 10.7" 8.2" 94" 10.4" mean 9-69' whence for the salt deprived of solvent of cryst'allisation [.ID + 10.6" in agreement wit,h the value 10.6" calculated from Graham's value (T.1912,161, 747) for the camphorsulphonic-ion. There was no resolution of the p-eucaine. dl- p-Eucaine d-camphor-10-sulphonate crystallises from alcohol in large tablets containing one molecule of alcohol of crystallisation, which is lost gradually on exposure to the air (Found loss a t 100" = 8.7. ClSH2102N,C,,H,,0,S,C,H,.0H requires loss = 8.8 per cent.). This salt is weakly triboluminescent and melts a t 228-229" (corr.). Its specific rotation was determined in water : c = 1.02; 1 = 2 dcm. ; aD + 0.19"; [.ID + 9-37'" whence for salt without solvent of crystallisation [RID + 10.3" 50 ICING STEREOISOMERISM AND LOCAL Crystallisation with Re.solution.-29.7 Grams of p-eucaine were neutralised with 31.2 grams of d-camphor-10-sulphonic acid in alcoholic solution A large crop of leaflets was obtained weighing 55-9 grams melting at 223-225' and having [.ID + 9-85" in water.On recrystallisation this commenced to crystallise in leaflets but on keeping over-night partial transformation into massive tablets had taken place and after another twenty-four hours transformation was complete. This salt proved to be the partial racemate described in the foregoing section. It weighed 52 grams melted at 225" and had [mlD + 9.3" in water. It was recrystallised from alcohol the leaflet form of crystal separating first. By exercising care and patience it was found possible to carry out the successive recrystal-lisations in the absence of the partial racemate but once the tablet's of the partial racemate appeared as frequently happened when the cryst'allisation was allowed to proceed over-night solution of the less stable partially resolved phase rapidly followed.When, however the resolution was nearly complete this no longer occurred, as the solubility limit of the partial racemate could no longer be attained. After seven crystallisations I-p-eucaine d-camphor-10-sulphonate (8-6 grams) was obtained pure. By working through the mother-liquors a further 7.8 grams were obtained pure repre-senting a total yield of 54 per cent. I-p-Eumine d-camphor-10-sulphonate crystallises in rectangular leaflets m. p. 248-249" (corr.) (Found C = 62.9; H = 7.9.C,,H,,O,N,C,,H,,O,S requires C = 62.6; H = 7.8 per cent.). The specific rotation was determined in water; c = 1.04; I = 2 dcm. ; aD + 0.10" 0.10"; [a]= + 4-78" + 4.83" whence it is calcu-lated for the I-p-eucainium-ion [.ID - 11.0". Another preparation gave [a]5461 + 7.3" whence for the 1-p-eucainium-ion [a]5461 - 12-7". It was not found possible to isolate d-p-eucaine d-camphor-10-sulphonate from the mother-liquors as the two salts d-p-eucaine d-camphorsulphonate and I - p-eucaine d-camphorsulphonate form a continuous series of mixed crystals. The isolation of the d-p-eucaine salt was rendered feasible as follows After removal of 6 grams of partially resolved salt the solution was crystallised as the partial racemate. Seventeen grams of this salt were obtained and from the final combined mother-liquors now rich in d-p-eucaine d-camphorsulphonate the base was recovered and neutralised with 1 -camphor- 10-sulphonic acid.d- p-Eucaine I-camphorsulphonate crystallised readily and after three crystallisations was pure. The yield was 10.2 grams or 34 per cent. of that possible. d- p-Eucaine l-cam~hor-lO-suZpho?zate was identical in its gross properties with I- p-eucaine d-camphor-10-sulphonate described above. Its rotation was determined in water c = 1.01 ; I = ANBSTHETIC ACTION IN THE P-EUCAINE GROUP. 51 dcm.; aD - 0.1"; [.ID - 5-09' whence it is calculated for the d-p-eucainium-ion [.ID + 10.6". dl- p-Eucaine dl-camphor-10-sulphonic acid was prepared from its components in alcoholic solution.It crystallised at f i s t in very fine needles but on keeping these disappeared and were replaced by six-sided plates. It also crystallises in rectangular plates. It melts a t 217-219" (corr.) (Pound C = 62.7; H = 7.8. - 1FjH2 1°2N,C10H 16'4' requires C = 62.6; H = 7.8 per cent.). The Active Eucaines and Salts. I-p-Eucuine Base.-7.5 Grams of I - p-eucaine d-camphorsulphonate were decomposed by the a,id of dilute ammonia and the free base was taken up in ether. On removal of the ether the free base crystallised readily and was obtained quite pure by crystallisation from low-boiling petroleum (40-60"). It crystallises in large prisms or columns and melts at 57-58' (corr.). It is more readily soluble in petroleum than r-p-eucaine base. 1- p-Eucaine Hydrochloride.-This salt was prepared from the base by neutralisation with hydrochloric acid.It crystallises readily in large rectangular plates with some of the corners bevelled and is more soluble than r-p-eucaine hydrochloride. It melts a t 244-245" (corr.) The specific rotation was determined in water : c = 1.21 ; I = 2 dcm. ; aD - 0.27"; [.ID - 11.3" whence for the E-p-eucainium-ion [a], - 13-0" as compared with the value [ a]D - 11 .O" calculated from the d-camphorsulphonate. Another preparation of the hydrochloride gave [a]5461 - 12.4" whence for the ion [a]5161 - 14.2". I- p-Eucuine Picrate.-This salt prepared from the base and saturated picric acid solution is very sparingly soluble even in boiling water. It is conveniently recrystallised from spirit and separates in fan-shaped clusters of small prisms m.p. 198-199" (corr.) without decomposition. d- p-Eucuine Base.-Prepared similarly to the hvo-base this melts a t 57-58' (corr.) and crystallises from low-boiling petroleum in large columns. d- p-Eucaine hydrochloride was identical in its gross properties with I- p-eucaine hydrochloride. Its specific rota1 ion was determined in water c = 1.21 ; I = 2 dcm.; aD + 0.28"; [.ID + 11.5", whence for the d-p-eucainium-ion [aID + 13.1" as compared with the value [ a]D + 10.6" calculated from the hamphorsulphonate 52 KING STEREOISOMERISM AND LOCAL Racenzic Eucaine and its Salts. r-p-Eucuine Hydrochloride.