摘要:

J O U R N A L OF THE CHEMICAL SOCIETY. H. E. ARMSTBONG Ph.D. F.R.S. A. DUPRB Ph.D. F.R.S. C. GRAHAM D.Sc. F. R. JAPP M.A. Ph.D. HUGO MULLER Ph.D. F.R.S. W. H. PERKIN F.R.S. H. E. ROSCOE LL.D. F.R.S. W. J. RUSSELL Ph.D. F.R.S. J. MILLAR THOMSON F.C.S. R. WARINGTON F.C.S. C. R. A. WRIGHT D.Sc. F.R.S. @;biiax : HENRY WAITS B.A. F.R.S. Snb- @%tar : C. E. GROVES F.C.S. Vol. XXXIX, 1881. TRANSACTIONS. L O N D O N : J. V A N V O O h S T 1 P A T E R N O S T E R ROW. 1881 LONDON : HARRTSON AND SOXS. PRTNTERS IN ORDINARY TO HER MAJESTY ST. MARTIN’S LANE C 0 E T E N T S. PAPERS READ BEFORE THE CHEMICAL SOCIETY :-PAGE I.-Aluminium Alcohols. Part I. Their Preparation by Means of the Aluminium-Iodine Reaction. By J. H. GLADSTONE, Ph.D. F.R.S. and ALFRED TRIBE Y.C.S.Lecturer on 11.-Synthetical Prodnction of New Acids of the Pyruvic Series 111.-The Ancient Alum Well at Harrogate. By R. HAYTON 1V.-Contributions from the Laboratory of Gonville and Cabs College Cambridge. No. VII. On Bismuth and Bismuth Compounds. By M. M. PATTISON MUIR M.A. F.R.S.E., Caius Prdector in Chemistry ; G. BERNARD HOFFMEISTER, B.A. B.Sc.; and C. E. ROBBS Scholars of Caius College, V.-On a New Class of Colouring-matters from the Phenols. V1.-On Nitroso - p - Naphtholsulphonic Acid. By RAPHAEL VI1.-Note on the Formation of Carbon Tetrabromide in the By J. C. HAMILTON Student in VII1.-Communications from the Laboratory of the University On the Volumes of Sodium Bromine, By D. ORME By LAURA M. PASSA-VANT Brown Scholar in the Yorkshire College Leeds.. 53 By W. N. HART-LEY F.R.S.E. Professor of Chemistry Royal College of XI.-Analyses of Queensland Soils. By Professor LIVERSIDGE, Assoc. R.S. Mines F.I.C. &c. . . . 61 XIL- Communications from the Laboratory of University Col-lege Bristol. On the Volumes of some Compounds of the Benzene Naphthalene Anthmcene and Phenanthrene Chemistry in Yulwich College . . 1 (continued). By EDWAUD MORITZ . . 13 DAVIS F.C.S. . . 19 Cambridge . . 21 By RAPHAEL MELDOLA . . . . 37 MELDOLA . . 40 Manufacture of Bromine. the Yorkshire College Leeds . . 48 College Bristol: and Phosphorus at their Boiling Points. MASSON M.A. B.Sc. and W. RAMSAY Ph.D. . . 49 1X.-On the Specific Volume of Chloral. X.-On the Absorption Spectrum of Ozone.Science for Ireland Dublin . . . . 57 Series. By W. RAMSAY Ph.D. . . . 6 iv CONTENTS. XII1.-On the Atomic Volume of Nitrogen. By W. RAMSAY, Ph.D X1V.-On Pentathionic Acid. By VIVIAN LEWES Assistant in the Laboratories Royal Naval College . XV.-Contributions from the Laboratory of the University of T8ki6 Japan. No. IV. On Menthol or Peppermint Cam-phor. By M. MORIYA Graduate in Chemistry in the Uni-versity of T6ki6 . . XV1.-On the Position taken by the Nitro-group on Nitrating the Dibromotoluenes. By R. NEVILE and A. WINTHER . XVI1.-On Some Derivatives of Toluene and the Toluidines. XVII1.-On the Estimation of Nitrogen by Combustion includ-ing the Nitro-compounds. By JOHN RUFFLE M.R.A.C. &c. X1X.-On khe Estimation of Organic Carbon in Air. By A.DUPR~ Ph.D. F.R.S. Lecturer on Chemistry at West-minster Hospital and H. WILSON HAKE Ph.D. F.C.S., Lecturer on Chemistry and Physics at Queenswood Col-lege Hants . . XX.-On the Action of the Copper-zinc Couple upon Nitrates, and the Estimation of Nitric Acid in Water Analysis. By M. WHITLEY WILLIAMS . =I.-On the Absorption of Solar Rays by Atmospheric Ozone. By W. N. HARTLEY F.R.S.E. &c. Professor of Chemistry, Royal College of Science for Ireland Dublin. (Part I) . XXI1.-On the Synthetical Production of Ammonia by the Combination of Hydrogen and Nitrogen in presence of Heated Spongy Platinum (Preliminary Notice). By GEORGE ST~LLINGFLEET JOHNSON King’s College London . XXII1.-On the Synthesis of Ammonia. By GEORGE STIL-LINGFLEET JOHNSON King’s College London.(Second XXIV.-Researches on the Laws of Substitution in the Naph-thalene Series. No. 1. By HENRY E. ARMSTRONG F.R.S., and N. C. GRAHAM . XXV.-The Action of Hydrochloric Acid on Ethylene Alcohol. By C. SCHORLEMMER F.R.S. . XXV1.-On the Estimation of Organic Carbon and Nitrogen in Water Analysis simultaneously with the Estimation of Xitric Acid. By M. WHITLEY WILLIAMS i . . XXVI1.-On a New Theory of the Conversion of Bar-iron into Steel by the Cementation Process. By R. SYDNEY MARSDEN, XXVII1.-Researches on the Relation between the Molecular Structure of Carbon Compounds and their Absorption By R. NEVILE and A. WINTHER . . . Notice) . . . . D.Sc. F.R.S.E. F.C.S. . . . PAOX 66 68 77 83 84 87 93 100 111 128 130 133 143 144 14 CONTENTS.Spestra. By W. N. HARTLEY F.R.S.E. &c. Professor of Chemistry Royal College of Science for Ireland Dublin . XX1X.-On Absorption-bands in the Visible Spectrum pro-duced by Certain Colourless Liquids. By w. J. RUSSELL, Ph.D. F.R.S. and W. LAPRAIK F.C.S. . By FRANCIS R. JAPP M.A. Ph.D., Demonstrator in the Chemical Research Laboratory Science Schools South Kensington and C. COLBORNE GRAHAM, A.I.C. XXX.-On P-Diquinolyline. Anniversary Meeting. . . . XXX1.-Volume of Mixed Liquids. By FREDERICK D. BROWN, B.Sc. Demonstrator in Chemistry at the University Museum, Oxford . XXXI1.-On Boron Hydride. By FRANCIS JONES F.R.S.E., and R. L. TAYLOR . XXXIIL-On the Action of Benzoic Acid on Naphthaquinone. By FRANCIS R. JAPP M.A. Ph.D.Demonstrator in the Chemical Research Laboratory Science Schools South Kensington and N. H. J. MILLER XXX1V.-On the Action of Aldehydes on Phenanthraquinone in Presence of Ammonia. (Second Notice.) By FRANCIS R. JAPP M.A. Ph.D. Demonstrator in the Chemical Research Laboratory Science Schools South Kensington and EDGAR WILCOCK . XXXV.-Note on the Appearance of Nitrous Acid during the Evaporation of Water. By ROBERT WARINGTON . . XXXV1.-Note on Usnic Acid and Some Products of its De-composition. By the late J. STENHOUSE F.R.S. and CHARLES E. GROVES . XXXVI1.-Note on the Sweet Principle of Smilax GZycyphyZEa. By C. R. ALDER WRIGHT D.Sc. (Lond.) Lecturer on Chemistry ard E. H. RENNIE B.Sc. (Lond.) M.A. (Sydney) Demonstrator in Chemistry in St. Mary’s Hos-pital Medical School .XXXVII1.-Contributions from the Laboratory of the Royal College of Chemistry Science Schools South Kensington. On New Zealand Kauri Gum. By EDWARD H. RENNIE M.A. (Sydney) B.Sc. (Lond.) . By RICHARD COWPER F.C.S. Assoc. R.S.M. Demonstrator of Chemistry Royal Naval College . XL.-On the Action of Bacteria on Gases. By FRANK HATTON . XL1.-On the Oxidation of Organic Matter in Water by Filtration through Various; Media and on the Reduction of Nitrates . XXX1X.-On the Action of Alcohol on Mercuric Nitrate. . V PAQE 153 168 174 177 202 213 220 225 229 234 237 240 242 247 by Siwage Spongy Iron and other Agents. HATTON . . 258 By FRAN Vi CONTENTS. PAGE XL1I.-On the Modern Development of Faraday's Conception XLII1.-On the Distillation of Mixtures of Carbon Disulphide and Carbon Tetrachloride.By FREDERICK D. BROWN B.Sc., Demonstrator of Chemistry in the University Museum, Oxford . . 304 XL1V.-Contributions from the Laboratory of the Royal College of Chemistry South Kensington. On the Reduction of Cinnylic Alcohol. By FRANK HATTOW and W. R. HODGKIN-S O N . . 319 XLV.-Organic Matter in Sea-Water. By WILLIAM JAGO . 320 XLVI.-On the Action of Compounds inimical to Bacterial Life. By WILLIAM M. HAMLET . . 326 XLVI1.-On the Amylamines Corresponding to the Active and Inactive Alcohols of Fermentation. By R. T. PLINPTON, Ph.D 331 XLVII1.-On the Products of the Action of Alkalis on Ethylic ,&Ethylaceto - succinate. By LEONARD TEMPLE THORNE, Ph.D.(late Jodrell Scholar) . . 336 XL1X.-On the Action of Sodium Alcoholates on Fumaric Ethers. By T. RURDIE B.Sc. Ph.D. . . 344 L.-On Ammonium Nitrite and the Reaction between Hydrogen and Nitric Oxide in presence of Spongy Platinum. By LEWIS T. WRIGHT . . 357 L1.-On the Colour Properties and Colour Relations of the Metals of the Iron-Copper Group. By THOMAS BAYLEY . 362 LI1.-Action of Humic Acid on Atmospheric Nitrogen. By E. W. PR~EVOST Ph.D. . . 370 LII1.-Experimental Researches on the Amalgamation of Silver L1V.-On Potable Waters. (Part 11.) Determination of Total LV.-Chemical Examination of the Ruxton Thermal Water. LV1.-Modified Form of Apparatus for Collecting the Gases LVI1.-On the Sulphides of Copper. By SPENCER UMFREVILLE PICICERING; B.A. Oxon Assistant Master at Highgate School ; Lecturer in Chemistfry at the Bedford College .401 LVII1.-On the Isomeric Acids obtained from Coumarin and the Ethers of Hydride of Salicyl. By W. H. PERKIN F.R.S. 409 L1X.-The Alkaloids of Nux Vomica. By W. A. SHENSTONE . 453 LX.-On the Estimation of the Value of Zinc Powder and on a Gauge for Measuring the Volume of Gases without Calcula-tion for Temperature and Pressure. By JOSEPH BAILKES . 462 of Electricity. By Professor HELMHOLTZ . . 277 Ores. By C. RAMMELSBERG. . . 374 Solids. By EDMUND J. MILLS D.Sc. F.R.S. . . 385 By J. C. THRESH B.Sc. . . 388 Dissolved in Water. By J. C. THRESH B.Sc. . . 39 CONTENTS. vii PAGE LXL-On the Synthesis of a-Isoheptane. By THOMAS PERDIE, B.Sc. Ph.D. . . 464 LXII.-Contributions from the Laboratory of the Royal College of Chemistry.On a New Derivative of Quinine. By RDWARD H. RENNIE M.A. (Sydney) B.Sc. (London) . 469 LXII.1.-On the Synthetical Production of Urea from Benzene, Ammonia and Air by the Action of Heated Platinum. By E. F. HERBOUN Daniel1 Scholar of King’s College, London . . 471 LX1V.-The Effects of the Growth of Plants on the amount of Matter removed from the Soil by Rain. By E. W. PREVOST Ph.D. . . 475 LXV.-Metallic Compounds containing Bivalent Hydrocarbon Radicles. Part 11. By J. SAKURAI F.C.S. . . 485 LXV1.-Note on the Formation of an Alcoholic Fluoride. By SYDNEY YOUNG B.Sc. Student in the Laboratory of Owens College Manchester . - 489 LXVI1.-Contributions to the History of the Mineral Waters of Yorkshire.From the Laboratory of the Porkshire College. LXVII1.-Fractional Distillation with a Still-head of Uniform Temperature. By FREDERICK D. BROWN B.Sc. Demonstrator of Chemistry in the University Museum Oxford . . 517 LX1X.-On the Action of Oxides on Salts. Part 111. By EDMUND J. MILLS D.Sc. F.R.S. and C. W. MEANWELL . 533 LXX.-On the Action of Tertiary Amines upon Acetylene Di-bromide. By R. T. PLIMPTON Ph.D. . . 536 LXX1.-Suberone. By R. S. DALE B.A. and C. SCHORLEMMER, F.R.S. . . 539 LXX1I.-On Dimethylmalonic Acid and Dimethylbarbituric Acid. By L. T. THORNE Ph.D. . 543 LXXII1.-On Phenylnaphthalene. By WATSON SMITH Demon-strator and Assistant Lecturer in Chemistry in the Owens College and T. TAKAMATSU . . . 546 LXX1V.-Sulphonic Acids derived from Isodinaphthyl (PS-Dinaphthyl). By WATSON SMITH Demonstrator and Assistant Lecturer in Chemistry in the Owens College and T. TAKAMATSU . . 551 LXXV.-On Citraconic and Mesaconic Ethers and Maleic and Communicated by T. E. THORPE Ph.D. F.R.S. . . 497 Fumaric Acids. By W. H. PERKTN F.R.S. . . 55

ISSN:0368-1645    

DOI:10.1039/CT88139FP001

出版商:RSC    

年代:1881

数据来源: RSC

摘要:

13 11.-Synthetical Production of New Acids of the Pyruvic Series. (Continued.) By EDWARD MORITZ. PART 11. liobutyryl- and Butyryl-formic Acids. IN accordance with my intentions I have applied the reactions which I used for the preparation of propionylformic acid to the formation of higher acids of the same series. Before starting the regular work I endeavoured to hit upon a better method for preparing the cyanide and in doing so I obtained a very fair yield by heating 50 grams of silver cyanide with 40 grams of isobutyryl chloride on an oil-bath for about three-quarters of an hour and as this lightened the work considerably I preferred to use this modification of the method to the old one. However when I had used up all my substance (about 400 grams) I found on fractioning the crude product that I only obtained just about as much cyanide as the preliminary experiment yielded for which I had only used about 40 grams.Naturally there was none to spare for an analysis so I converted the 6 grams of cyanide into the amide. IsobutyryZformic Amide.- The amide was prepared exactly in the same way as has already been described. From the 6 grams of iso-butyryl cyanide I obtained about i2G gram of amide. It fuses at 125-126". One analysis made unfortunately came to grief. Di-isobutyry 1 Dicyanide.-In the preparation of the cyanide there was a vast qnantity of substance which boiled above 160". This was carefully fractioned and about 70 grams of nearly pure substance obtained. A small portion for analysis was then purified by repeated fractional distillation.It boils at 226-228". The following were the results obtained by analysis :-(1.) 0-195 gram substance gave 0.4442 gram CO and 0.1309 gram (2.) 0.2223 gram substance gave 0.5055 gram CO and 0.1487 gram Nitrogen determination 0.2091 gram sfibstance gave 0.209 gram Pt. I first experimented on isobutyryl compounds. The cyanide boils a t 117-120". H,O. H,O. Theory. Found. C,. . 60 61.8.5 (I) 62.12 62-01 H i . . . . . . . . . 7 7.21 7.45 7-42 N 14.1 3 - 14 14.43 0 16 16-51 97 100*00 - -- -. 14 MORITZ ON SYNTHETICAL PRODUCTION OF The vapour-densi ty determined according to Hofmann's method gave results which leave no doubt as Do its being a di-cyanide. The specific gravity of the liquid is 0.96. It does not solidify a t -15".It is intensely poisonous-traces of its vapour produce giddiness head-ache and nausea ; large quantities illness for several days. On being saponified with the theoretical quantity of hydrochloric acid (sp. gr. 1-22> in closed tubes it gave the amide of isobutyryl-formic acid agreeing approximately in melting point to the amide obtained from the monocyanide. The difference is caused by traces of polymeric cyanide from which it ca,nnot be purified by fractional sub-limation or by solution and crystallisation from ether. This admix-ture naturally lowers the melting point and increases the percentage of nitrogen so that an analysis of the amide for nitrogen came about 5-10 per cent. too high. 0.1734 gram substance gives 0.1562 gram Pt. Theory.Found. -A,- c H -N . . 14 12-17 12-77 . . . . . . . . . I101 87.83 02 J - .-115 100 Acid.-The acid was prepared in the following way -7i grams of the polymeric cyanide and 10 grams of hydrochloric acid (sp. gr. 1.22) were brought into a small stoppered bottle and left for two days. The mixture was then brought into a flask to which was now added 14 grams of hydrochloric acid (sp. gr. 1.1). The fluid was not homo-geneous. There were two distinct layers which did not mix with one another. Three or four other portions were treated in a similar way, and when all were prepared up to t'his point the whole was divided into two portions and each was boiled separately on the water-bath for about an hour after which each part was shaken up with ether. The ethereal solution after separation from the aqueous part by mechanical means was dried over calcium chloride the ether driven off and the residue fractioned in VCICUO.After the isobutyric acid had come over that portion was retained as the ketonic acid which boiled a t 85-95' a t the above-mentioned pres-sure. The thermometer was constant a t 92-93" ; 18 grams of liquid were obtained between these degrees. The product smelt strongly of isobutyric acid although B burnt smell (characteristic of ketone acid) was also perceptible. It was as will be seen by the analysis a mixture of isobut,yric and isobutyrylformic acids. Isobutyrio acid boils a t 68" at a pressure of 45 mm NEW ACIDS OF THE PYRUVIC SERIES. 15 The following are the analytical results :-(1.) 0.2829 gram substance gave 0.2215 gram H,O and 0.558 gram (2.) 0.2205 gram substance gave 0.1722 pam H,O and 0.4328 gram A third analysis was made by Dr.Claisen of which I append co,. co,. results :-Theoiy. Found. Ketonic I-- 7 r---- 7 acid. (1-1 (2.1 (3.) C5 . . . GO 51.72 53-79 53.52 53-53 H,. . . . . . . . . 8 6.9 8-69 8.68 8-60 0 3 . . . . 48 41.38 - - -- -116 100 f---Thpory. Isobutyric acid. 54.54 2 Ci 9.09 8 H* 36.37 32 0,. These results agree so closely that they leave little doubt as to tho mixture of the acids. A silver salt was prepared (indirectly from the calcium salt) which points to the same percentage composition of the mixture 0.2364 gram substance gave on ignition 0.1298 gram Ag. Ketonic acid Isobu ty ric salt.Theory. Found. Theory. acid salt. f-- -3 rd- 7 44-62 87 :,\I15 51-57 -03 J Ag 108 48.43 54.90 55.38 108 4 - -_ -- -223 1I!O 100 195 Nothing more could be done with the acid; its salts could not be separated from the corresponding salts of the fatty acid series nor could the acids be separated by fractional distillation. Two interesting bodies were obtained from the di-isobutyryl di-cyanide in the following way:-If in the preparation of the acid (from the polymeric cyanide) after the addition of the dilute hydro-chloric acid the mixture be not boiled but poured into cold water, oily drops form at the bottom which presently solidify. These oily drops cannot consist either of di-isobutyryl dicyanide or of isobutyric acid as both are lighter than water. If after complete solidification (which generally takes about two hours) the solid be filtered off an 16 MORITZ ON SYNTHETICAL PRODUCTION OF afterwards dried it will be found on further investigation that this white amorphous substance can be separated into two substances both white and amorphous.Both are nitrogenous but they are loth to give up their nitrogen ; no trace of ammonia can be perceived till they have been heated for some time in the solid state with dry soda-lime. They can be separated by their difference in solubility in sodium carbonate. The soluble one fuses at 1S7-1S8° the insoluble one at 207-208" ; i t is soluble however in sodium hydrate but is reprecipitated from its solution by carbonic acid. I could not investigate these substances any further as I had not sufficient of them nor had I sufficient polymeric cyanide left to prepare any more.They are both very light and voluminous substances and thus deceive one at first as to the quantity obtained. I now close this chapter and pass on to the normal butyryl com-pounds. This time I had recourse again to Huebner's preparation of the cyanide from the chloride. 750 grams of butyryl chloride were alto-gether used portions of 16 grams being heated up in closed tubes with 20 grams of silver cyanide. It was found best to first fill into the tube seven-eighths of the silver cyanide then to pour in the liquid by means of 5 thistle-funnel arid then to add the remaining silver cyanide after which the tube was immediately sealed. This arrange-ment causes the liquid and solid to come more into contact with each other than any other.After all the tubes had been heated up for the required time they were opened and the contents brought into six smali flasks which all fitted on to the same distilling appa,ratns. Ea,ch flask was then heated in turn on the sand-bath over a 15-flame Bunsen burner finishing with the free flame of an ordizary burner. The crude product so obtained was distilled up to 110" with Linne-mann's apparatus so as to effectually get rid of all prussic acid and undecomposed butyryl chloride ; after this an ordinary T-tube was substituted and the rest fractioned in the ordinary way. The crude product repeatedly fractioned gave about 40 grams of cyanide boiling between 133-140". When perfectly pure it boils at 133-137".I considered it unnecessary to analyse the cyanide. Butyryljiorrnic Amide.-6 grams of the cyanide mere saponified in the usual way for the preparation of the amide of which -& gram were obtained pure. It melts a t 105-106". The following are the analytical results :-0.1621 gram substance gave 0.3084 gram CO and 0.1185 gram Nitrogen estimation 0.188 gram substance gave 0.157 gram Pt. H,O NEW ACIDS OF THE PYRUVIC SERIES. 17 Theory. Found. r-- 7 Cs 60 52.1 7 51.88 Hg 9 7-77 8.12 N 14 12.17 11.84 0 3 . . . . . . 32 27.89 --115 100 Di-butyryl Di-cya.nide.-The residue in the preparation of the cyanide was fractioned again but instead of as usual getting a stable polymeric cyanide I only obtained 10 grams out of an exceptionally large quan-tity of residue.This is due to its unstability ; even below its boiling point it splits up into a number of decomposition products among others the monocyanide. When pure itboils at 232-235'. The following are the analytical results :-0.1855 gram substance gave 0.1328 gram H20 and 0.422 gram CO,, 0.1835 gram substance gave 0.1825 gram Pt-nitrogen determi-nation. Theory. Found. T-h,-C 60 61-82 61-88 H7 7 7-46 8.12 N 14 14.43 11.84 0 16 16.26 - -97 100 It will be noticed that in the last analyses the water comes excep-tionally high ; this was due to the extreme heat of the weather and to the fact that closed tubes were always used. Butyrylformic Acid.-36 grams of cyanide were used for the pre-paration of the acid and were divided into six portions.6 grams of the cyanide and 2 grams of hydrochloric acid (sp. gr. 1.22) were brought together in a small flask provided with a well-fitting cork and left to stand in iced water for some hours. When the mass had become apparently solid 2 grams more of the same hydrochloric acid were added. All the rest was treated in the same way and then 11 grams of hydrochloric acid of sp. gr. 1.1 were added to each por-tion. The whole contents of the six flasks were now divided into two portions and a little water added to each. Instead of boiling as had always been done before the acid was extracted at once with ether the ethereal solution separated dried over chloride of calcium, and the ether distilled off. The residue was now fractioned in vacuo.Pure butyric acid boils at 100" at a pressure of 82-84 mm. ; about 15" higher the ketonic acid comes over. It has a characteristic burnt VOL. XSSLX. 18 MORITZ ON SYNTHETICAL PRODUCTION ETC. ~mell but after standing for some days it gradually evolves a smell of butyric acid ; in fact it can be seen by the analyses that follow that it gradually becomes impure ; nevertheless it is moderately stable it can be distilled at the ordinary pressure with only partial decomposition ; it then boils at 180-185". I t was not pure enough to give by reduc-tion normal a-oxyvaleric acid. The following are the anaIytica1 results the fifth combustion being done 5y an assistant according to Kopper's method which gives the water more correctly than other methods :-(1.) 0.2199 gram substance gave 0.4179 gram C02 and 0.149 gram H,O.(2.) 0.1744 gram substance gave 0.335 gram COr and 0.1283 gram H,O. (3.) 0.2919 gram substance gave 0.576 gram CO and 0.2144 gram (4.) 0.175 gram substanee gave 0.3346 gram GO and 0.1275 gram The fourth analysis was with the substance distilled at the ordinary . HZO . H20. pressure. Theory. Pound. Eetonic c-h-> r--acid. (1.) (2.) (3.) (4.) c5.? C5 . . 60 61.72 51.83 52.3 53.81 52.14 52.55 H,. . . 8 6.9 7.53 8.17 8-16 8.08 7-3 03 48 41.38 - - - - - -116 100 Theory. 7-7 54.54 48 C4 9.09 8 H, 36.37 32 0 2 100 88 -This finishes my results on these ketonic acids. Certainly the higher the number in the series the more difficulty experienced in the prepa-ration of the corresponding cyanide amide and acid. What is essen-tially necessary to the success of furtiher investigations on the subject is an improved method for the preparation of the cyanides of the acid radicles. I may mention that some months ago a method of preparing the cyanides of substituted acid-radicle (trichloracetyl cyanide) was found which gives 75 per cent. of the theoretic. It consists in heating in an apparatus provided with an inverted condenser DAVIS ON THE ANCIENT ALUM WELL AT HARROGATE. 19 mixture of the bromide of the substituted acid radicle with the corresponding amount of mmcuric cyanide and then distilling off. I tried similar experiments with the acid-radicle bromides themselves, but obtained only negative results

ISSN:0368-1645    

DOI:10.1039/CT8813900013

出版商:RSC    

年代:1881

数据来源: RSC

摘要:

DAVIS ON THE ANCIENT ALUM WELL AT HARROGATE. 19 111.-The Ancient Alum Well at Harrogate. By R. HAYTON DAVIS F.C.S. DR. THOMAS GARNETT a physician in practice at Harrogate in the year 1791 and afterwards Professor of Chemistry at the Royal Institution, London in his treatise on “ The Mineral Waters of Harrogate,” mote as follows :-“ In one of the sulphur wells situated in the bog I have discovered alum and I suspect salited clay. In a chalybeate water near the road, and not far from the Crescent garden the iron is dissobed by the mnriatic acid.” Dr. Adam Ilunter a physician resident in Leeds in his book entitled “ The Waters of Harrogate and its Vicinity,” published in 1830 commenting upon these st:ttements says :-“ The reader will I believe look in vain for alum or muriate of iron in the waters referred to.” The discovery of ferrous chloride in! 1865 in one of the Zrrrogate Spas near the site indicated by Dr.Garnett and the substance of my paper this evening strongly support Dr. Garnett’s observations. So far back as 1733 lk. Thomas Short of Sheffield B.R.S. mentions an alum well in the bog-field at Harrogate describing its position the nature uf the ground and the experiments he made with the water. DT. Garnett referring to these observations says :-‘‘ From Dr. Short’s experiments it seems to have been a chalybeate water in which the iron is held in solution by the sdphuric acid;” then he adds “ I have found two or three springs of this kind in the bog very near some sulphur wells.” Since Dr. Garnett’s residence in Harrogate a period of 80 years elapsed and the existence of the alum well passed quite out of memory.It was not until 1870 when excavations were made in the bog-field €or the purpose of increasing the supply of sulphur-water that this aluminous water again came to light ; the excavation was afterwards deepened earthenware pipes were put down forming a well about 4 feet deep and 14 inches diameter where the water slowly collects. c 20 DAVIS ON THE ANCIENT ALUM WELL AT HARROOATE. This aluminous water is of a pale reddish-brown colour strongly acid to litmus and very astringent taste; after keeping a short time if Jxposed to the air a portion of the iron is precipitated as basic aul-phate and the protosulphate gradually changes into the ferric salt. The ground in its vicinity is strongly acid to litmus tastes austere, even after heavy and continuous rains ; depressions in the ground after a shower more particularly in summer are found filled with water corresponding in colour and taste with that in the well.Imniediately under the peaty soil in various places around the well there is a layer of deposit having a sulphur-yellow colour ; its appear-ance has no doubt given rise to the statements of Dr. Short and other old writers respecting the prodigious quantities of sulphur to be found in the locality. I find on examination it contains about 60 per cent. soluble in hydrochloric acid consisting of SO3 1460 FeaOt 29-82 Snd small quantities of Ca Mg Na &c. ; it bears a remarkable resemblance to two of the ferruginous deposits found in the neighbourhood of the Caspian Sea the analyses of which by A.Frenzel are published in the September number of the Journal of this Society. To revert to the alum well its position is remarkable in being almost surrounded by sulphur wells which circumstance together with the surface of the soil being so strongly impregnated with the con-stituents of the water strengthens the opinion that the water is of comparatively superficid origin and is continually produced by natural causes. The old deposits from the chalybeate waters situate on higher ground and the sulphur waters rising through the stratum of shale at a lower level appear to be the factors in the production of this remark-able water. The Ancient Alzlm Well at Harrogate. The Quantities are irt Graiflzs per Gallon. Xp. gr. 1OC3.43. Fe 47.59 Ferric sulphate. . Mg 11.47 Calcium ,. K . . 1.40 Magnesium , NH 0.59 Ammonium , SOa 265.44 Sodium chloride Cl 20.60 Silica SiO 3.27 394.70 A1 1424 Ferrous snlphate Ca 16-74 Aluminium sulphate ??a 13.36 Potassium , Total residue dried 360-380" 397.25 78.76 69.33 89.47 56-91 57.38 3.14 2-19 33.96 3.27 394.4