-Equal weights of d- and I-p-eucaine hydrochlorides were dissolved in water. The relatively sparingly soluble r- p-eucaine hydrochloride separated readily in small tablets which were almost rectangular and often possessed an opaque appearance.It melts a t 277-279" (corr.) without decomposition, either in an open or sealed capillary A relatively large proportioii of d-p-eucaine hydrochloride mixed with a small proportion of r- p-eucaine hydrochloride shows a depression of melting point of about 4". r-p-Eucuine baw prepared from the pure r-p-eucaine hydrochloride, crystallises well from low-boiling petroleum in large diamond- or hexagonal-shaped plates m. p. 70-71" (corr.). A small quantity mixed with a preponderating quantity of the dextro-base melted a t 53" (corr.) whereas the d-base melted simultaneously a t 60". r-p-Eucaine base is therefore a true racemate unless indeed the melt-ing-point curve shows a discontinuity where the racemic base phase passes into a pseudo-racemic.r-p-Eucaine picrate prepared from the pure racemic base in alcoholic solution is very sparingly soluble in boiling alcohol and crystallises 'in diamond-shaped plates m. p. 230.5-231-5O (corr.) (Gadamer " Lehrbuch der chem. Toxicol.," gives 230"). Hydrolylsis of d-P-Eucukne. Two grams d- p-eucaine hydrochloride were boiled for an hour with 20 C.C. of 15 per cent. hydrochloric acid when the reaction with Mayer's reagent was negative. After removal of benzoic acid the acid liquors were concentrated to a small volume when the hydrochloride of the required base crystallieed readily. d-a- Vinyldiacetonalkamine hydrochloride crystallises readily from water in many-faced tablets which are anhydrous.It is unmelted at 300". Its rotation was taken in water c == 1-2 ; 1 = 2 ; aD + 0.32" ; [.ID + 13.3" whence for the d-or-vinyldiacetonalkammonium-ion Iii a similar manner 1-or-vinyldiacetonalkamine hydrochloride was prepared by hydrolysis of 1-p-eucaine. It was unmelted a t 300" Its rotation was determined in water c = 1.22 ; I = 2 ; a - 0.45" [a]5461 - 18-5" whence for the 1-u-vinyldiacetonalkammonium-ion I-a- VznyZdiacetonaZkami~ze buse is liberated as an oil which soon solidifies on making the solution of its hydrochloride strongly alkaline (about 33 per cent. sodium hydroxide) by addition of solid sodium hydroxide. Crystallised from benzene it separates in large [.ID + 16.5". [a15461 7 23.1" ANESTHETIC ACTION IN THE P-EUCAINE GROUP.53 prisms often 1 em. long and 0.4 mm. wide melting a t 79-81' (corr.). A mixture with a small proportion of dl-a-vinyldiaceton-alkamine melted definitely lower by about 2". I-ct- Vinyldiacetonalkamine picrate prepared from exact molecular proportions of its components is very readily soluble in water. It separates on concentration in fine needles m. p. 242-244" (corr.). Preparation of N- and 0- Benxoyl- p -uinyldiacetonallcarnines, (a) From p- Vinyldiacetonalkumine Base.-The finely powdered p-base (2.35 grams) was treated with 2.6 grams of benzoyl chloride. On keeping for r? few minut,es a vigorous reaction took place with solution of the crystals. The product was now examined without further heating. Ethereal extraction of the acid aqueous solution gave after removal of benzoic acid by dilute alkali 1.2 grams of crude N-benxoyl p-vinyldiacetonalkamine.It was crystallised from benzene and separated in filmy leaflets melt'ing at 121-122" (corr.). The acid aqueous liquors made alkaline with ammonia and ex-tracted with ether gave a 35 per cent. yield of O-benzoyl-p-vinyldi-acetonalkamine and on making strongly alkaline (equivalent to 33 per cent. sodium hydroxide) gave 0.9 gram of unchanged &vinyl-diacetonalkamine, (b) From p- Vinyldiacetonalkamine Hydrochloride .-Pure p-vinyl-diacetonalkamine (14-3 grams) was neutralised with N-hydro-chloric acid and evaporated dry under reduced pressure with repeated addition of absolute alcohol. After removal of solvent as completely as possible the residual syrup often crystallised through-out.The reaction with benzoyl chloride proceeded more smoothly with the syrupy salt than the crystalline. Benzoyl chloride (13 c.c.) was added and the mixture heated a t 150" for two hours. The vinyldiacetonalkamine hydrochloride gradually passed into solution, if crystalline and the whole conteiits set to a crystalline magma of 0-benzoyl-p-vinyldiacetonalkamine hydrochloride. The product is best recrystallived direct from water after extraction with ether, which removes benzoic acid a little ethyl benzoate buf no N-benzoyl derivatives. The yield of pure 0-benzoyl- p-vinyldi-acetonalkamine hydrochloride is 90 per cent. of the theoretical. 0-Benzoyl-p-vinyldiacetonalkamine (iso-@-eumine hydrochloride) crystallises froin double its weight of hot water either in silky needles or in diamond-shaped plates.Both forms are anhydrous and the latter is the more stable conversion of the needle form into the plate form taking place on seeding with the plate form. The appearance of the needle form in solutions of the pure salt is fortuitous but in working up the mother-liquors of the benzoylation this form appears more frequently. Both forms melt a t 269-271 54 KING STEREOISOMERISM AND LOCAL (corr.) (Found C = 63.4; H = 7.9. C,5H,10,N,HCl requires C = 63.5; H = 7.8 per cent.). 0-Benxoyl-p-vinyldiacetonallcamine picrate prepared from the hydrochloride is sparingly soluble in boiling water. Crystallised from diluted alcohol it separates in delicate rectangular leaflets with bevelled corners.It melts without decomposition a t 256-258' (corr.). The free base is a syrup showing no signs of crystallisation when kept for twenty-four hours a t - 5". Resolution of iso- p-Eucaine. (a) With d-mmphor-10-sulphnic acid an extremely readily soluble salt was formed which could not be crystallised. (b) With d - a - Bromo - r - mmphrsulphonate. - Experiment A . Twenty-six grams of iso- p-eucaine d-a-bromo-r-camphorsulphonate were fractionally crystallised from absolute alcohol the successive crops showing rapidly increasing rotations the fourth amounting to 2.8 grams having + 66' whereas pure d-iso-p-eucaine d-a-bromo-rr-camphorsulphonate has [ a]5461 68-5". As considerable difficulties were encountered in effecting further separation of the contents of the mother-liquors it was decided to prepare a much larger batch.Experiment B. iso- p-Eucaine d-bromocamphorsulphonate (104 grams) was fractionally crystallised from absolute alcohol. The first crop 74.5 grams had [a]5461 + 59.3" and after six more crystallisations gave pure 1-iso- p-eucaine d-bromocamphorsulphonate (11.2 grams) having [a]5461 + 52.3". On working through the mother-liquors once 11-85 grams of d-iso-p-eucaine d-bromo-camphorsulphonate having [a]5461 + 68.3" were obtained. On working through a second time 6.95 grams of d-iso- p-eucaine d-bromocamphorsulphonate having [a15461 + 68.8" were obtained. Repeating the process a third time 17-25 grams of I-iso-p-eucaine d- bromocamphorsulphonate having [ a]5461 + 52.0" were obtained and finally 7-4 grams of d-iso-p-eucaine d-bromo-r-camphorsulph-onate having [a]5461 + 68.6".The yield of pure I-iso-p-eucaine d-bromocamphorsulphonate was thus 55 per cent. and that of d-iso-p-eucaine d-bromocamphorsulphonate 45 per cent. of that possible. 