ISSN:0368-1645    

DOI:10.1039/CT8813900019

出版商:RSC    

年代:1881

数据来源: RSC

摘要:

21 IV.-CONTRIBUTIONS FROM THE LABORATORY OF GONVILLE AND CAIUS COLLEGE CAMBRIDGE. No. VII. On Bismuth nnd Bismuth Compounds. By M. M. PATTISON MUIR M.A. F.R.S.E. Caius’Prdector in Che-mistry; G. BERNARD HOFFMEISTER B.A. B.Sc. ; and C. E. ROBBS ; Scholars of Caius College Cambridge. PART 1.-On the Oxides and Hydrates of Bismuth. A SERIES of papers has been published in this Journal by one of us, on various compounds of bismuth. It is proposed now to study in more detail the chemical habitudes of groups of these compounde. §. Preparation of Oxides and Hydrated Oxides of Bismuth. A large amount of work on the oxides of bismuth has been pub-lished ; methods for preparing these salts are not yet however clearly established. Observers are all agreed as to the preparation of bismuthous oxide this forms the starting point in the preparation of the other oxides.1. Our experiments have convinced us that by boiling previously prepared bismuthous oxide with potash and alkaline hypochlorite it is very difficult if not impossible to obtain a pure oxide higher than bismnthous oxide (see Arppe Pogg. Ann. 64 237; and Schrader, A?miLZen 121 204). A brown substance is certainly produced but ana.1yses show that the composition is not homogeneous in one instance we found 91.5 in another 94.5 per cent. of bismuth. This brown substance does not lose weight until heated to 250” ; it does not, therefore contain bismuthic oxide. It dissolves slowly in strong nitric acid with evolution of oxygen ; it therefore contains an oxide higher than bismuthous oxide.We obtained from Messrs. Hopkin and Williams a black-brown powder labelled “ peroxide of bismuth,” which as Messrs. Hopkin and Williams kindly informed us was prepared “ by boiling oxide of bismuth with hypochlorite of soda containing a considerable excess of caustic soda.” This substance contained 85.67 per cent. of bismuth (mean of 85.5 and 85-85) 0.76 per cent. moisture and 1.5 per cent. sodium. The percentage of bismuth calculated on the dry salt free from soda amounted to 88.10 (Bi,04 requires 86.78 and Bi,O 89.75 per cent.). This salt when boiled for some hours with very dilute nitric acid became brown and was then free from soda. Dried a 22 MUIR HOFFMEISTER AND ROBBS ON BISMUTH 130° it now contained 82.46 per cent. bismuth (mean of 62-57 and 82*35) and 0.30 per cent.moisture. The original black " peroxide '' began to change colour and lose weight at 250-260'. It dissolved in hydrochloric acid with evolution of chlorine and in hot nitric acid with evolution of oxygen. We there-fore conclude that this substance although containing much hypobis-muthic oxide was not a pure salt. 2. In a paper by one of us the preparation of hypobismuthic oxide has been described (this Journal 1877 i 28); we have somewhat modified that method and have obtained good results. Bismuthous oxide is suspended in a large excess of potash solution of about 1-35 sp. gr. ; the potash is kept nearly boiling and chlorine is passed in until the precipitate is homogeneous and of a dark chocolate-red colour ; the precipitate is washed free from potash with hot water kept in contact with dilute nitric acid (about 1 acid to 20 water) for 12 or 16 hours, until the colour of the solid has changed to brownish-yellow washed free from acid boiled for about an hour with a strong solution of sodium or calcium hypochlorite (preferably the former) till a per-fectly homogeneous yellow-brown heavy powder is produced which settles readily.This is washed with hot water till free from chlorine and alkali and dried at 180-200" for two or three hours. A specimen thus prepared contained 86.81 per cent. of bismuth (mean of 86-59 and 87-08) and lost 3.17 per cent. when converted into bismuthous oxide by heating. Bi,Oa requires 86.78 per cent. bismuth and loses 3.30 per cent. on heating. The prolonged digestion with nitric acid serves to dissolve any bismuthous oxide which may have escaped oxidation and also to deoxidise the bismuthic oxide which has been formed ; subsequent treatment with alkaline hypochlorite appears to convert any traces of bksmuthous oxide yet present into hypobismuthic oxide.: 3.The foUowing method of procedure yields pnre bismuthic oxide : -Bismuthous oxide is suspended in a large excess of very concentrated potash solution; specific gravity 1.37 to 1.38. The liquid is kept nearly boiling and chlorine is passed in until the precipitate is quite homogeneous and of a dark-red colour ; the precipitate is then washed with hot water until free from potash and then with cold water, until every trace of chloride is removed ; if any chloride is allowed to remain it is decomposed by the nitric acid subsequently added with formation of hydrochloric acid which acts on the bismuthic oxide ; it is then boiled for a very few minutes with concentrated nitric acid (whereby any remaining bismuthous or hypobismuthic oxide is removed) until all is distinctly scarlet washed repeatedly and quickly with boiling dilute nitric acid each quantity of acid being more dilute Its specific gravity was 6.77 AND BISMUTH COMPOUNDS.23 than the preceding and finally the acid is completely removed by washing with cold water ; the scarlet precipitate is then dried at 125" for three or four hours. A specimen thus prepared contained 83.87 per cent. bismuth (BizOa requires 84.0 per cent.). Heintz (Pogg. Ann,. 63 559) recommends it method of preparation very similar to the above.Arppe states that anhydrous bismnthic oxide is obtained by the action of chlorine on bis-muthous oxide suspended in moderade excess of strong potash solution. We have however failed (as Schrader did) to obtain the oxide by this process the product being always a hydrated oxide or mixture of hydrated oxides. Arppe does not state the temperature or conditions under which the salt which he obtained was dried. We have attempted but without success to prepare oxides inter-mediate between bismuthic and hypobismuthic oxide (see Arppe loc. 4. No hydrates of hypobismuthons oxide are known with certainty. Facts will be mentioned in the sequel which seem best explained by supposing that hydrates of this oxide are really formed during the oxidation of the oxide in presence of water.About 0.5 gram of moist hypobismuthic oxide prepared as described in par. 2 was placed over sulphuric acid for 1 2 hours ; it then lost 6.5 per cent. on heating to 190-200'; a portion of the same sub-stance dried at 100") lost 6.9 per cent. at 200". The salt contained 81.16 per cent. bismuth. Bi2O4.2H?O requires 80*7!3 per cent. bismuth, and 6.92 per cent. water. Thus the dihydrate Bi204.2H20 is produced by drying the product of the oxidation of bismuthous oxide under the conditions stated in par. 2 over sulphuric acid or at 100". A similar result was obtained by Schrader (loc. cit.). Another specimen after drying at 110" lost 4.5 per cent. at 200", which is rather more than the loss required by the monohydrate, BizOa.H20 viz.3.59 per cent. One of us has described the monohydrate Bi,04.H20 prepared by the action of chlorine in presence of aqueous potash on bismuthous oxide (this Journal 1877 i 28). The greater part of the hydrated oxide now prepared was a product of the deoxidation of Biz05.zH20. It would appear that hrpobismuthic dihydrate is produced by the deoxi-dation of hydrates of bismuthic oxide in presence of water and hypo-bismuthic monohydrate by the oxidation of bismbthous oxide in presence of water and under special conditions of concentration of potash, amount of chlorine used &c. ; probably if the hydrate Bi,O~.H,O be formed ah an early stage of the process the oxidised product is Biz04.Hz0 ; if Bi,O3.2H2O be produced oxidation results in the forma-tion of Bi,0,.4H20 (see paragraphs 8 and 9).cit.) 24 MUIR HOFFMEISTER AND ROBBS ON BISMUTH About 0.25 gram of hypobismuthic oxide was exposed to the action of ordinary and of moist air with the following results:-€lpobisnzzcthic 0x;iole. Gained 0.92 p. c. in 70 hours Gained 8.98 p. c. in 70 hours ) 1-30 7 140 ,? , 9-58 ) 140 ,, ,? 2-19 9 210 Y , 10-23 ,) 210 ,, 9 9 2-81 9 9 280 , ,) 10.23 , 280 ,, In air. Over water. Biz04 to Bi204.H20 requires 3.72 per cent. Bi204 to Bi204.2Eo requires 7-44 per cent. In ordinary air the monohydrate is therefore slowly produced ; but in moist air the oxide quickly passes into the dihydrate and goes towards the trihydrate but before this is completely reached deoxida-tion begins (see paragraphs 8 and 9).5. The following results show the rate of hydration of bismuthous oxide ; About 0.35 gram was used. Bi20a to Bi2/3,.3H,0 requirm 11.16 per cent. Bisrnzdhous Oceide. Gained 0.15 p. c. in 24 hours Gained 1.83 p. c. in 24 hours Y ? 0.30 9 70 9 , 1.83 ,) 70 ,* 9 9 0.30 , 140 1 , 1.98 , 140 ,, This oxide does not therefore take up a single molecule of water of hydration in moist air even after six days' exposure ; in ordinary air only traces of water probably hygroscopic are assumed. The hydrates of this oxide are it is well known easily dehydrated ; boiling with potash or heating to a temperature below loo" suffices to render these compounds anhydrous. 6. A quantity of moist bismuthic oxide prepared as described in par. 3 after drying over sulphuric acid for seven days lost 5.53 per cent.at 125" ; after four days' further drying it lost 3.47 per cent., and contained 80.81 per cent. bismuth. Bi,05.H,0 requires 81-08 per cent. bismuth and 3.47 per cent. water. The salt was therefore bis-muthic monohydrate. The rate of hydration of bismnthic oxide is shown by the following numbers ; about 0.5 gram was used :-In air. Over water. Bimzcthic Owide. Qained 0.79 p. c. in 70 hours Gained 3.36 p. c. in 70 hours In air. Over water. ,' 1.09 , 140 , 9 3-92 ,? '140 9 9 , 1.42 , 210 , n 4 . a Y? 210 Y AND BISMUTH COMPOUNDS. 25 The monohydrate Bi205.HP0 is therefore quickly produced in moist air but the hydration scarcely proceeds fnrther ; in ordinary air on the other hand even after nine days the oxide is only partially con-verted into the monohydrate.Bismuthic oxide therefore undergoes hydration rather less readily than hypobismuthic oxide ; the hydration does not extend beyond a single molecule of water. Bismuthic monohydrate also parts with its water of hydration at a lower temperature (125-130") than that at which hypobismuthic dihydrate is rendered anhydrous (160"). When bismuthic oxide is repeatedly moistened with water and allowed to remain in the air or when it is placed in contact with a large excess of water it undergoes deoxidation with production of it noticeable quantity of the white hydrate Bi203.2H20 and also of a, hydrate or hydrates of Bi204. The brown oxide BizO4 after taking up rather more water than required to convert it into Bi20a.2H20 began to appear whitish st the edges and to lose weight slightly; showing that deoxidation was com-mencing.Arppe (Zoc. d.) states that bismuthic oxide does not take up water directly but is converted into the monohydrate by the action of chlorine in presence of potash. Our experiments we think show that when exposed to moist air this oxide does become hydrated ; but inasmuch as t h e moist hydrate readily undergoes deoxidation the best method of preparing the monohydrate is undoubtedly to proceed as described in par. 3 and to dry the product over snlphuric mid. 7. Boedeker (AnnuZen 123 61) describes a brown salt to which he gives the formula BL05.2H,0 prepared by the action of potassium cyanide on bismuth-n=iPate solktion. We have prepared Boedeker's salt and analysed it with results which agree fairly with the formula Bi205.2H20.The properties of this salt are however so peculiar that a fuller account of it is reserved for a future communication. 6. Properties of @ides a?td 3ydrates of Bismuth. 8. When moist hypobismnthous oxide is exposed in air it rapidly undergoes oxidation to the white hydrate Bi20,.2HZO ; when the dry salt is moistened with water and exposed in air oxidation proceeds much more slowly. V e explain these facts by supposing that hydrates of hypobismuthous oxide are produced during the drying of the moist substance and that in the oxidation of the dried oxide in presence of water formation of a hydrate of Bi202 precedes that of the hydrate Bi203.2H20. An attempt to dry hypobismuthous oxide by heating in a current of carbonic anhydride did not give satisfactory results 26 MUIR HOFFMEISTER AND ROBBS ON BISMUTH Hypobismuthous oxide when kept in a stoppered bottle very slowly passes into the white hydrate already mentioned.A quantity of the oxide so kept for three years had suffered oxidation to the extent of about 10 per cent. The passage of Bi202 to Bi203.2H20 is attended with the evolution of a considerable quantity of heat ; the oxidising substance is sensibly warm tu the touch. It has been already mentioned that bismuthic and hgpobismuthic oxides or t'he hydrates of these oxides are partly deoxidised in pre-sence of an excess of water with production of Bi,03.2H,0. The deoxidation especially of Biz05.xH20 is hastened by the action of direct sunlight.If a few drops of nitric acid be added to the water less deoxidation apparently occurs hut this seeming decrease is due to the solvent action exerted by the acid on the hydrates of bismuthons oxide which are produced. 9. The first product of the action of nitric acid on bismuthic oxide or hydrate is the hydrate BizO4.2H2O (Schrader) this has been fully confirmed. Thus a quantity of Biz06.H20 was boiled with 1 1 nitric acid until all was of an orange-red colour the residue was washed and dried at 160". The brown salt thus produced contained 87.11 per cent. of bismuth and began to give off oxygen at 230". Bi204 requires 86.78 per cent. bismuth. Very dilute nitric acid does not, however bring about this change unless the time of action be very prolonged Two portions about 5 grams each of pure Bi205.H,0 boiled with 100 C.C.water and 6 to 10 drops concentrated nitric acid, did not change colour the residues when washed and dried over sul-phuric acid contained 81.47 and 82.2 per cent. bismuth respectively, and 5-50 and 3.30 per cent. water. Bi206.Hz0 requires 81-08 per cent. bismuth and 3.47 per cent. water. That dilute nitric acid exerts no oxidising action on hypobismuthic oxide is evident from the fact that portions of this oxide were not visibly changed when boiled with exceedingly dilute nitric acid and that the residues dried at 160" contained 87.1 per cent. and 86.9 per cent. bismuth respectively. Bi20a requires 86.78 per cent. Somewhat more concentrated acid exerts a visible deoxidising action on Bi,O : this oxide dissolves in concentrated nitric acid and more slowlyin concentrated sulphuric acid with evolution of oxygen and in hydro-chloric acid with evolution of chlorine.Hypobismuthous oxide is rapidly oxidised to the white hydrate of bismuthous oxide by a few drops of nitric acid; addition of a little more acid dissolves the hydrate formed ; if a moderate quantity of acid be added directly to the oxide part of it goes into solution as nitrate and metallic bismuth simultaneously separates ; 3Bi202 + 12HN03 = 2Biz.6NOs + Bi + 6H20 AND BISMUTH COMPOUNDS. 27 When hypohismuthous oxide was warmed with aqueous potassium permanganate either alone or in presence of potash the permanganate was reduced to manganate and a dark brownish-red heavy substance was formed which after washing dissolved slowly in concentrated nitric acid with evolution of oxygen showing it to be Bi,04 or more probably a mixture of this oxide and Bi,Os.Bismuthous oxide was not oxidised by boiling with aqueous permanganate ; when potash was added and boiling was continued for some time there was a very slight production of a higher oxide. 10. Arppe (Zoc. cit.) states that a red liquid resembling dilute potassium permanganate solution and containing bismuth and potas-sium is obtained by boiling bismuthic hydrate with potash. Heintz (Pogg. Ann. 63 559) says that Arppe conducted experi-ments in his presence and that he obtained a liquid with a faint shade of green and containing only traces of bismuth. We have altogether failed to effect any change either in bismuthic or hypobismuthic hydrate by long-continued boiling with potash solu-tion ; the potash was all removable by washing with water.In the preparation of these hydrates (by the action of chlorine on bismuthous oxide in potash) a red liquid is certainly produced and if hydrochloric acid is added to this liquid a reddish-white precipitate, containing bismuth and potassium slowly separates. But we find that the colour of this liquid is due to small quantities of hydrates of the higher oxides suspended therein in au extremely finely divided state ; if the red liquid be filtered through good paper the filtrate is colourless and contains neither bismuth nor potassium. We think that Arppe's so-called " potassium bismuthate" was a mixture of potash and hydrates of Bi,O and BizO5 obtained from this liquid.11. Some details of the action of heat on various oxides of bismuth have been already given in previous papers. The following results concerning this action and also the action of oxygen hydrogen and carbon monoxide show the reciprocal stabilities of the oxides of this element :-In each experiment about 0.5 grant of the oxide was placed in a test-tube carrying a cork and two tubes one to deliver the other to carry off the gas ; the test-tubes were heated in a water- paraffin- or air-bath ; the temperatures are approximate only and may be regarded as correct within 5". The test-tube and its contents were weighed at the end of each period noted in the tables ; the course of reduction was therefore discontinuous.Oxygen was purified by passing through potash and then through boiled sulphuric acid ; hydrogen by passing successively through pumice soaked in potash and in silver nitrate and finally through boiled eulphuric acid ; carbon monoxide was stored in a gas-holder and passe 28 MUIR HOFFMEISTER AND ROBBS ON BISMUTH through potash and boiled sulphuric acid before use. The gases were passed at approximately the same rate in each experiment ; no special device was however adopted. The temperature of initial action of carbon monoxide was determined by the met,hod described by Wright (this Journal Trans. 1878 1). Heating in air was conducted with the same arrangement of tubes, lint 12.0 current of air was passed over the heated oxides. Hypo bismuth ous Oxide.On account of the difficulty of obtaining this salt perfectly free from bismuthous oxide and hydrates we have only a few results to offer. It has been previously shown that this oxide when heated in an open vessel in air begins to absorb oxygen at 180" (this Journal, 1877 ii 136) ; we find that oxidation begins in oxygen at about lM", and is complete at 240" after ten minutes' heating ; that reduction begins and is rapidly completed in hydrogen at 300-310" and begins in carbon monoxide at about 250". Bis mu t hous Oxide. I. Temperature of Initial Action of Carbon Monoxide (about 0.5 gram taken). Temp. Time in mins. Turbidity in baryta-water. 100" 4 none 150 4 none 200 4 very faint Reduction in carbon monoxide begins therefore at about 200'.11. Reduction in Hydrogen (0.553 gram taken). Temp. Time in mins. Loss in mgms. Percentage loss. 245" 15 4 0.72 255 10 1 0.18 300 10 8 1.45 Total loss = 2.35 per cent. Reduction to Bi,O is therefore not complete in hydrogen at 300" Appearance of residue at 300" was black-grey mixed with yellow Bismuthous oxide is not altered by heating in air or in oxygen. Bi203 to Bi20z loses 3.44 per cent. after 35 minutes' (discontinuous) action. specks AND BISMUTH COMPOUNDS. 29 Hypobisrnuthic Ozide. 111. Reduction in Carbon Monoxide (0.247 gram taken). Time in Turbidity in Loss in Percentage Temp. mins. baryta-water. mgrms. loss. - - 80" 4 none 90 4 none 95 4 none - --- 4 very faint - 100 4 decided - - 115 115 10 - 3.0 1.21 125 10 - 0.3 0.18 155 10 _ _ 1.2 0.50 175 10 - 1.5 0.60 205 10 - 0.5 0.20 225 10 - 0.5 0.20 245 10 - 0.5 0.20 Total loss = 3.03 per cent.Hypobismuthic oxide is almost wholly reduced to bismnthous oxide by heating in carbon monoxide at 245-250" ; reduction begins a t about 105". Bi20 to Bi203 loses 3.30 per cent. IV. Reduction in Hydrogen. No. 1. 0.459 gram taken. Temp. Time in mins. Loss in mgrms. Percentage loss. 21 5' 10 1-75 0.39 235 10 2.25 0.46 No. 2. 0.366 gram taken. 245" 10 4 1-09 255 10 1 0.27 265 10 21 5.74 Temp. Time in mias. Loss in mgrms. Percentage loss. Total loss (No. 2) = 7.10 per cent. Bi204 to Bi,O loses 6.61 per cent. Appearance of residue was black with a few greyish specks. Hypobismuthic oxide is therefore reduced to hypobismuthous oxide in hydrogen at about 265-270" after 30 minutes' (discontinuous) action but bismuthons oxide is not wholly reduced to the lower oxide in hydrogen even at 300".(See above Table 11. 30 MUIR HOFFMEISTER AND ROBBS ON BISMUTH V. Heating in Air. 0.2592 gram taken. Temp. 245" 2 55 265 275 285 295 305 315 325 Time in mins. 10 10 10 10 10 10 10 10 10 Loss in mgrms. 1.5 0.0 0.5 1.0 0.4 2.4 2.0 0.7 0.2 Percentage loss. 0.5 7 0.0 0.19 0-38 0.18 0.92 0.76 0.27 0.09 Total loss = 3.36 per cent. Hypobisrnuthic oxide is therefore reduced to bismuthous oxide by Bi,04 to Bi,O loses 3.30 per cent. heating in air to about 325". VI. Heating in Oxygen. 0.249 gram taken. Temp. 245" 255 265 275 285 295 305 Time in mins.Loss. in mgrms. 10 2-0 10 0 0 10 2.0 10 1.0 10 2.1 10 1.1 10 0-0 Perceutage loss, 0-8 0-0 0-4 0.9 0.5 0.0 0.8 Total loss = 3.4 per cent. Hypobismuthic oxide is therefore reduced to bismuthous oxide in a current of oxygen at about the same temperature as that at which it suffers reduction when heated in air. 0.30 gram heated at 100" for 15 minutes and then at 140' for 15 minutes in a slow current of ozonised oxygen underwent no change in appearance or in weight. Therefore this oxide is not oxidised by direct action of oxygen or of ozone. Heated t o 200" in oxygen no change of weight, Bimuthic Oxide. VII. Temperature of Initial Action of Carbon Monoxide (about 0.5 gram taken). Temp.Time in mins. Turbidity in baryta-water. 70" 4 very faint. 80 1 faint. Therefore reduction begins at about 75" AND BISMUTH COMPOUNDS. 31 VIII. Reduction in Hydrogen. 0.5875 gram taken. Temp. Time in mins. Loss in mgrms. Percentage loss. 105" 15 5.0 0.86 125 15 2.0 0-35 145 15 3.0 0.46 165 10 1.5 0.26 205 1.0 3.0 0.46 215 10 3.0 0.46 255 10 19.5 332 Total loss to 215" = 2.85 per cent. Bi,O to Bi2Od loses 3.2 per cent. Total loss = 6.17 per cent. Bi2O6 to Bi203 loses 6.4 per cent. Therefore bismuthic is almost wholly reduced to hypobismuthic oxide at about 215O and to bismuthous oxide at about 255" by heating in hydrogen. IX. Heating in Air. 0.5117 gram taken. Temp. Time in mins. LOSS in mgrms. Percentage loss. 135" 10 0.0 0.0 1'45 10 2.1 0-4 155 10 1.0 0.2 165 10 0.5 0.1 175 10 1.4 0.3 185 10 0.0 0.0 195 10 0.0 0.0 205 10 0.0 0.0 215 10 1.0 0.2 225 10 1.5 0.3 235 10 1.4 0-3 245 10 3.4 0.7 255 10 5.7 1.1 0.5545 gram taken.135" 10 0.5 0-1 145 1e 1.1 0.2 155 10 0.5 0.1 165 10 1.2 0.2 175 10 0.8 0.15 185 10 0.8 0.15 193 10 1.8 0.3 205 10 2.1 0.4 215 10 0.0 0.0 225 10 0-5 0-1 235 10 1.1 0.2 245 10 3.8 0.7 255 10 7.8 1.4 305 10 8-4 1.5 Total loss = 3.6 per cent. X. Heating in Oxygen. Temp. Time in mins. Loss in mgms. Percentage loss. Total loss to 255" = 4.0 per cent. Total loss = 5.5 per cent 32 MUJR HOFFMEISTER AND ROBBS ON THE Bismuthic oxide heated in air to about 250° or in a current of oxygen to about the same temperature is therefore reduced to'hypa-bismuthic oxide; heated in a current of oxygen to about 305" it is almost wholly reduced to bismuthous oxide.Heated in oxygen at 160" and at 200' under a pressure of '780 mm. bismuthic oxide suffered almost the same loss of weight as when heated under the ordinary pressure ; therefore an additional pressure of 20 mm. mercury did not impress upon the oxide any greater stability than is possessed by it at the ordinary pressure. 12. We thought it advisable to examine the action of chlorine and bromine on the oxides B&O and Bi,O,. One of us had previously found that chlorine acts on Biz03 to give BiCl, and bromine (when heated with the oxide) to give (BiO),,02Br7 (this Journal 1877, 1 24). The oxides were subjected to the action of dry chlorine and of dry carbonic anhydride charged with bromine vapour in hard glass tubes, Action began between chlorine and bismuthic oxide as soon as the oxide was gently warmed ; with bismuthous oxide action did not begin until a higher temperature was reached.Bromine did not act on either oxide so readily as chlorine ; no distinct difference could be noticed between the readiness with which the bromine acted on the higher and on the lower oxide. The main product of the action of chlorine on bis-muthous oxide was bismuthous chloride recognised by its general properties and by estimation of bismuth ; a very small quantity of the oxy-salt Bi3OZCl3 already described as the product of the action of air, or nitrogen trioxide on heated bismuthous chloride was also formed. In the case of bisinnthic oxide the products were the same but a relatively larger quantity of the oxychloride was obtained.Bromine reacted on both oxides to form bismuthous bromide and the oxy-bromide formerly described as produced by heating together bis-muthous oxide and liquid bromine viz. (BiOj 1102Br7. Relatively more of the oxybromide than of the oxychloride was obtained; the deoxidising action of bromine on bismuthous and bismuthic oxides is therefore not so complete under similar conditions as that of chlorine. 13. The following data are given as approximate only. The specific gravities were determined by weighing in pure benzene the specific gravity of which had been determined to be 0.881 (20') :-Specific gravity at 20' of-Bi,O . . . . = 5.60 referred to water at same temperature.Bi,O . . . . = 3-10 9 9 9 , Bi,Oa.HzO = 5.75 9 ?, Bi,04.2H2O = 5.80 7 7 7 HALOGEN COMPOUNDS OF BISMUTH. 33 PART 11.-On the Halogen Co?npounds of Bismuth. By M. M. PATTISON MIJIR G. BERRTARD HOFFXEISTER and C . E. ROBBS. 1. The only point with regard to the preparation of the chloride, bromide or iodide of bismuth which we save t o note is that bis-muthous iodide is very easily prepared in well-marked crystals by subliming together bismuth and iodine in proportions to form BiI,. Heintz prepared the salt by subliming the constituent elements in an atmosphere! of dry carbonic anhydride (Pogg. Ann. 63 55). A sample of the iodide prepared by the direct union of the elements contained 35 44 per cent bismuth (theory requires 35.53). A specimen prepared three years ago by Rammelsberg’s wet method, now contained 35.31 per cent.bismuth (mean of 35-77 and 34.85 per cent.) showing that no decomposition had occurred. An attempt was made to prepare Bi,Br4 by heating BiBrB in hydrogen; 0.5 gram of the salt lost only 3-6 per cent. at 220° at which temperature sublimation of the original bromide proceeded rapidly (BiBr to Bi2Br4 loses 17.7 per cent.). Bismnthous iodide was heated in hydrogen but no reduction occurred ; the salt sublimed in hard steel-grey crystals consisting of pure BiI,. One specimen contained 35-58 per cent,. bismuth ; another, which had been repeatedly sublimed in hydrogen 34.63 per cent. ; BiI requires 35.53 per cent. 2. The action of hydrofluoric acid on bismuthons oxide results, according to Berzelius in the productiqn of bismuth fluoride which is soluble in water and separates therefrom as a white powder.We heated bismuthous oxide with aqueous hydrofluoric acid in a platinum dish replacing the acid as it evaporated. When action had apparently ceased the liquid was decanted and evaporated on the water- bath ; we thus obtained a deliquescent crystalline greyish-white mass which after drying between filter-paper contained 62.5 per cent. bismuth. Another specimen prepared in this way but dried by warming over a low flame for 6-8 hours contained 65-37 per cent. bismuth (mean of 64.80 and 65.95 per cent.). BiF3.3HF requires 64.22 per cent. bismuth. Another quantity of the same substance was heated in a closed platinurn crucible till fumes of hydrofluoric acid were no longer evolved.The residue which was a distinctly crystalline grey, heavy powder contained 79.2 per cent. bismuth (mean of 80.4 79.0, and 76.1 per cent.). On boil-ing the deliquescent salt mentioned above with successive quantities of water a heavy white non-deliquescent powder was obtained which contained 86.50 per cent. bismuth; BiOF requires 85.71 per cent. BiF3 requires 78.65 per ccnt. bismuth. YOL. XXXIX. 34 MUIR HOFFMEISTER AND ROBBS ON THE The greater part of the bismuthous oxide which was acted on by bydrofluoric acid remained as a heavy colourless powder ; when this had been washed with cold water till the washings were nearly neutral and dried a t loo" it contained 73.72 per cent. bismuth (mean of 74.0 72.10 79-40 and 74-42 per cent.).BiOF.2HF requires 73-69 per cent. bismuth. When washing of the insoluble in hydrofluoric acid had been con-tinued with hot water till the washings were perfe~t~ly neut,ral-this required about 80 or 100 washings-the residual colourless powder dried at 100" contained 85.51 per cent. bismuth (mean of 85.70 and 85.31 per cent.). Bismuthic fluoride was also obtained in crystalline form by very strongly heating the double salt BiOF.2HF mentioned above in a closed platinum crucible for about an hour. Closely agreeing num-bers were obtained on analysis. Bismuth JcEuoride BiF3 is quite insoluble in and is unncted on by water is decomposed and dissolved by hot hydrochloric sulpliuric or nitric acid and is scarcely altered or volatilised by heating in an open platinum basin a t a full red heat.The double salt BiF3.2HF is slowly decomposed by cold more quickly by hot water with formation of BiOF.2HF. If a little free hydrofluoric acid be present in the wash water a considerable amount of bismuth goes into solution. The final product of the action of aqueous hydrofluoric acid on bis-mutlious oxide is bismuthyl fluoride ; bismuth fluoride is however, much more stable towards water and towards heat than any of the other halogen compounds of bismuth. 3. It has been before shown that bismnthous iodide is much more stable towards oxidising agents and towards water than the corre-sponding chloride or bromide (this Journal Trans. 1878 192). The results of the experiments to be described exhibit this greater stability.About 0.5 gram of bismuthous iodide was shaken up with cold water in the proportion of 3,000 mols. H,O to 1 mol. Bi13 for 30 and for 60 minutes when the solution was filtered and hydriodic acid determined in the filtrate :-BiI prepnred in Wet W q . BiOF requires 85.71 per cent. bismuth. Percentage decomposition after 30 minutes = 13.3 > Y 60 , = 24.3 BiI prepared in Dry Way. Percentage decomposition after 30 minutes = 17.4 7 9 9 9 60 , = 19.9 Gnder similar conditions BiC13 or BiRr, would be entirely decom-posed t o BiOCl or BiOBr. The complete decomposition into BiOI b HALOGEN COMPOUNDS OF BISMUTH. 35 heating with water of crystalline bismuthous iodide prepared '' in the dry way " is much less readily effected than the decomposition of the iodide prepared " in the wet way." The action of N,03 on bismuthous chloride and bromide has been shown to result in the production of the oxy-salts Bi302C13 and Bi,O,,Br respectively.About 5 grams of BiI (prepared in the wet way) were heated in 5t V-tube in a current of dry N,Oj (prepared by heating starch with nitric acid). Action began before the salt sublimed iodine was evolved and a crystalline sublimate which on examination and analysis proved to be Bi13 collected in the cold part of the tube and in a long attached exit-tube. About 0.3 gram (6.0 per cent. of the iodide used) of a red substance remained in the bend of the V-t,ube when the action was finished ;. this gave a slight red milki-ness when boiled with water but the greater part was nnacted on; it contained 56.50 per cent.bismubh; BiOI requires 59.50 per cent. Bismuthous iodide is evidently much less fully decomposed by N,O, than the corresponding chloride and bromide. The oxidised product of the action is BiOI which i s also produced by slowly subliming the iodide in air ; no tendency to form complex oxyiodides corresponding to or analogous with the complex oxychlorides or bromides appears to exist. When snlphur is heated with bismuthous chloride sulphobismuthyl chloride (BiSCl) is produced. Bismnthous bromide and sulphur were heated in a subliming vessel in molecular proportions ; much sulphur vapour was given off crystals of bismuthous bromide sublimed, and a reddish crystalline mass remained containing 47.44 per cent. bismuth and 51.30 per cent.bromine (mean of 4'7.17 and 47-60 and of 51-08 and 51.52 respectively) which does not differ much from the numbers required for BiBr, viz. bismuth 46.66 and bromine 53.53 per cent. The substance contained a little sulphur ; it was readily de-composed by water yielding a nearly white apparently crystalline body which contained 22.38 per cent. bromine and a little sulphur ; RiOBr requires 26.11 per cent. bromine. These results show that bismuthous bromide is scarcely decomposed by sublimation in contact with sulphur or if decomposed that the sulphobromide formed is again easily resolved into its constihent substances; hence BiSCl is a more stable salt than BiSBr if the latter exists. When bismuthons iodide and sulphur were heated together both substances sublimed unchanged ; sulphur-vaponr therefore has no action on vnpour of bismuthoiis iodide.The oxyhaloid salts of bismuth as is usually the case are more stable than the sulphohaloid salts. When dry sulphur dioxide is passed over hot bismuthous bromide no action ensues; it has been D 36 ON THE HALOGEN COMPOUNDS OF BISMUTH. before shown that neither is bismuthous chloride decomposed by this gas ; it seemed unnecessary to make m experiment with bismuthous iodide undoubtedly it would be unaltered by the action of hot sulphur dioxide. No action is exerted 'by dry carbonic anhydride on heated bismuthous bromide. 4. I t is stated in Roscoe and Scherlemmer's Chepni,dry that bisrnuthyl iodide when sublimed in air is resolved into a crystalline oxide.We find that only a very small quantity of this salt is decomposed with formation of Biz03 by heating even in an open vessel for some days. 5. Another attempt (see'this Journal 1877 2 136) was made but only with negative results to =prepare a chlorobromide of bismnth by passing carbonic anhydride charged with bromine vapour over hot bismuthous chloride contained in one bend of a W-tube the other limb being surrounded by x freezing mixture no action occurred the second limb contained liquid bromine only. 6. The final distribution of salts *hen bismuthous oxide is acted on by aqueous hydrochjoric acid has been shown by one of us (No. II of these " Contributions " j to be represented by the symbols on the right hand side of the equation-Biz03 + 2HC1 + zHzO = 2BiOCl + (a + 1)H20-We have now examined the distribution of salts which occurs when the same oxide is acted on by3aqueous hydriodic acid and find $bat it is not quite analogous to that just dwcribed ; the reaction may be for-mulated thns :-B&03 + 6HI + zH,O = 2BS3 + (x + 3)Hz0.If however x be made very large relatively to the amount of HI present if the temperature be raised or if the changing sjstem be exposed to the action of direct sunlight BiOI is produced. The reaction <which occurs when aqueous hydriodic acid is added to bismuthyl chloride on the one hand and aqueous $hydrochloric acid to bismuthyl iodide on the other may be thus expressed :-3RiOC1 + x E I 4- a'H20 = 2Bi13 + BiCI -t (a - 6)HI + (z' + 3)H,O. 4BiOIe + d3C1 + z'H20 = 3BiC13 + BiI + (z - 9)HC1 + HI + (a' + 4)HzO.The amount of change in a given t,ime in the first reaction may be greatly decreased by adding a 'large quantity of water whereby the BiCt is reconverted as soon as produced into BiOCl unless the value of x' be very large in this reaction little or no BiOI is produced. In the second reaction the course of the change may be modified b MELDOLA ON COLOURING-Mi%TTER.S FROM THE PHENOLS. 37 making X' very large ; the BiCl produced is thus partly decomposed, and a secondary reaction occurs between the BiOCl thus produced and HI set free in the primary change in accordance with the first of the two equations given above. The actions which occur between the components of a syst'em com-prising BiC13 BiI, BIOCl,.BiOI HC1 HI and HzO mols. is thus seen to be very complex ; the final equilibrium is conditioned chiefly by the relative quantities of the salts (largely the quantity of H20), and by the temperature inasmuch as BiI is more stable than BiCI, the iodide tends to be produced in relatively large quantities Thermal measuremeats would undoubtedly throw much light on these phe-nomeEa of equilibrium most probably the " heat of formation " of BiI is greater than that of RiC13 and the difference between the '* heats of formation " of BiCl and BiOCl greater than that between the " heats of formation " of BiI and RiQl. The specific gravities were determined by weighing in benzene :-7. The following numbers- are given as approximate only. Specific gravity of BiRr3 at 20" = 5.4 referred to water at 20". 9 9 5 BiOBr , = 6.7 > 9 9 7 7 ) 7 BiOCl , = 7.2 9 7 > ? Specific gravity of Bib is given in text-books as 4.56 and of BiC13 as 5-65