1-iso-p-Eumine d-a-bromo-n-cumphrsulphonate crystallises from three parts of boiling alcohol in microscopic needles. It also crystallises from water in glistening silky needles. It melts a t 236-238" (corr.). Its rotation was determined in water two different preparations giving the following results : c = 0.80; 2 = 2 ; a + 0-84"; [cc]s4BI + 52-26' c = 0.81 ; I = 2 ; a + 0.84" ; [a]5461 + 51-96" ANBSTHETIC ACTION IN !J!HE (3-EUCAINE GROUP. 55 whence mean value [a]5461 + 52.1" and [MI5461 + 290.0".Using the value [MI,, + 346.5" given by Pope and Read (T, 1910 97, 2200) for the d- bromocamphorsulphonic-ion it is calculated that [N]5461 for the I-iso-p-eucainium-ion is - 55.6" and [a]5461 - 22.4". Thc salt is anhydrous (Found C = 54.2 ; H = 6.5. requires C = 53.7 ; H = 6.5 per cent .). d-iso - p-Eucaine d- C( - bromo-7i.-cam~horsuZphonate crystallises from alcohol in minute needles. It dissolves in two parts of boiling alcohol and the air-dried salt contains between one-half and one molecule of water of crystallisation (Found on various preparations, loss at 100" = 1.65,2.5,2.1; on anhydrous salt C = 53.5 ; H = 6.7. Cl,H,102N,CloH1504BrS requires C = 53.7; H = 6.5; 3/4H,O = 2.4 per cent .). Its rotation was determined in water three different preparations giving the following values for the air-dried salts : CI15H2 1°2N,C10H 15°4BrS c = 0.81 ; l = 2 ; cc + 1.11"; -+ 68.3" c = 0.80; I = 2; a + 1.11"; [ c ~ ] ~ ~ ~ ~ + 68.8" c = 0.80 ; l = 2 ; a + 1-10' ; [a]6461 + 68.6" Correcting for the water content of each and taking the mean gives [a]5461 + 70.0" for the anhydrous salt whence [MI,,, + 391" and from this it may be calculated for the d-iso-p-eucainium-ion [a]5461 + 17-8".d-iso- 8-Eucaine Hydrochloride.-The free base was liberated from the bromocamphorsulphonate by ammonia extracted with ether, and obtained as an uncrystallisable spup. It was converted into the hydrochloride which crystallised extremely well from water in bold glistening needles. It melts a t 271-273" (corr.) and is anhydrous.Its rotation was determined in water c = 1-00; 1 = 2 ; cc + 0-3" ; [a]5461 + 14.9" whence for the d-iso-p-eucainium-ion [a]5461 + 17-0". This compares favourably with the value + 17.8" calculated above from the rotation of the bromocamphor-sulphonate. I-iso-B-Eumine Hydrochloride.-T~ salt melted at 271-273" (corr.). Its Totation was determined in water c = 1.0 ; I = 2 ; tc - 0.28"; [a]5461 - 14-25' whence for the I-iso-p-eucainium-ion [a]5461 - 16.3" a value close to that of the d-salt but showing considerable variation from that - 22-4" calculated from the bromocamphorsulphonate . 1-iso- p-Eucuine Picrate.-This salt is very sparingly soluble in boiling water. It separates from diluted alcohol in fine needles and melts a t 280" (corr.) 56 STEREOISOMERISM AND LOCAL ARBSTHETIC ACTION ETC.Hydrolysis of I-iso- p-Eucaine. I-iso-p-Eucaine hydrochloride (10 grams) was boiled for three hours with 15 per cent. hydrochloric acid when the reaction with Mayer's reagent was negative. After removal of benzoic acid the solution was evaporated to dryness under reduced pressure with addition of alcohol and the residue crystallised from a mixture of absolute alcohol and dry ether. d- p- Vinyldiacetonalkamine hydrochloride crystallises in tablets and melts a t 217-219" (corr.). Its rotation was determined in water; c = 1.34; 1 = 2 ; a + 0.61"; + 22-85' whence for the d-p-vinyldiacetonalkammonium-ion [a]5461 + 28.5". d- p- Vinyldiacetonalkamine was prepared by addition of 3 grams of sodium hydroxide to a solution of 5-3 grams of the hydrochloride dissolved in 10 C.C.of water. The free base separated in six-sided plates. It was recrystallised from benzene and separated in well-formed tablets melting a t 121-123" (corr.). d-p- Vinyldiacetonalkamine picrate prepared from exact molecular equivalents of the components is extremely soluble in boiling water, but much less soluble in cold. It crystallises in fine radiating needles and melts at 181-182" (corr.). Action of Sodium Amyloxide on d- p- Vinyldiacetonalkamine. d- p-Vinyldiacetonalkamine (3.6 grams) was boiled for thirty-two hours with 7.5 grams of sodium dissolved in 75 C.C. of amyl alcohol (b. p. 130"). The solution was steam-distilled so long as any alkaline-reacting material passed over. The distillate was acidified with hydrochloric acid t'he amyl alcohol removed by a separator and finally by ether and the solution evaporated to dryness under reduced pressure with addition of alcohol.The product was digested with 10 C.C. of absolute alcohol and filtered after standing for a few hours. The alcohol-soluble fraction amounted t o 0.9 gram and the alcohol-insoluble to 2-95 grams. The latter was uiimelted a t 300" and had [ M ] ~ ~ ~ ~ + 17-6" in water (c = 1.2). As the rotation of pure d-a-vinyldiacetonalkamine hydrochloride is [a]5461 + 18.5" the product was almost pure d-a-vinyldiaceton-alkamine hydrochloride ; a mixture containing 2.4 per cent. of the 1-salt would give [a]5461 + 17-6". To confirm its identity 2.5 grams were converted into the free base and crystallised from benzene. It separated in perfectly formed long prisms of hexagonal outline and melted a t 79-81" (corr.) as did the pure 1-base in the same bat'h. Preparation of ON-Dibenxoyl- o(- and - p-vinyldiacetonalkamines. ON-Dibenxoyl-a-vinyldiacetonalkamine was prepared by heating p-eucaine base (3.6 grams) with benzoic anhydride (1 mol.) at 160 THE RAPID ADMIXTURE OF HOT COMBUSTIBLE GASES WITH AIR. 67 for two hours. The crude non-basic portion containing the di-benzoyl derivative amounted to 1.7 grams. It was deeply pig-mented but crystallised readily. It was best recrystallised from alcohol and separated in six-sided plates m. p. 142-143" (corr,). From the basic portion of the liquors 3.0 grams of p-eucaine hydro-chloride were recovered (Found C = 75.1 ; H = 7.2. C22H2503N requires C = 75.2 ; H = 7.2 per cent.). ON-Dibenxoyl- 8-vinyldiacetonalkamine was prepared in a similar manner from iso-p-eucaine base. It crystallises best from ether, separating in flattened prisms m. p. 114-115" (corr.). DEPARTMENT OF BIOCHEMISTRY AND bHARMBCOLOGY, THE NATIONAL INSTITUTE FOR RqEDICAL RESEARCH, HAMPSTEAD N.W. 3. [Receiwed November 1 Dtlr 1923.

ISSN:0368-1645    

DOI:10.1039/CT9242500041

出版商:RSC    

年代:1924

数据来源: RSC

摘要:

THE RAPID ADMIXTURE OF HOT COMBUSTIBLE GASES WITH AIR. 67 VII1.-The Rapid Admixture of Hot Combustible Gases with -4ir. By FRANK MAURICE CRAY and WILLIAM EDWARD GARNER. MIXTURES of combustible gases and air after attaining the ignition temperature pass through a rapidly accelerating process of com-bustion which finally culminates in the appearance of flame. The interval of time which elapses between the attainment of the normal ignition temperature and the commencement of ignition is known as the pre-flame period and the duration of this period depends on the temperature coefficient of the combustion process and on the magnitude of the thermal changes accompanying the chemical reactions. The pre-flame period for a few gaseous mix-tures has been studied by several investigators.Dixon Bradshaw, and Campbell (T. 1914 105 2027) have shown that the period of pre-flame for a mixture of hydrogen ar,d oxygen when heated by compression is of the order of 1/100 of a second and recently, Tizard and Pye (Phil. Mag. 1922 [vi] 44 79) have determined the delay in ignition which occurs when mixtures of heptane ether or carbon disulphide with air are ignited in the same manner. From the latter investigation it appears that delays of the order of one second may occur when a gaseous mixture is heated just above its ignition temperat'ure but that the delay decreases with increasing temperature ; at temperatures 50" above the ignition temperature, the delay is very small though still appreciable. Also Will (2. ges. Schiess- u. Sprengstoflzu.1909 4 302 323 343) has observed the occurrence of a period of pre-flame when the gaseous products from the detonation of high explosives were rapidly projected into 58 CRAY AND GARNER THE RAPID ADMIXTURE OF cold air. In the case of several explosives containing insufficient oxygen for complete self-combustion ignition did not occur immedi-ately after admixture of the combustible gases with the surrounding air and photographs of the explosion showed two distinct emissions of light one due to the hot unignited gases and the other after an interval of time due to their secondary combustion in the air. The duration of the interval between the two flashes was 2-6-thousandths of a second for explosions of picric acid and trinitro-toluene. In these circumstances the occurrence of ignition is dependent not only on the temperature of the hot gases and on the time of pre-flame but also on the rapidity of admixture of the hot gases with the cold air.In some of Will's experiments with trinitrotoluene the second flash was not observed and in these cases it appears that the hot combustible gases were mixed so rapidly with the surrounding air that they were chilled below their normal ignition temperature within the time of pre-flame. The factors which determine the " after-ignition " of the gases from the explosive processes are so complex that it is not easy to devise a promising line of at,tack on the problem. I n the present paper two attempts have been made to study the behaviour of hot gases on admixture with air and although their original purpose has not been achieved it is thought that the results obtained are of sufficient interest to warrant their publication especially as there is little likelihood of our continuing the investigation in the near future.In the first series of experiments the source of the hot combustible gases was picric acid contained in small steel containers, and in the second acetylene and oxygen mixtures contained in thin glass bulbs. Part I . Detonation of Picric Acid in S'teel Conduiners. The object of these experiments was to invest'igate the effect of variations in the ratio of the volume of the explosive gases to the volume of the air into which they were projected the other con-ditions for example the work done on the container per gram of explosive the density of the explosive etc.being kept as uniform as possible. With this end in view the explosive was contained in cylindrical steel containers drilled out of solid steel with an internal diameter of 0.4 inch and with walls and base-0.25 inch thick and fired under standard conditions by a lead azide detonator in a large closed vessel of 86.7 litres capacity in an atmosphere of air. This volume of air gives sufficient oxygen for the complete com-bust)ion of approximately 55 grams of picric acid and on this account tJhe amounts of explosive were not allowed to exceed 50 grams. The length of the container and the weights of th HOT COMBUSTIBLE BASES WITH AIR. 59 explosives were the only variables in these experiments. The density of the picric acid which was in the form of pellets was 1 -30 throughout.In addition a few detonations were carried out in containers with an internal diameter of 1 inch and with a wall thickness of 0.25 inch. It was hoped that the results of these experiments would throw light on the part played by the cooling of the gases due to the work done on the container. The cooling due to this cause should not be so great in this as in the first series for the amount of explosive operating on a sq. cm. of steel surface is much greater. To obtain a measure of the combustion the volume of carbon monoxide in the residual gases was determined and compared with FIG. 1. Grams of picric acid. that found when the explosive was detonated under similar con-ditions in a vacuum.The carbon monoxide was nnalysed by the iodine pentoxide method. The results which were obtained are given in Tables I and 11 and are summarked in the curve (Fig. 1). TABLE I . Containers 0.4 inch internal diameter. Pic& No. of acid expt. (grams). 1 2.145 2 3.67 3 5.2 4 10.84 5 12.48 Vol. of Per cent. CO (c.c./ CO. gram). 0.87 334 1.48 338 2.12 346 4.05 332 0.44 32 Picric No. of acid expt. (grams). G 12.64 7 12.84 8 12-56 9 14-65 10 22.35 VOl. of Per cent. CO (c.c./ CO. gram). 5.70 410 1.01 72 4.49 317 0.76 46 0.28 11 Volume of CO from explosion in a vacuum = 323 c.c./gram 60 CRAY AND GARNER THE RAPID ADMIXTURE OF TABLE 11. Containers 1.0 inch internal diameter. No. of expt. .................. 1 2 3 4 Picric acid (grams) .........8.0 21.04 41.59 46-77 Per cent. CO .................. 