ISSN:0368-1645    

DOI:10.1039/CT8813900021

出版商:RSC    

年代:1881

数据来源: RSC

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MELDOLA ON COLOURING-MATTEM FROM THE PHENOLS. 37 V.-00n a New Class of Colburing-Matters from the Phenols. By RAPHAEL MELDOLA. I x a preliminary note published last year (Ber. 1379,2063) 1 pointed out the existence of a new class of bodies formed by the action of nitroso-dimethylaniline on phenols not containing a methyl-group. The mode of performing the reaction i.s described in the note referred t 0 and need not he here repeated. Preparation of Nit roso - dime t h y l m iliito. The following method of preparing this substance which is based on tJhe insolubility of the nitrate in alcohol will I think be found more advantageous than that of Baeyer and. Caro (Ber. 7 1074 809 and 963) especially in cases where large quantities are required as it dispenses with the use of amyl nitrite :-50 parts by weight of dimethylaniline are mixed with an equa 38 MELDOLA ON A NEW CLASS OF weight of hydrochloric acid and 200 parts of alcohol the mixture being well cooled by immersing the vessel in iced water.A standard solution of sodium nitrite containing the necessary quantity of this salt is then gradually stirred in and the mixed solutions allowed to stand for about half an hour after which the theoretical quantity of nitric acid necessary to convert the nitroso-compound into nitrate is gradually poured in. The nitric acid must be diluted with its own volume of alcohol and cooled in ice before being added to the ot.her solution. In a shortl time the crystals of tlhe nitrate begin to separate out and in about 30 minutes the solution solidifies to a pasty mass, which must be collected on a vacuum-filter washed once or twice with alcohol and finally with alcohol-ether.The dried nitrate can easily be converted into the free base in the usual manner by agitating with dilute NaHO and ether and separating the ethereal solution of the base. On distilling off the ether the nitroso-dimethylaniline is ob-tained in the usual form the yield being from 60 to 70 per cent. of the theoretical quantity. /%Naphthol Vio 1 et . Specimens of the hydrochloride of this substance prepared in the manner already described after purification by several crystallisations from alcohol gave the following results on analysis :-I. 0,5930 gram dried in vnci~o over H,SO gave 1.4987 gram CO, and 0.2943 gram H,O. 11.0.3160 gram gave 0.8042 gram C02 and 0.1525 H20. 111. 0.2158 gram gave 0*0968 AgC1. IV. 0.3324 gram gave 0.1518 AgC1. Theory. r--&-- -7 Theory for { &yz!& Cl,HS.HO,HCl. I. 11. 111. IT:. (Mean). Cis . . 216 69.12 68.92 63.40 - - 69.16 H I 7 1 7 5.44 5.51 5.35 - - . 5-43 N 28 8-96 0 16 5.12 c1 . . 35.5 11.36 - - 11.09 11-29 11.19 - - - - I - - c - --312-5 10040 These results show that when nitroso-dimethylaniline acts upon m phenol not containing the methyl-group the oxygen of the nitroso-group directsly attacks the aromatic nucleus of the phenol in accord-ance with the equation COLOURING-MATTERS FROM THE PHENOLS. 39 N<CH3 N<CH3 I cH3 I CH3 -. .- CsH4.N 0 + H,H,C,rpHO = C:sH4.N=CJ&.HO + HZO. @Naptho1 violet. The hydrochloride of p-naphthol violet forms large bronzy needles, readily soluble in hot water and alcohol and much resembling potas-sium permanganate in appearance.The aqueous solution has an in-tense violet colour which is changed t o a deep blue on adding an excess of strong sulphuric acid. The nitrate and sulphate form small bronzy-green needles. By the action of reducing agents a colourless leuco-base is obtained which I have been unable to isolate owing to the great readiness with which it oxidises a few minutes’ exposure to the air causing the regeneration of the violet colouring-matter. This leuco-Ease can howtver only have the formula-according to which two atoms of hydrogen are required for its pro-duction.* It is of theoretical interest to note that the leuco-bases of these colouring-matters may be considered as derivatives of diphenylamine, r1 apht h y 1- p hen yla mine 8 c .Thus-C,H,.NMe, N C1oH,.HO N { p { H N{S% { H C,H,.NMe2 N C,H,.HO Diphenylamine. Leuco-base of Naphthyl-phenyl- Leuco-base of phenol colour. amine. naphthol violet. Although p-naphthol violet possesses great intensity of colour when in solution it is not readily taken up by silk or wool and is not there-fore of much value as a dye-stuff. By properly adjusting the strength of the bath and using the acetate of the base it can how-ever be made to gradually dye these fabrics. It t h u s imparts to silk a dull violet colour and to wool a deep shade of indigo-blue. A strong solution of the colour (either aqueous or alcoholic) appears red * My friend Mr.R. J. Friswell at my request was good enough to co&m this stfatenlent by reducing B standard solution of the violet with stannous chloride. ‘l’he reaction did not readily take place in the cold but on adding the stannous chloride solution to that of the violet and boiling the latter after each additio,i, results were obtained which su5ciently accorded wi!h t!ie theory 40 MELDOLA ON NITROSO-b-NAPETHOLSULPHONIC ACID. by transmitted light and changes to violet on dilution. The cause of this dichroism will be seen on referring to the following absorption spectra :-1. 11. u'l gritill in GOu C.C. wtwr. 0.1 gram in 6,000 C.O. water. Solutim in tube 14 millim. in diameter. The free base can readily be obtained from [%naphthol violet by decomposiiig any of its salts with an alkaline carbonate when it is thrown down as a dark flocculent powder which dissolves in benzene with B red colour when dry but is not easily crystallisable. The hydrochloride is completely precipitated from its alcoholic solutioir by PtCI, the double salt forming microscopic bronzy crystals. The corresponding colours from phenol resorcinol and a-naphthol have been prepared but owing to the aificulty of obtaining them in a crystalline form their investigation is not yet completed