0.3 0.26 1.58 3.76 W-hen weights of picric acid ranging from 2 to 12 grams were taken in the containers (0.4 inch in diameter) the volume of carbon monoxide per gram of explosive (column 4) in the final gases agreed with that obtained when the explosive was detonated in a vacuum. The curve shows the regular manner in which the percentage of carbon monoxide increases with the weight of acid over this range. It is evident that under these conditions no appreciable " after-ignition " has taken place. When the weight of explosive exceeds 12 grams the percentages of carbon monoxide become irregular and in general less than the values obtained in a vacuum. The break in the curve which occurs at about this point indicates that ignition with the air now takes place to a greater or less extent.When picric acid was detonated in the containers (1.0 inch in diameter) ignition was found to occur even with the smallest weight taken for example with 8 grams of explosive. Also a detonation in a container with internal diameter 1 inch and walls 0.625 inch thick that is with the same ratio of diameter to thickness as in series I gave when loaded with 9.672 grams of picric acid 0.68 per cent. of carbon monoxide. The low percentage of carbon monoxide shows that ignition has taken place. The minimum percentage of carbon monoxide is obtained when 20 grams of explosive are detonated in the bomb. Above this weight the percentage rises (curve) until with.47 grams nearly 4 per cent.of this gas is present in the final gaseous mixture. The increase in the percentage of carbon monoxide as the weight of explosive increases may be ascribed to an increased dissociation of carbon dioxide as the excess of oxygen diminishes or to an irregular admixture of the hot combustible gases with the air of the bomb. The cooling of these gases by radiation of heat to the walls takes place so rapidly that an appreciable amount of the carbon monoxide escapes combustion during the cooling process. From the figures in Table I it will be observed that the hot gases from the detonation may burn in the air if the weight of explosive exceeds 12 grams. This is approximately the limiting weight for the conditions ruling in this series of experiments.The heat of detonation of this amount of explosive suffices to raise the whole mass of air enclosed in the bomb to 500" if no energy is expended on the container or lost by radiation. The actual tem HOT COMBUSTIBLE GASES WITH AIR. 61 perature rise owing to radiation and other losses will be much lower than this and even with larger weights of explosive the calculated temperature of the gaseous mixture would be con-siderably below the; ignition temperature. Thus if the gaseous products from a detonation had been completely mixed with the air of the bomb within the time of pre-flame that is before an appreciable amount of combustion occurred the break in the curve would be expected to occur not a t 12 grams of explosive but a t some much higher value.The actual volume OI air with which the gases mix before combustion occurs to any appreciable extent cannot be determined from the above results. Part I I . Explosion of MixturM of Acetylene and Oxygen. Mixtures of acetylene and oxygen contained in thin glass bulbs, were exploded in a small bomb containing air. The glass bulbs were shattered by the explosion and the gaseous products rapidly admixed with the air in the bomb. I n order that combustihle gaseous products with varying compositions and temperatures might be obtained the proportions and total amounts of the com-ponents of the explosive gas mixtures were varied. It was expected that the amount of “ after ignition” which occurred would be dependent on these factors. It was found under the conditions of our experiments that the gaseous products of the explosion always ignited in the air although the combustion was never complete.Thus carbon monoxide acetylene and methane were present in the final gaseous mixture. For mixtures of acetylene and oxygen in the ratios 1 I 2 1 and 3 1 about 6-5 per cent. of the acetylene was converted into carbon monoxide what-ever the quantities of the combustible gases and their pressures in the glass bulbs. As would be expected those mixtures richer in oxygen gave somewhat smaller percentages of carbon monoxide. The ma8ximum percentage of carbon monoxide was obtained with that mixture possessing the highest velocity of explosion. It is difficult to understand why the amount of “ after ignition ” should be practically independent of the amounts of acetylene taken.The slow rate a t which carbon monoxido and air mixtures burn (Bone and Haward Proc. Bog. I.soc. 1921 [ A ] 100 67) is conceivably the cause of the incompleteness of the ignition. One of the intermediate steps in the oxidation of acetylene is the form-ation of carbon monoxide and this stage in the oxidation takes place more rapidly than the subsequent conversion of the carbon monoxide into carbon dioxide. I n our experiments the com-bustion to carbon monoxide is probably complete before the ’hot gases from the bulb strike the walls of the bomb after the explosio 62 GRAY AND GARNER THE RAPID ADLLdIXTURE OF and the whole of the space is thus fdled with a carbon monoxide-air mixture. A definite fraction of this gas about 6-43 per cent.is chilled by the cold air and the walls of the bomb. The dilution of the products was not sufficiently rapid to prevent ignition even in those experiments where the heat liberated was insufficient to raise the whole of the gases in the bomb (air and combustible products) to their normal ignition temperature. A true detonation wave is not set up in mixtures of acetylene and oxygen within a distance of 2.5 inches (Dixon Phil. Trans. 1903, [ A ] 200 3151 and since this distance is greater than the radius of the largest bulbs the velocity of propagation of the explosion wave may not have exceeded the velocity of uniform movement of the flame. However it is probable that the amount of after ignition could be reduced and even avoided altogether as occurred in the above experiments with picric acid provided that a detonation wave be set up in the mixture.An apparatus has been devised (Fig. 2) which is suitable for the study of the rapid chilling of the products of gaseous explosions. It is hoped that the apparatus will render possible the isolation of some of the intermediate compounds produced during the various stages of the combustion of hydrocarbons. That such compounds are produced by this method was shown in a series of experiments, in which mixtures rich in acetylene were exploded in a thin glass bulb surrounded by an atmosphere of nitrogen. A gaseous product was obtained which exerted a strong reducing action on a solution of ammoniacal silver nitrate. This substance does not appear to be an aldehyde since it is without effect on Schiff’s reagent.E X P E R I M E N T A L . Apparutus.-A diagram of the bomb with a glass bulb in position, is given in Fig. 2. The bomb consisted of a cylindrical vessel of phosphor-bronze of 1600 C.C. capacity with an internal diameter of 12.7 cm. and an internal height of 12.5 cm. The top of the bomb carried three gas outlets an insulation plug E and an earthed terminal. The outlet A which could be closed by a coned joint at the bottom was used for the evacuation and filling of the glass bulbs with the mixtures of gases. The glass bulb terminated a t each end by short lengths of glass tubing was closed at the lower end C by means of fusible alloy contained in a small brass cup of 1 inch depth and 2 inch diameter.Two enamelled copper wires, used in firing the gaseous mixture passed through the fusible alloy in this cup into the centre of the bulb. The insulated wires carried a piece of fine iron wire which could be readily fused by a current from an 8-volt battery. The top eBd of the bulb was immerse HOT COMBUSTIBLE CASES WITH AIR. 63 in another fusible alloy cup attached to the outlet A in the top of the bomb. In making the glass-to-metal joints the fusible metal was heated at loo" poured into the heated brass cups and the end of the glass bulb inserted. The fusible alloy was raised by suction to the levels marked on the glass side tubes between which the volume of the bulb had been determined and maintained at these points until the metal had solidified.This method of sealing gave vacuum-tight joints but occasionally some of the bulbs cracked under the strain set up by the solidifying fusible FIG. 2. alloy. The weight of a 90 C.C. bulb was about 5 grams and the glass side tubes accounted for the larger proportion of this weight, the bulbs being made as thin as possible. In carrying out an experiment a glass bulb of known capacity was cemented in position and the bomb closed by making the joint B. The air in the bomb mas adjusted to atmospheric pressure and the bulb evacuated through the outlet A and the three-way tap D. Mixtures of acetylene and oxygen saturated with water vapour were introduced into the bulb at atmospheric pressure, through the other arm of the three-way tap D which was the 64 CRAY AND GARNER THE RAPID ADMIXTURE OF closed and the cone F was raised to close the end of the outlet tube.The gases were fired by the fusion of thin iron wire carried by enamelled copper leads passing through the bottom fusible-alloy cup attached to the bulb. After firing the bomb was allowed to cool to room temperature and the pressure of the gases measured. About 500 C.C. of these gases werr removed for analysis and the pressure was again measured. From the difference between the two pressures the exact volume removed could be calculated. A determination of the ratio of carbon dioxide to carbon monoxide gave a measure of the amount of " after ignition " which had occurred. The accuracy of the methods of mixing was checked by analysis of several acetylene-oxygen mixtures after dilution with nitrogen over copper oxide.Analysis of the Gaseous Products.-The iodine pentoxide method for the analysis of gaseous mixtures containing small quantities of carbon dioxide carbon monoxide acetylene and saturated hydro-carbons offers considerable difficulties. The main source of uncertainty is the removal of the acetylene before passage of the mixture over iodine pentoxide. Levy ( J . SOC. Chenz. Ind. 1911, 30 1437) recommends the use of a solution of bromine in potassium bromide for this purpose This method was adopted for the majority of the results reported in this paper (Tables 111 IV and V). Experiments carried out in the course of this work have shown however that about 30 per cent. of the acetylene in a 1.5 per cent. mixture with air is not retained by this reagent.Pos-sibly volatile bromides or unchanged acetylene pass through the alkali and thence to the iodine pentoxide. Recently Siiinatt and Slater (Fuel 1922 1 241) have drawn the same conclusion and instead recommend fuming sulphuric acid which they state is satisfactory. This absorbent was discarded in the present work on account of the sulphur trioxide fume. To avold the use of this reagent a method of separation was developed involving the freezing out of the carbon dioxide and the acetylene from the carbon monoxide and saturated hydrocarbons by passing the gases through a spiral immersed in liquid air. Carbon monoxide is not retained by the solid mixture of carbon dioxide and acetylene. The carbon dioxide was usually determined by absorption in baryta solution before freezing out the acetylene.In the series of experiments described below (Tables 111 IV and V) in which an analysis was made of carbon monoxide carbon dioxide and saturated hydrocarbons it was assumed that the acetylene could be removed completely by bromine in potassium bromide and the carbon monoxide was estimated by the iodin HOT COMBUSTIBLE GASES WITH AIR. 65 pentoxide method. On this account the percentages of carbon monoxide obtained in this series may be a little too high by about 0.2 per cent. The results have however been checked in some cases by the freezing-out method (see p. 68). The carbon dioxide was removed by passing through two bubblers containing N / 5 -baryta solution and the carbon monoxide converted into dioxide over iodine pentoxide at 140" according to Levy's method.After passing through a cooling worm containing a little mercury and immersed in ice the carbon dioxide from the oxidation of the carbon monoxide was absorbed in two more bubblers containing N 10 - baryta solution. Saturated hydrocarbons were estimated by combustion over copper oxide in silica tubes and the absorption of the carbon dioxide produced in N/lO-baryta solution. The type of the absorption bubbler employed is shown in Fig. 3 as this type per-mitted the titration of the excess baryta without risk of introducing carbon dioxide from the air. Burettes could be inserted very quickly into the narrow necks of these bubblers, and during the titration the solution could be stirred by drawing a slow current of carbon dioxide-free air through the apparatus.The air space between the bulbs and the walls of these bubblers should be as small as possible. On account of the difEculty of removing the gas dissolved in the solutions in the bubblers and the large volume of air which had to be displaced in the analysing apparatus each complete analysis took about six hours. Results.-The results obtained when the gaseous mixtures were exploded in an atmosphere of air are given in Table 111. The nature of the metamorphosis of the explosive mixtures varied to some extent from one experiment to another depending on con-ditions governing the fragmentation of the bulb which were not under our control and it was necessary to carry out a number of experiments under each set of conditions.Typical results are given in each case. The percentage of acetylene converted into carbon dioxide and carbon monoxide and the ratio [CO,]/[CO] are given for a number VOL. cxxv. 66 GRAY AND GARNER THE RAPID ADMIXTURE OF VOl. of Gas bulb mixture. in C.C. 30,+C,H2 95-70 20,+C,H2 94.80 O,+C,H 90.80 0,+2C,H 92-70 0,$3c2H 88.3 TABLE 111. Bomb filled with Air. VOl. of C.C. of dry gas CO, at at N. T.P. N . T.P. 90.0 44.0 88.2 56-1 84.9 75.0 87.3 102.1 83.7 95.5 C-C- of % of origiFa1 C,H co appearmg as at ,-Apy [COJ N.T.P. CO,. CO. Carbon. Ico] ' 1.7 97.8 3-8 Nil 25.9 2.9 93.7 4.9 Nil 19.0 7.1 88.3 8.4 Nil 10.6 8.2 137.7 7.0 4.9 12.5 '7.3 76.1 5.8 6.3 13.1 of mixtures of acetylene and oxygen.The ratio decreases from 25.9 for the mixture 30 + C,H to 10.6 for 0 + C2H2 and then increases slightly to 13.1 for 0 + 3C,H2. This ratio is thus a minimum and the percentage of carbon monoxide a maximum for that mixture with the highest velocity of explosion. This is in agreement with the view expressed above that the rate of admixture with the air is a factor in the phenomena of ignition. Occasionally an abnormal result was obtained and in these cases the bulb was not finely powdered by the explosion but broken into large pieces. These results have been omitted from the summary. The appear-ance of the glass in these cases suggested that the velocity of explosion was abnormally low and consequently it was expected that the " after ignition" would be greater than usual and the ratio [CO,]/[CO] higher.This was found to be the case in every instance. For one particular result with the mixture 0 + 3C,H,, the ratio [CO,]/[CO] rose to 86.0 and the carbon deposit