ISSN:0368-1645    

DOI:10.1039/CT8813900037

出版商:RSC    

年代:1881

数据来源: RSC

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40 MELDOLA ON NITROSO-b-NAPETHOLSULPHONIC ACID. VI.-On Nitroso-P-Nuphtholsulphonic Acid. By RAPHAEL MELDOLA. THE ideas which have prompted the investigation which has led to the discovery of this nitroso-sulphonic acid are briefly as follow :-The colouring-mat,ters described in the preceding paper are as already stated of but little value as dye-stuffs and it therefore became of interest t o investigate the derivatives of these bodies containing acid radicles it being uow well known that the tinctorial value of t3he “diazo-colours” is greatly increased by the introduction of one OF more such radicles into one or both of the aromatic nuclei linked together by the diazo-group. As the “@-naphthol violet” did not appear to readily form a sulphonic acid by the direct action of sulphu-ric acid upon it I was led to iuvestigate the action of nitrous acid upon the sulphonic acids of the naphthols with a view to producing by this means the nitroso-sulphonic acids which would furnish MELDQLA ON NITROSO-P-NAPHTHOLSULPHONIC ACID.4 1 means of forming bodies of the type of the ‘‘@naphthol violet ” containing the group HSOs. When a solution of sodium nitrite is mixed with a solution of a salt of P-naphtholsulphonic acid the two salts being in exact mole-cular proportions on adding dilute HC1 to the well-cooled mixture a solution of a deep orange colour is formed and no trace of nitrous gas is evolved. These facts led me to believe that some definite reac-tion had taken place and on adding t o the orange solution a large excess of caustic soda a green colour was produced and on stand-iiig in the cold for some time minute green needles of the sodium salt of nitroso-P-naphtholsulphonic acid separated out.The extreme solubility of this sodium salt in water the readiness with which it decomposes on evaporating the solution on a water-bath and the difficulty of isolating in a state of purity a substance requiring excess of caustic soda for its precipitation led me to seek for some other method of obtaining a salt fit for analjbis. This process which will be described later on is based upou the insolubility of the Ba or Ca salt of the new acid. The p-naphtholsulphonic acid employed in these experiments was prepared from commercial @-naphthol purified by distillation and crystallisation from toluene till it possessed a melting point of 122”.This @-naphthol was mixed with about 2-43 times its weight of strong sulphuric acid and heated on a water-bath for about half a2u hour. As the free acid was not required the contents of the flask were poured into a large bulk of water neutralised with milk of lime boiled and filtered. The calcium salt was then converted into the ammonium salt by decomposition with ammonium carbonate and filtering off the calcium carbonate. The filtrate on cooling de-posits a certain amount of thc ammonium salt and a further quantity can be obtained by evaporating t,he mother liquor. The ammonium salt was chosen because of the readiness with which it crjstallises, and the ease with which it can thus be obtained in a state of perfect purity.Ananzonium P-.naphtholsu~TLoiiate crystallises in long flat transparent prisms with pointed extremities or when a large bulk of the solution is allowed to cool slowly in large plates sometimes half an inch i n length. Analysis showed it to possess the formula C,,H,.HO.NH,SO,. At 2 4 O 100 parts of water dissolve nearly 3 parts of the salt. The latter is very stable and can be boiled with dilute sulphuric or hydro-chloric acid without parting with its ammonium group. Barium Nitroso-/3-Naphtholsdph.onate. To prepare this salt 16-18 parts of distilled water are poured upon One part of the finely powdered ammonium salt and a standard solu 42 MELDOLA ON NITROSO-P-NAPHTHOLSULPHONIC ACID. tion of sodium nitrjte added in the proportion of one molecule of the latter salt to one of the sulphonate.Dilute hydrochloric acid is then gradually poured into the well-cooled solution till it shows a strongly acid reaction and all the ammonium salt has dissolved. The deep orange solution is then made alkaline with ammonia and barium chloride fiolution added as long as a precipitate forms. The latter is collected on a filter where it remains as a bright green paste which is well washed first with cold and finally with boiling water till a few drops of the filtrate no longer give a crimson colour on the addition of dilute hydrochloric or sulphuric acid. Tho green paste is then transferred to a flask and agitated with dilute hydrochloric acid, which changes its colonr to orange and on standing for some time a heavy crystalline deposit settles down which is collected and washed with cold water.Both the green paste and orange crystals are barium salts of nitroso-P-naphtholsnlphonic acid and will be desig-nated by their respective colours. The orange salt may be purified by two or three crystallisatioiis from boiling water or in cases where there is much associated impurity the hot aqueous solution may be precipitated by ammonia and the green salt collected washed and again converted into the orange salt by dilute hydrochloric acid and recrystallised. Analyses of Orange Ba salt. I. 0.4944 gram dissolved in hot water and decomposed by K,SO* gave 0.1742 gram BaS04. 11. 0.5914 gram gave 0.2097 gram BaS04. 111. 0.3309 , 0.1168 7 9 IT;. 0.8440 gram fused with RHO and KNO gave 0.5852 gram BaS04.V. 0.36'75 gram fused as above gave 0.2670 gram RaS04. VI. 0.2951 gram dried at loo" burnt with lead chromate gave 0.0632 gram H,O (1 mol. of water of cryatallisation sub-tracted) and 0.3930 gram CO,. Water of Crystallisation,. VII. 0.7153 gram dried at loo" and heated in an air-bath t o 140-150° till the weight was constant lost 0.017 I gram H,O. VIII. 0,6453 gram treated as above lost 0.0168 gram HzO MELDOLA ON NITROSO-/3-NAPHTHOLSULPHOXIC ACID. 4 3 Theory. Found (mean). C Z 0 . . . . . . . . . . 240 36.41 36.32 H, . . . . . . . . 12 1.82 2-37 N,. 4.25 - . . . . . . . . . 28 Ole . . . . . . . . 160 24.30 S,. . . . . . . . . . 64 9.71 9.74 Ba . . . . . . . . 137 20- 78 20.76 H,O . . . . . . . . 18 2.73 2.49 659 100~00 --These results show tJhat the orange salt has the formula :-ClOH,.HO.NO. so3 >Ra H,O, C,,H,.HO .NO. SO A determination of Ba in a specimen of the anhydrous salt dried at 140-150" gave 21.33 per cent. ; theory requiring 21.37. The orange salt crystallises in large tufts of flattened needles with a golden lustre crystals nearly three-quarters of an inch long having sometimes been obt,ained by the slow crystallisation of a large bulk of the solution. It is but very sparingly soluble in cold water; a t 30" 100 parts of water dissolve about. two parts of the salt. The green Ba salt was prepared for ana,lysis by dissolving the orange salt in a considerable quantity of hot water and adding ammonia. The bright green bulky precipitate thus obtained wa,s seen under the microscope to consist of minute needle-shaped crystals.Analysis showed it to possess the formula :-C1,H5.NO< S03>Ba,2H20. 0 The action of. an alkali upon the orange salt is therefore represented by the equation :-(ClOH,.NO.HO.SOJ),Ba + NH4H0 = CloH5.NO<S03>Ba 0 + C1oH,.NO.HO.NH*SO3 + HZO. The ammonium nitroso-$naphtholsulphonate formed in this reaction is most obstinately retained by the green Ba salt so that for the purposes of analysis it was found necessary t o add sufficient BaCl to the ammoniacal iolution to decompose the whole of the ammonium salt present. The green salt is then collected and well washed with boiling water in which it is practically insoluble. Analysis of CSreen Ba Salt. I. 0.370 gram (di-ied a t looo) gave on decomposition with dilute H,SO1 0.2039 gram BaSO, 44 MELDOLA ON NITROSO-P-NAPHTHOLSULPHONIC ACID.11. 0.6156 gram fused with KHO and RNO gave 0.3396 gram 111. 0.3029 gram (dried a t 100') burnt wit,h lead chromate gave 0.3153 gram COz and 0.0422 gram H,O (water of crystal-lisation subtracted). BEI SOa. Water of Crystnllisution. IV. 0.5198 gram dried at loo" and in an air-bath to 240-250" till the weight was constant lost 0,0438 gram H20. V. 0.4056 gram treated as above lost 0.0354 gram H,O. Theory. Found. C1" 120 28.30 28.31, H5 . . . . . . . . 5 1.1 7 1.54 N 14 3.30 0,. . 80 18.88 S 32 7.55 7.3 7 Ba 137 32.31 32.37 2H2O . . . . . . 36 8-49 8.57 (mean) ---424 100.00 The wat,er of crystallisation is not given off completely till the salt is heated to the temperature mentioned above (240-250") when partial decomposition takes place but the weight remains constant a>s long as this temperature is not exceeded.Nitroso-P-naphtholsnlphonic acid thus forms two classes of salts represented by the green and orange Ba salts. In cases where large quantities of a salt of this acid are required calcium chloride can be used for precipitating the ammoniacal solntion of the acid after its first formation from ammonium P-naphtholsulphonate by the action of nitrous acid (NaNO and HCI). By decomposing a solution of the Ba salt with an equivalent quantity of €€,SO4 and evaporating the solution in a vacuum the free acid was obtained in microscopic orange nodular crystals extremely soluble in water and decomposed by heating to a very moderate temperature in a dry tube so that its melting point could not be determioed.Of the other salts of nitroso-6-naphtholsulphonic acid I hare pre-pared the following :-Silver anzrrionium (double) salt formed by adding AgNOa to a solution of the ammonium salt of nitroso-P-naphtholsulphonic acid in the presence of an excess of ammonia. Dull olive-green microscopic needles decomposed by boiling water. Analysis gave the formula :-CloH,.NO.NHaO.AgS03 + CloH,.NO.NH4O.NHISO + HZO MELDOLA ON NITROSO-P-NAPHTHOLSULPHONIC ACID. 45 Found 15-87' per cent. Ag 9.69 per cent. S ; theory 15.83 par cent. Ag 9-58 per cent. S. Magnesium salt formed by decomposing the orange Ba salt with an equivalent (2 mols.) of MgS04 and adding ammonia to filtrate.Dull orange needles moderately soluble in cold readily soluble in boiling, water. Analysis gave the formula :-Found 7.27 per cent. Mq 16.70 per cent. H,O; theory 7-29 per cent. Mg -16.41 per cent. H20. Water of crystallisation not given off till 250". Large scaly crystals doll green by reflected light orange by transmitted light. Modcmtely soluble i n cold water more readily soluble iu hot water. Analysis gave the formula :-Zinc salt formed i n the same manner as the Ng salt. Found 17.81 per cent. Zn 8.86 per cent. S. and 1462 per cent,. H,O ; theory 17.56 per cent. Zn 8.64 per cent. S 14.59 per cent. H,O. Water of crystallisation only given off completely at 280" with partial decomposition of the salt. Lead salt preeipitated on adding a solution of lead acetate to a solution of the sodium or ammonium salt of nitroso-6-naphtholsulphonic acid acidulated with acetic acid.Minute ochreous needles insoluble in boiling water. Analysis gave the formula :-C10H5.XO< gO,>Pb,H,O. Found 43.60 per cent. P b ; theory 43.48 per cent. Pb. No loss of water at 250". Copper 8aZts.-On adding a solution of CuSO4 to a solution of the free nitroso-sulphonic acid containing an excess of H2S04 a bulky brown gelatinous precipitate almost insoluble in boiling water, separates out. On suspending this gelatinous salt in cold water and adding ammonia a double copper-ammonium salt settles down aftor some hours in the form of small brown glistening scales. The consti-tution of this salt has not been determined. Analysis gave 17.92 per cent.Cu and 8.55 per cent. S. An attempt was made to prepare an acetyl derivative of nitroso-/3-naphtholsulphonic acid by acting upon the sodium salt of acetyl-(3-naphtliolsulphonic acid with sodium nitrite and dilute hydrochloric acid bui the acetyl-group appears to be eliminated in the course of the reaction as on adding ammonia and barium chloride the ordinar 46 MELDOLA ON NITROSO-&NAPHTHOLSULPHONIC ACID. green Ba salt was precipitated. An attlempt to prepare a nitroso-derivative of methyl-/3-naphthol in a similar manner was also unsuccessful. The nitroso-group is readily reducible by any reducing agent but I have not yet been able to obtain the corresponding nitro-sulphonic acid, either by the action of dilutIe nitric acid or of an alkaline solution of potassium ferricyanide the molecule apparently completely breaking up under the action of these reagents.On agitating a solution of the nitrososuIphonic acid with 1 mol. of bromine the lnttcr is absorbed, but no definitely crystalline brom-nitroso acid was separable. Nitroso-&naphtholsnlphonic acid is very easily decomposable. Cons fit ution of hi;ltroso-P-Nap h t holsu lp honk Acid. I have made numbers of experiments with a view to determine the constitiition of this acid. The free acid when repeatedly eva-porated with dilute nitric acid gave no phthnlic acid neither did the nitroso- nor amido-acids when oxidised with an alkaline solution of potassium permanganate. Phthalic acid was however obtained by repeatedly evaporating the nmido-acid wit.h dilute nitric acid.This result is of interest as showing that in nitroso- and amido-/3-naphthol-sulphonic acid all these substitnents are in the same benzene-ring. In their recently published monograph upon naphthalene Reverdin and Nolting (“ Ueber die Const’itution des Naphtalins und seiner Abkomm-linge,” Genf. 1880 p. 25) assign to B-naphtholsulphonic acid a formula in which the HSO3 and HO-groups are in different benzene-nuclei but no reasons are assigned for adopting this constitution. I n a communication t o this Society last November Armstrong gave reasons for believing that in this acid the two substituents are both in the same benzene-ring being in the two $-positions. Although I have made repeated attempts to confirm this view by oxidising 6-naphtholsulphonic acid with an alkaline solution of permangznate 1 have not succeeded in obtaining phthalic acid from this compound.The production of ph thalic acid however from amido-@-naphthol-sulphonic acid in the nianner above described goes to support Arm-strong’s view of the constitution of this sulphonic acid and shows that the nitroso-acid has the NO constitution :-N MELDOLA ON NITROSO-P-NAPHTHOLSULPHONIC ACID. 4 7 Among the reactions of nitroso-B-naphtholsulphonic acid which I have investigated the most interesting appears to be that with the phenols and certain primary and secondary monamines. The phenol or amine is dissolved in glacial acetic acid the finelypowdered barium or calcium salt of the nitroso-acid added and after the addition of a small quantity of sulphuric acid the mixture is warmed.The follow-ing colouring-matters have been obtained in this manner :-Resomii~.oZ and ordinaryphenoi! give a deep blue clianging to red on dilutim with water. Diphenylamine gives a similar blue which retains its colour on dilution but becomes red on neutmlising with an alkali. BenzyI-ol-rza~hthyzainine gives a fine red which is not changed by dilution. These bodies are probably built on the type of the @-naphthol-violet described in the last paper and containing HSO in the naphthalene-group. Their value as dyes does not appear however to be increased by the presence of the acid radicle. I hope to investigate these substances more fully at a future period. On mixing solxtions of ammonium nitroso-P-naphtholsulphonate and ammonium sulphite and allowing the mixture to stand for some hours in the cold white scaly crystals separate out which have not yet been further investigated.Anaido-P-naphthol.szc1phonic Acid. This acid was prepared by boiling a solution of the nitroso-acid with tin and hydrochloric acid removing the tin by sulphuretted h-ydrogen and evaporating the cold solution in a vacuum. The acid then separates out in the form of long white needles which after one or two washings with cold water are sufliciently pure for analysis :-0.2380 gram fused with KHO and KNO gave 0.2380 gram 0.4984 gram gave 0.4928 gram BaS04 = 13.57 per cent. S. BaSOd = 13.73 per cent. S. Theory for CloH5.NH2.H0.HS03. Found (mean). S . . . . . . . . . . 13-38 Its aqueous solution and especially that of its salts oxidises on exposure to the air and turns brown. A hot solution undergoes this change rapidly. The melting point of the acid could not be determined as it decomposes on heating. I n concluding this paper I may take the opportunity of announcing that I have recently succeeded in obtaining an iodine derivative of &naphthol by acting upon this substance dissolved in glacial acetic 13-65 Amido-P-naphtholsulphonic acid is readily soluble in water 48 HAMILTON ON THE FORMATION OF CARBON ETC. acid with iodine in the presence of lead acetate. I hope shortly to lay before the Society an account of this substance and some of its derivatives. It is also my pleasing duty to express my thanks to the firm of Brooke Simpson and Spiller in whose laboratory at the Atlas Woi.ks these investigations have been conducted

ISSN:0368-1645    

DOI:10.1039/CT8813900040

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年代:1881

数据来源: RSC

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48 HAMILTON ON THE FORMATION OF CARBON ETC. VlI.-Note on the Forn7ntion qf Carbon Tetrabromide iri the Manufacture of BronJne. By J. C. HAMILTON Student in the Porkshire College Leeds. A QUASTITY of a white crystalline substance which had been obtained as a residue after the distillation of a quantity of commercial bromine was given to me by Professor Thorpe with the request that I would ascertain its nature and composition. From its physical properties Dr. Thorpe was of opinion that i t was carbon tetrabromide a suppo-sition which my analysis *has confirmed. It had the characteristic smell of this compound melted a t 90*1" and solidified at 88.6'. Recrystallisation from alcohol made no. appreciable alteration in the fusing point. Boiled with an alcoholic solution of soda it was a t once decomposed with formation of a white precipitate of sodium bromide, which readily dissolved on addition of water. On acidulating the liquid with nitric acid and adding silver nitrate silver bromide wa4 formed. An analgsis made by means of this decomposition yielded the following results :-0.3424 gram gave 0.7754 AgBr and 0.0036 Ag = 97.1 per cent. Br. Carbon tetrabromide contains 96.4 per cent. Br. The formation of this body in the manufacture of bromine has not hitherto b e e ~ noticed. It is probably formed by the action of the halogen on the organic matters derived from the sea-weed from which the bromine made in this country is procured

ISSN:0368-1645    

DOI:10.1039/CT8813900048

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年代:1881

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49 VII1.-COMMUNICATIONS FROM THE LABORATORY OF THE UNIVERSITY COLLEGE BRISTOL. 1. On the VoZwr~e of Sodium at its Boiling Point. By W. RAMSAY Ph.D. THE method applied to the determination of the specific gravity of sulphur at i0s own boiling point and described in the Chemicnl Society's JounzaZ 1879 p. 4'71 was extended with slight modificst-tions to metallic sodium. The vessel containing the sodium consisted of an iron tube contracted to a narrow orifice a t the top and com-municating with a narrow iron tube at the lower end; the narrow tube was bent twice at right angles so that its extremity was level with the orifice at the top of the wider tube ; in fact it was as near an approach in form to the apparatus used for the specific gravity of boiling sulphur as the difference in properties of iron and glass would allow.After the iron " bulb " had been filled with liquid sodium it was suspended in the cast-iron pot and about half an ounce of sodium was placed in the pot. An iron cover through which a small hole had been drilled was luted on to the pot. The heat of a charcoal fire was employed to vola-tilise the sodium. After the metal had been boiling briskly for about ten minutes and its vapour had been burning at the orifice in the lid, the cover was lifted off ; the iron " bulb " was withdrawn and plunged into heavy paraffin oil while still red-hot and after cooling it was freed from oil and weighed. A cast-iron vessel was used as the bath for sodium vapour. The following data were obtained :-Capacity of iron " bulb " 6.61 C.C.Weight of sodium at its own boiling point filling bulb 4.90 grams. SpecSc gravity of sodium at its own boiling point = 0.7414. Specific volume (reciprocal of specific gravity) = 1.349. Specific volume multiplied by atomic weight (atomic volume) This number represents the volume of liquid sodium at its boiling point condensed from 11,163 volumes of gaseous sodium assumed to exist at 0". This result from the method employed can Iay claim to only a rough approximation t o correctness for i t is evidently influenced by the expansion of the iron vessel the oxidation of the sodium and the dif-ficulty of working a t such a high telsperature. It would appear, = 31.0. VOL. XXXIX. 50 MASSON AND RAMSAY ON THE however from this experiment that the coefficient of expansion of sodium is not high since between the ordinaq temperature and its boiling point i t expands only from 1 to 1,331.2. 0% the Volume of Bromine at its Boiling Point. Four determinations by the method described in the Jownal of tJ8e Chemical Society 1879 p. 471 gave the following results :-Specific gravity. Specific volume. Atomic volume. 1. 2-9503 0.3390 27.12 2. 2.9474 0.3393 27-14 3. 2,9483 0.3392 27.13 4. 29471 0.3393 27-15 Mean specific gravity 2.9483. Mean specific volume 0,3392. Mean atomic volume 27.135. The bromine used for this experiment was distilled with strong sul-phuric acid and manganese dioxide to free it from water and hydro-bromic acid and with potassium bromide to remove any trace of chlorine which might have been present.The number obtained is somewhat in excess of that given by Thorpe viz. 26.74. 3. On the Volume of Phosphorus at its Boilivag Point. By D. ORME MASSON M.A. B.Sc. and W. RAMSAY Ph.D. The apparatus was very similar t o that used by one of us'in deter-mining the density of sulphur under the same circumstances. It will therefore be necessary to dcscribe the difference only. The phosphorus was melted in a wide tube through which a stream of dry carbonic anhydride passed and the bulb which was connected with a tube pass-' ing through the cork was filled by suction. When cold it was reversed, so that the two capillary openings were uppermost and the phos-phorus in the wide tube was boiled by the heat of a saud-bath. When liquid phosphorus had ceased to expand and flow out frqm the capil-laries the operation was stopped and the bulb the capacity of which had been previously ascertained was cooled cleaned externally with carbon disulphide and weighed.The mean results of four experiments were as follows :-Specific gravity 1.4850 Specific volume 0.6734 Specific volume x atomic weight = 20.91 with a probable error of 4 + 0.3987 on the mean result VOLUME OF PHOSPHORUS AT ITS BOILING POINT. 51 4. Discussiort of Results. These observations add two to the number of elements the atomic volumes of which have been determined in the free condition. Com-parison of the values in the elementary and combined states is given in the following table :-Free. Combined. Br 37.135 28.1 S 21.60 22.6 and 28.6 P 2091 25.3 Na 31.00 (?I The numbers obtained by Thorpe (Chem.Soc. Jour. 1880 385) for bromine in combination are in CHBr3 29.0 ; in POBrC12 28.7 ; in PBr, 27.7 ; in CBrC13 29.4 ; in C2H4BrZ 26.7 ; and in CH2BrC1 29. The mean result is the one given in the above ta,ble. The values for combined sulphur are those given by Kopp. Ramsay found (ZOC. cit.) the same values as those of Kopp in CS2 and 22.65 in SzCl, assuming the value of chlorine to be 22.8. The value of combined phosphorus is the mean of ten estimations, varying between 24 alid 26.1. The value of sodium in combination has not as yet been determined. It is evident that the atomic volume of bromine is the same (or nearly the same) whether it be taken in the free or thecombined con-dition viz.:-Free 27.135 Combined 28.10 This is to be expected as the halogens have only one atomic volume when in combination. Turning to sulphur we find the ralue in the free state to be nearly identical with the lower of the two values which it pcssesses in combination. The element nitrogen which is closely allied to phosphorus is known to possess various atomic volumes according as it exists in amines members of the pyridine series and in combiliation with carbon as cyanogen or nitriles or with oxygen as the nitro-group. It is therefore not at all unlikely that phosphorus possesses more than one value. The value of phosphorus has been deduced from the following determinations by Pierre Buff and Thorpe (Thorpe Chem. Xoc. J., Zoc. cit.) which it is necessary to review in their order :-I.PC13 93.3 ; P = 25.2 C1 being taken as 22.7. 2. PBr, 108.3; P = 24.0 Br being taken as 28.1. 3. YCl2(C2H,O) 128.6; P = 25.9 C1 having the previous valu 52 MASSON AND RAMSAY BOILING POINT OF PHOSPHORUS. assigned to it and Kopp’s values (C = 11 H = 5.5 and 0 = 7.8) being assumed for the elements of the alcoholic group. 4. POCl, 101.4; P = 25.5 0 = 7.8 C1 as before. 5. PSC13 116.1 ; P = 25.4 S = 22.6 C1 as before. 6. POBrC12 107.4; P = 26.1 0 = 7.8 Br and C1 as before. On what grounds are the values 7.8 and 22.6 assigned to oxygen and sulphur respectively in the last three compounds ? So far as we can judge the only reason is that a uniform value may be assigned to phosphorus in all its compounds. From general considerations POCl and PSCl must hare one of the following constitutional formulae :-X Cl-F-Cl I or X It Cl-P-C1 I c1 I c1 where X stands for 0 or S.represented by the formula :-PCl, on the other hand can only be CI-P-c1 If the second formula be assigned to PXCI then phosphorus remains a triad and would naturally have the same value as in PCl, but if the former formula represents the constitution of the body then phosphorus becomes a pentad. In this case there is likelihood that phosphorus should have two values one in the PCl type of compound and another in the PC1 type. Moreover oxygen has been proved to have the value 12.2 when attached by both bonds to the same atom instead of 7.8 as it has in hydroxyl and similar groups. Supposing then that the formula is XPCl, the value of phosphorus may be calculated in the following manner :-(The numbers are those of the above determinations.) 4.Molecular volume of POCl, 101.4 Less (0 = 12.2 + Cl = 68.1) 80.3 Atomic volume of phosphorus Less (S = 28.6 + Cl = 68.1) 21.1 5. Molecular volume of PSC1 116.1 96.7 Atomic volume of phosphorus 19.4 6. Molecular volume of POBrClz 107.4 85.7 Less (0 = 12.2 + C1 = 45.4 + Br = 28.1) Atomic volume of phosphorus . 21. PASSAVANT ON THE SPECIFIC VOLUME OF CHLORAL. 53 The mean of these results is 20.7. On comparing this with the atomic volume of free phosphorus it is evident that the two numbers are identical :-Free. Combined. Phosphorus . . . . . . . . . . 20.9 20.7 The arguments for this value are-(1) that there is much more.probability that POCI has the formula OPC1 than P(OCl)Cl, for it is obtainable from the pentachloride by a direct simple reaction ; (2), that bromine in the free state has the same value as in combination ; and that sulphur possesses one of its combined values; (3) that this one is the lower of the two. It is therefore necessary to ascribe two atomic volumes to phos-phorus viz. 20.8 in compounds in which it acts as a pentad and when free and 25.3 in its triad capacity. As ortho-phosphoric acid is obtainable directly from the oxychloride by the action of water there can be no doubt whatever that the for-mulae of the phosphoric acids must be represented thus :-Orthophosphoric Pyrophosphoric Metaphosphoric acid. acid. acid. /OH O=PCOH / O H O'P-OH -0 O=P-OH >O - \OH O=P.-OH \OH From the known analogy between vanadium and phosphorus it is highly probable that similar results will follow on investigation. It remains to mention one conclusion deducible from the facts detailed in the foregoing paper that as elements enter into combina-tion with a volume which they possess in the free state the theory of " steres," as applied by Schroder to boiling liquid compounds is abso-lutely untenable