was much smaller than usual the large pieces of glass being covered with only a very light covering of carbon. The total carbon present in the gases after explosion was estim-ated by combustion of a sample of gas over copper oxide; from these results and the quantity of acetylene taken the free carbon given in column 8 has been deduced. These figures are in agree-ment with the visual examination of the fragments of glass. Except for traces of a dark deposit on the larger glass fragments there was no evidence of the presence of any carbon in experiments with the first three mixtures but in the last mixtures the glass was covered by a deposit of carbon and also the walls of the bomb were frequently covered with a fine carbon dust.Methane or other saturated hydrocarbons were usually present to 0-2 per cent. A visible precipitate of silver acetylide was obtained when the gases from mixtures rich in acetylene were passed through ammoniacal silver nitrate. The ratio [CO,]/[CO] was slightly affected by variations in the size of the bulb (Table IV) decreasing from 12.3 to 9.1 as the siz HOT COMBUSTIBLE GASES WITH AIR. 67 of the bulb changed from 32-0 to 175 C.C. This may be due to an increasing velocity of flame as the volume of gas is augmented. The percentage of acetylene converted into carbon monoxide was practically unaffected by changes in the ratio of the volume of explosive mixture to the volume of air.A series of results obtained for 0 + C2H2 mixtures is given in Table IV. TABLE IV. Bomb $filled with Air. Gas mixture C,H + 0,. % of C,H % of C,H, Size of bulb appearing Siz of bulb appearing in C.C. as CO. [CO,]/[CO]. in C.C. as CO. [CO,]/[CO]. 32-0 7.6 12.3 115.0 7.3 11.0 61.0 7.8 12.0 150.0 7.7 9.4 90.s 8-4 10.6 176.0 9.0 9-1 In one experiment the pressure of the gaseous mixture was increased to 130 cm. of mercury and here the percentage of acetylene converted into carbon monoxide was 7.3 compared with 8.4 for atmospheric pressure. A series of experiments (Table V) in which the air in the bomb was replaced with nitrogen gave a gaseous product which readily reduced ammoniacal silver nitrate solution.From the mixtures 3C2& + 0 and 2C2H + 0 a large black precipitate was obtained, but the amounts of this reducing substance were variable from one experiment to another. The reducing substance did not appear to be an aldehyde but time was not available for its complete investigation. From mixtures richer in oxygen blue colloidal silver sols were obtained. The results obtained with 0 + C,H mixtures agree with those of Bone and Drugman (T. 1906 89 660). TABLE V. Bomb jilled with Nitrogen. VOl. of Gas bulb mixture. in C.C. 3oZ+C,H2 87.7 20,+ C,H 88.0 O,+C,H 92.3 0,+2C2Hz 87.2 o,+ 3C,H2 88.7 1-01. of dry gas at h'. 1'. P. 82-8 82-2 86.6 81.5 81.1 C.C.of at AT. 1'. P. 37.1 30.6 1.1 Nil Nil co2 C . C . of co at N. T. P. 3.7 23.1 84.0 53.8 43.4 "/o of original appearing as CZH, co,. co. [CO,]/[CO]. 89-6 8.9 10.1 55.8 42.2 1.3 Nil 49.5 Nil 35-7* 1.3 97.0 0.01 * This percentage may include a small amount of the reducing substance, as this was not removed during the analysis. A further series of experiments has been carried out by Mr. R. G. Fitter in which the acetylene was condensed out of the gaseous D 68 THE RAPID ADMIXTURE OF HOT COMBUSTIBLE GASES WITH AIR. mixture after removal of the carbon dioxide by passing the gaseous products through a spiral immersed in liquid air and the carbon monoxide and methane were converted into carbon dioxide over copper oxide.The total percentage of carbon monoxide and saturated hydrocarbons recorded by this method is somewhat higher than that obtained for carbon monoxide by the iodine pentoxide method. Thus for C,H + 02 9.3 per cent. against 8-4 per cent. for 2C,H + O, 9-07 per cent. against.7.0 per cent., and for 3C2H2 + O, 8-8 per cent. against 5.8 per cent. but allowing for the methane included in this percentage the confirmation of the results of the first series may be regarded as satisfactory. Remarks on Part I I . The explosion of acetylene and oxygen mixtures in thin glass bulbs gives rise to gaseous products which inflame in the air of a closed vessel. The ‘‘ after ignition ” is only partial about 6-8 per cent. of the total hydrocarbon being converted into carbon monoxide.The conversion into carbon monoxide is slightly affected by changes in the ratio of the volume of explosive mixture to the volume of air. The degree of chilling is a t a maximum and the ratio [CO,]/[CO] a t a minimum for the mixture possessing the maximum velocity of combustion. Free carbon is produced from mixtures containing less than equimolecular proportions of oxygen and small per-centages of acetylene and saturated hydrocarbons are found in the products of the explosion. The conditions under which these explosions are carried out should be favourable to the appearance of carbon if this is one of the initial products in the combustion of acetylene in oxygen. Carbon was only observed in those experiments where there was insufficient oxygen to convert all the carbon into carbon monoxide.The absence of carbon from the products of the explosion of the first three mixtures confirms Bone’s view of the mechanism of the combustion of hydrocarbons. According to this view oxidation of the hydrocarbon takes place through aldehydes and acids to carbon dioxide without the liberation of carbon at any of the stages of combustion. Summary. Experiments have been described in which high explosives in steel containers and acetylene and oxygen mixtures in glass bulbs, have been exploded in a limited volume of air. The products have been analysed to determine the degree of ignition which occurs. It is shown in the case of high explosives that the phe-nomenon of “ after ignition ” is to some extent determined by the vdume of air into which the gases are projected ignition occurrin THE DISSOCIATION CONSTANT OF BORIC ACID.69 when the ratio of weight of explosive to volume of air exceeds a definite value. The interpretation of the results is rendered diEcult by the unknown amount of cooling brought about by the disruption of the container. On the other hand the gaseous products from the acetylene-oxygen mixtures on account of their much slower rates of explosion as compared with the velocity of detonation of high explosives always underwent partial ignition on admixture with air and the degree of ignition is dependent to some degree on the ratio of volume of air to volume of explosive, and slightly affected by changes in the composition of the gaseous mixture. The ignition is the more complete the slower the velocity of explosion of the gases and this confirms the view that t,he ignition temperature of hot gases projected into cold air is dependent on the rapidity of admixture. We wish to express our best thanks to the Director of Artillery for permission to publish that part of this work carried out a t the Research Department Royal Arsenal Woolwich and to the Department of Scientific and Industrial Research for a grant to one of us. TEE SIR WILLIAM RAMSAY INORGANIC AND PHPSICAL-CHEMICAL LABORATORIES UNIVERSITY COLLEGE LONDON. THE RESEARCH DEPARTMENT, ROYAL ARSENAL WOOLWICH. [Received October 22nd 1923.

ISSN:0368-1645    

DOI:10.1039/CT9242500057

出版商:RSC    

年代:1924

数据来源: RSC

摘要:

THE DISSOCIATION CONSTANT OF BORIC ACID. 69 IX. -Th,e Dissociation Constmt of Boric Acid. By EDMUND BRYDGES RUDHALL PRIDEAUX and ALFRED THOMAS WARD. ON account of their utility as buffer mixtures various borate solutions have been standardised with the hydrogen electrode, and from these results the apparent dissociation constants of boric acid in these solutions may be calculated. Such constants depend on the agreed status of the hydrogen electrode as repre-senting the best measure yet available of the activity of the hydrogen-ion. If the activities or effective concentrations of the ion and the undissociated acid are put equal to the neutralised and the unneutralised part of the acid respectively complete dissociation of the salts is assumed. The constants are then apparent constants, useful in the calculation of the p H of mixtures not too far removed in concentration from the standards.The apparent constant is calculated by the usual equation which is conveniently stated i 70 PRIDEAUX AND WARD : the form k = Rh/(1 - R) in which R is the ratio of equivalents of alkali to mols. of acid. It is usually found that E varies with (1) degree of neutralisation, (2) total concentration and (3) presence of neutral salts. (1) The following results refer to borax Na~H,BO,,H,BO, in which R is 0.5 and h = k p H = p k . Schmidt and Finger. Sorensen. Palitzsch. Clark and Lubs. C 0.25 0.10 0.05 0-05 (0.2 KC1) PH 9.3 9-24 9.24 9-14 k x 1O1O 5.0 5.6 5.6 7-2 The authors at C = 0.02 find p~ = 9-02 and k x 1O1O = 9.55. A decrease in total concentration thus brings about an increase in E .This change is in the opposite direction to that which has been noted in the case of phosphoric acid (second constant). The result for boric acid may perhaps be attributed to the break-ing up of the anionic complexes H,BO,',nH,BO, which are formed in partly neutralised borate solutions especially a t higher con-centrations (Auerbach 2. anorg. Chem. 1904 37 352 ; Prideaux, Trans. Faraday Xoc. 1915 15 76). In the most dilute solutions the constant is not far from the conductivity constant 1.7 x (2) The change in k with degree of neutralisation R may be obtained from the results of Palitzsch and of Clark and Lubs. We have added some determinations in more dilute solutions. Palitzsch's solutions were made from 0-2M-boric acid mixed with 0-OZM-borax.The total concentrations were therefore not constant. C.C. of b0raxfc.c. of boric acid 0.3/9-7 9.6/9.4 8-0/2.0 9.0/1-0 C 0.196 0.195 0.080 0.065 R 0.00383 0.007 0.25 0.345 k x 1010 6.5 5.75 3.6 4.1 Clark and Lubs's solutions were made by adding 0-2N-sodium hydroxide to 50 C.C. of O.2M-boric acid and diluting to 200 C.C. They were therefore 0-05 molar with respect to borate. C.C. of sodium hydroxide/50 C.C. of boric acid 2.61 12-00 21-30 26-70 43.90 PH 7.8 8.6 9.0 9.2 10.0 k x 1010 8.4 7.9 7.4 7.4 7.1 Our solutions were 0.02 molar with respect to borate and 0-06 molar with respect to sodium chloride. The temperature was about 18". R 0.25 0.50 0-75 Pr 9.02 9.02 9.08 kXl0" 9.6 9.6 8.25 PR 8-54 9.02 9.56 In each series an increase in R is associated with a decrease in k.Also by comparison (at corresponding concent'rations) o THE DISSOCIATION CONSTANT OF BORIC ACID. 71 series 1 with 2 and 3 respectively it is seen that the addition of neutral salt increases k. The Constant of Boric Acid Calculated from the Ionic Activities. The activity of the hydrion is taken as that given by the hydrogen electrode and the activities of the H,BO,’-ion as that of CIO,’ in solutions of the same ionic strength as given in the tables of Lewis and Randall’s “ Thermodynamics.” * By means of the activity coefficients a we get an expression for the ion activity constant k’ = ha[A]/a[HA]. The activity of the undissociated molecule in this case H$O,, may perhaps be taken as 1 in dilute solutions by analogy with glycerol and other non-electrolytes.In more concentrated solu-tions it would be greater than unity. The equation given in Lewis and Randall’s book (p. 288) when applied to the freezing-point depression of a 0-066 molar solution of boric acid 0.129” (Juttner-Arrhenius) gives an activity coefficient of 1.094. On this account and because the ionic strengths in the buffer solutions quoted above are too high for the application of Lewis and Randall’s tables the calculations must be restricted to the solutions measured by us. At R = 0.5 Cborate = 0.02 and CNaCl = 0.06. [H,BO,’] 0.01. The total ionic strength is equal to half the sum of Na’ = 0.07, The activity of H,BO,’ is taken as that of ClO,’ at this ionic C1‘ = 0-06 H,BO,‘ = 0.01 that is to 0.07. strength that is 0.65. The ion activity constant which allows for the effect of all ions present is thus smaller than the apparent constant calculated for the dilute borate. It happens to agree with the constant usually attributed to boric acid. The ion activity constant still shows a fall at higher values of R. We consider that this is to be accounted for in the same manner as the fall in the apparent constant. The correction for ionic strengths does not take account of complex ions. UNIVERSITY COLLEGE NOTTINCHAM. * In these tables the concentrations are expressed in molalities or mols. We have expressed them in mols. per litre the [Received July 25th 1923.1 in 1,000 grams of water. numerics being almost identical in such dilute solutions

ISSN:0368-1645    

DOI:10.1039/CT9242500069

出版商:RSC    

年代:1924

数据来源: RSC