ISSN:0368-1645    

DOI:10.1039/CT8813900049

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年代:1881

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PASSAVANT ON THE SPECIFIC VOLUME OF CHLORAL. 53 IX-On the 8pec;f;c Volume of Chloral. By LAURA M. PASSAVANT Brown Scholar in the Porkshire College, Leeds. AMONG the substances selected by br. Thorpe as constituting the experimental groundwork of his investigation " On the Relation between the Molecular Weights of Substances and their Specific E 54 PASSAVANT ON THE SPECIFIC VOLUME OF CHLORAL, Gravities when in the Liquid State" (Chem. 80c. J. March et sep., 1880) was chloral. The main point of interest connected with the determination of the specific volume of this body arises from its re-lation to aldehyde and from the fact therefore that its oxygen-atom would presumably have the same value as in that compound. It was part of Dr. Thorpe's original scheme of work to determine how far the introduction of the three chlorine-atoms in place of hydrogen would modify the specific volume of the compound.Considerable difficulty was met with in procuring this body in a fit state for physical exa-mination owing to the persistency with which gas-bubbles made their appearance in the liquid when it was heated much beyond 60". No two samples of chloral could be obtained of identical specific gravity even although prepared and dehydrated under similar con-ditions. This circumstance is uadoubtedly connected with the ten-dency of chloral to pass into a polymeric modification but unfortunately the causes determining this tendency arc too incompletely understood to be applied in maintaining this body in a stable condition. At Dr. Thorpe's suggestion I have again essayed to determine the specific volume of chloral.The greatest care was taken to dehydrate the liquid and to avoid the formation of free hydrochloric acid which appears to have a marked influence in polymerising the subatance. Although a considerable interval of time has elapsed since the obser-vations which form the subject of the present communication were made the chloi*al used has maintained its limpidity unimpaired and there is no evidence of the formation of metachloral within it. The liquid was prepared from commercial recrystallised hydrate by treating it with strong oil of vitriol and afterwards distilling it twice Over lime. It was observed that on adding the chloral hydrate to strong sulphuric acid the tmperature was reduced by 17" ; the tem-perature of the acid having been 13" and that of the mixture falling to -4".The dehydrated chloral was always redistilled before each operation. In order to verify its purity its vapour-density was determined with the following results. The apparatus employed was the modified Gay-Lussac-Hofmann apparatus described by Dr. Thorpe :-Weight of liquid Volume of vapour corrected for expan-sion of glass error of meniscus &c. Temperature 99.96" Barometer (reduced) 758.93 mm. Mercury column (reduced). . 426.9 ,, Found 72-21 Calculated. . 73.48 0.1898 gram. 91.74 C.C. Determindion of Boiling Point.-This was effected in the manne PASSAVANT ON THE SPECIFIC VOLUME OF CHLORAL. 55 described in the memoir above referred to and with the same ther-mometers.The liquid began to boil at 96" and that portion was collected separately which came over between 96.8" and 97.3" (uncorr.). Observed temperature 97.05" Length of the cooled column in degrees. . Temperature of t'he cooled column Barometer (reduced). . 747.7 mm. 25.8" 42 Corrected and reduced boiling point 97.73'. XpeciJc Gravity.-The specific gravity was determined upon two samples in separate bottles. The bottles used had graduated stems, and were fitted with ground-glass stoppers. The weighings were made by the method of vibrations and the weights are reduced to a vacuum. The specific gravities are finally reduced to the temperature of O" and compared with water at 4" by means of the tables of expan-sion given below :-Bottle 1.Weight of chloral at div. 40 and 15*4A Weight of water at div. 40 and at 15-04'. . Vol. of water at 15.4A 1.000904 Vol. of water at 15.04 1.000847 Sp. gr. at 15*4A compared with water of same temp. 1.5167 Vol. of chloral at 1 5 ~ 4 ~ 1.017424 Vol. of water at 15.4 1.000904 5.99126 grams. 5.92866 ,, Bottle 2. Weight of chloral at div. 35.5 and 15*4A . . Weight of water at div. 35.5 and 15-41 Vol. of water at 15*4A 1*000904 Vol. of water at 15.04 1.000847 Sp. gr. at 15-4A compared with water of same temp. 1.5166 Vol. of chloral at 15*4A 1.017424 Vol. of water at 15.4 1*000904 7.83577 grams. 5.16691 The results of the specific gravity determinations at 0" compared with water at 4" are :- , Determination I . 1.541 79 Determination I1 1.541 70 Dr.Thorpe obtained 1-5439 and 1.5466 but was disposed to give the former number double the weight of the latter as it was made upon a larger quantity of the liquid obtained from a much larger preparation 56 PASSAVANT ON THE SPECIFIC VOLUME OF CHLORAL, Both our numbers differ very widely from that obtained by Kopp, viz. 1.5183. The determination of the rate of expansion was made in one of the dilatometers employed by Dr. Thorpe ; this was filled and heated in the arrangement described in his memoir. The results are as follows :-Air-therm. degrees. Observed vol. Calculated vol. 0.0 2904.14 2903997 9-63 2934.19 2934.75 17.5 7 2960.10 2960.63 26.22 2989.22 2989.43 35.26 3020.60 3020.63 44.30 3052.18 3052.53 52.30 3080.92 3081.54 61.14 31 13.93 3114.53 70.12 31 49.10 3149.079 78.91 3183.56 3183.98 No observations could be taken beyond 79" owing to the formation These numbers lead to the for- of a bubble of gas in the liquid.mula-2903.997 + 3*1551025 + 0.0038007t2 + 0*0000149631t3, which after dividing through by the first term and correcting for the expansion of the glass of the dilatometer (0.00002303) gives-V = 1 + 0.0011094985 + 0*0000013338t2 + 0~0000000051827t3. By means of the formula the volumes of chloral at every 5A between 0" and looA have been calculated on the assumption that this ex-pression correctly represents the expansion between these limits :-A Volume. Difference. 0 100000 -5 100558 558 10 101123 565 15 101696 5 73 20 102276 580 25 102865 589 30 103463 598 35 104069 606 40 104685 616 45 105310 625 50 105946 636 55 106592 646 60 107249 65 7 65 107918 66 HARTLEY ON THE ABSORPTION SPEfXt"I'UM OF OZONE.57 A 70 75 80 85 99 95 100 Volume. 108598 109290 109995 110713 111444 112188 112947 Difference. 680 692 705 718 731 744 759 This formula agrees fairly well with that calculated by Dr. Thorpe from his observations but is quite different from that of Kopp (Annulen 95 307) as will be evident from the following com-parison :-20". 40". 60". L. M. P. 10228 10469 10725 Thorpe . . . . . . . . 10226 10462 10717 Kopp 10187 10385 10615 The relative volume of chloral at its boiling point (97.73A) is 1.12602, as calculated from my observations. Hence its specific gravity at this temperature is - - 1.3692 compared with water at 4" and 1.54179 -1.12602 147.01 -1.3b92 accordingly its specific volume is . - 101.37. This number agrees almost exactly with that calculated by means of the final values deduced by Dr. Thorpe from his observations viz., 107.8 (C = 11 C1 = 22.7 H = 5.5 0 = 12*2) and shows that the oxygen-atom in chloral has precisely the same value that it has in aldehyde

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DOI:10.1039/CT8813900053

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年代:1881

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HARTLEY ON THE ARSORPTION SPECI"IX,M OF OZONE. 57 X.-Ot& the Absorption Xpectrum of Ozone. By W. N. HARTLEY F.R.S.E. Professor of Chemistry Royal College of Science for Ireland Dublin. IN the year 1878 I made arrangements for investigating the absorp-tion spectrum of ozone having an idea derived from former expe-rience that it would be less diactinic than oxygen. Several gases were examined at this time and the general results as to the transparency of carbon dioxide sulphur dioxide and hydrochloric acid were similar to those obtained by the late Dr. W. A. Miller. In some expe-riments more recently made on the diactinic quality of ethylene and acetylene I have utilised the collimator tube of the spectroscope, which is 36 inches long by measuring into it the volume of gas to b 58 HARTLEY ON THE ABSORPTION SPECTRUM OF OZONE.observed. The tiibe orginally designed for the examination of cor-rosive gases like ozone chlorine and the oxide of nitrogen was made of glass and measured 2 feet in length and 1+ in diameter. Near one extremity a side tube of small dimensions was fitted. The ends of the tube were polished and fitted with slices of quartz luted on with paraffin. The reflections from the inner surface of the glass which it was at first thought would not affect the photographic plate led to a want of clearness in the photographs. The apparatus was conse-quently dismounted for the purpose of blackening the interior of the tube. Being much engaged in the examination of organic substances, I delayed these experiments on ozone until the announcement of the liquefaction of this remarkable body by Messrs.Hautefeuille and Chappuis (Compt. rend.,. 91 522) attracted my att'ention once more to the subject. The following arrangements were made for producing ozone and delivering exactly measured quantities of ozonised oxygen :-A reser-voir containing about 20 cubic feet of oxygen was connected first with a drying bottle E 12 inches high holding about half a litre of oil of vitriol. On the surface of the vitriol a large quantity of pumice crushed into pieces the size of a pea was placed and ignited with sulphuric acid previous to use. As the gas bubbles through the Titriol if keeps the pumice constantly moistened with acid at the same time that it is itself most thoroughly dried by the large surface of pumice.The gas then passed through a long glass worm-tube D, kept surrounded by ice. One of Tisly and Spiller's ozone tubes C, DIAGRAM SHOWING THE APPARATUS FOR DELIVEBINQ MEASURED VOLUXES OF OZONE. through which a stream of water was kept in circulation was attached to the worm-tube. The coil and Leyden jar used as the source of the r a p by which the photographs were taken served likewise to charg HARTLEP ON THE ABSORPTION SPECTRUM OF OZONE. 59 the ozone tube. The ozonised oxygen passed from the tube into a French drying bottle B 18 inches high containing pumice soaked in potash solution containing one part of potash in two of water and at the top small pieces of stick-potash were placed. This precaution was taken in order to absorb any possible traces of oxide of nitrogen or chlorine.The sticks of potash were subsequently found to be coated with a yellow efliorescence which proved to be potassium peroxide. Attached to this purifying tube was the apparatus for measuring the purified ozonised oxygen and delivering it into the collimator tube. This consisted of a T-piece A with two glass stopcocks joined to a gas-pipette capable of delivering 75 C.C. after each filling. The liquid in the gas-pipette was oil of vitriol. Oue limb of the T-piece was bent downwards at right angles and placed within a tube soldered on at right angles to the collimator tube the junction between the glass and the metal tubes being luted up with softened paraffin. The other limb of the T-piece was fixed on the purifying tube.All joints in the apparatus subject t o the action of ozone were either of paraffin luting fused glass or cork junctions at t and t' the Forks being soaked in melted paraffin. On commencing operations oxygen is biown into the collimator tube through the whole apparatus until it issues abundantly from the slit at the end. A photograph is now taken of the spectrum transmitted by the tube full of oxygen. Then the ozonising tube is charged and the gas passed into the apparatus for some time until no more absorption of ozone takes place in the potash-tube. To prevent the gas gaining access to the spectroscope at this stage of tht proceedings the stopcock just beyond the potash purifier is taken out of its setting in order that the gds may escape here. When the ozone coming off is of a proper strength it is unbearably strong in smell and exceedingly irritating to the mucous membrane.The stopcock is now replaced 'and turned so as to be open; that next the collimator tube is left closed. By drawing up the sul-phuric acid intlo the upper bulb of the gas-pipette the lower one is filled with ozonised oxygen of the same volume as the sulphuric acid withdrawn. By shutting the tap on the supply pipe and opening that communicating with the collimator tube a measured volume of gas is delivered into it. This operation may be repeated again and again with great rapidity; and as it takes but two or three seconds to take a photograph after each such additional volume of gas there is no time for loss of oxygen by diffusion or by oxidising action on the metal tube.About twenty photographs were taken in three or four different series the various degrees of absorption noticed being due t o different quantities of ozone delivered into the collimator tube. The first photograph taken showed a broad absorption-band stretching from wave-length about 285 to 233 millionths mm. In this case th 60 HARTLEY ON THE ABSORPTION SPECTRUM OF OZONE. collimator tube was filled with ozonised oxygen at a temperature of 16" C. and under a barometric pressure of 774 mm. The contents of the tube were 811.5 C.C. A series of photogra.phs was then taken, the tube being filled first with ozoiiised oxygen and this being gradually displaced by successive additions of atmospheric air or oxygen. The increased diactinic character of the gas caused by suc-cessive additions of air is well shown in Diagram 2.The tension of the ozone was found by filling stoppered cylinders with the gas and inserting the stoppers. These cylinders were made with funnel-shaped necks and into the funnel forming a hydraulic lute to the stopper, a solution of potassic iodide was poured. The stopper being gently loosened some of the liquid ran into the cylinder without allowing a single bubble of gas t o escape ; after standing some little time more of the liquid is allowed to run in ; the bubble or two of gas escaping is quite de-ozonised by the potassic iodide solution through which it passes. After the whole of the ozone has been absorbed starch-paste is added and the liquid titrated with centinormal solution of sodiiim thiodphate.. The potassium iodide was neutral hence two atoms of iodine would represent only one-third of it molecule of ozone. The actual amount of ozone found in the tube in two separate expe-riments was-I . . 0.00088 gram in 493 C.C. 11 OaO0054 , 9 , I . . . 0,236 C.C. in 493 C.C. or =lrn of its volume. I1 0-260 , 9 ori&ia 7, This may be considered as 1 volume of ozone in 2,000 of the oxygen. The mean wave-length of the rays intercepted by ozone is 256 millionths mm. From this the mean rate of vibration of the mole-cule of ozone may be calculated. When perfect absorption occurs, the molecule of the absorbing medium must be vibrating synchronously, and in the same plane with the ray absorbed from wpch it follows, if the velocity of light be taken as 315,364,000 metres* per second, the mean rate of vibration per second of the molecule of ozone must amount to 1,231,000,000,000,000 vibrations. f Fizeau estimated the velocity of light as equal to 78,841 leagues per second, a league measuring four kilomot,res

ISSN:0368-1645    

DOI:10.1039/CT8813900057

出版商:RSC    

年代:1881

数据来源: RSC