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Proceedings of the Chemical Society, Vol. 7, No. 100 |
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Proceedings of the Chemical Society, London,
Volume 7,
Issue 100,
1891,
Page 113-122
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摘要:
Issued 3/7/1891. PROCEEDINGS OF THE CHEMICAL SOCIETY. No. 100. Session 1891-92. Julie 18th, 1891. Professor A. Crum Brown, F.R,.S.,President, in the Chair. hlr. F. J. Bloomer was formally admitted a Fellow of the Society. Certificates were read for the first time in favour of Messrs. William P. R. Newlands, Rosa, North-West Province, India ; Laurence Priestley, Forest View. Noel Street, Nottingham ; Thomas Armistead Ward, Preston Road, Blackburn. The following were elected Fellows of the Society :-Tom St. John Belbin; Edward Brown ; Ernest A. Coiigdon, Ph.B. ; W. Porter Dreaper ; William Duncan ; Alfred John Gregory ; Frederick R'. Hollonian ; John Knowles ; Frank H. Leeds ; Robert Andrew Scott Macfie ; Arthur Michael ; Thomas Xitchell ; Harry Joseph Marston Mousley ; James Lane Notter, 11I.D.; F.&I.Perkin ; Edward Rhodes ; Edmund Charles Rossiter ; John Shields ; l'rank 0. Solomon ; Jolin Taylor; Frederick Tetley; Dr. Otto Carl Weber; Seivard W. Williams. The following papers were read :-29. " A note on some interactions of dehydracetic acid." By J. Norman Collie, Ph.D., F.R.S.E., University College, London. During the last six months the author has been woi-king with large qnantities of dehydracetic acid, and he finds that several important reactions of this interesting substance have hitherto escaped notice. In its prepamtion, by passing ethylic acetoacetnte t2ii.oug.h a red-hot tube, it is stntcd tliat a,lcohol is formed ; t'he author finds that large 114 quantities of ethylene gas and acetone are produced as well.He also finds that dehydracetic acid is vohtile to a considerable extent with steam, and is also decomposed by boiling with water to a small extent into carbon dioxide and dimethglpyrone : CsH,04 + H,O = CiH,O, + CO, + H,O. In the evaporation, therefore, of a solution of the acid a laqe quantity OF the acid is lost. This decomposition into dimethylpy~onc! is effected far more readily if the acid is boiled with strong chlor- hydric acid ; if 50 grams are boiled with the ordinayy fuming acid, in about half an hour the whole is converted into carbon dioxide and a ~olnble compound of dimethylpyrone with hydrogen chloride. This hydrochloride crystallises from strong solutions in magnificent groups of tabular crystals.Feist states (B~L~L&.‘IL,257, 253) that chlor-hydric acid i3 almost, without action on dehydracetic acid. The barium salt of dehydracetic acid seems to be riot :L salt of tlic compound CeH804,but of the true tetracetic acid, C,H,,,O,, and has the formula (C8H,05)2Ba. A curious copper salt has been obtained. If dehydracetic acid be added to a solution of copper acetate in a large excess of ammonia, on allowing to stand, a pink, insoluble salt separates. This salt is very stable, and is not decomposed even when boiled with sulphuretted hydrogen ; but,if chlorhydric acid is added it is at once decomposed and dehydracetic acid is re-formed. The formu!a of the salt seems to be C24H,50,N.jCu. Such a salt could be prodaced according to the following equation :-3CbH804 + 3NH3 + C~(C2H302)= C,,H,,O:,K.%C:L1+ 3HZO + 9(’,H,O,.30. “ The lactone of tiiacetic acid.” By J. Korman Collie, Ph.L)., F.K.S.E., University College, London. In a paper which the author commuicated to this Societ,y some short time ago (Trans., 1890, 189) on the constitution of dehydracetic acid, he pointed out that if the forinula which he proposed for dehydracet,ic acid were the correct’one, it would then be the &lactone of tetrncetic acid. The folloiving list, was then given, which was intended to show the connection between the condensed acids formed from acetic acid :-CH3*CO*CH,*CO*CH,*C0.CH,~COOH,tetracetic acid. CH,*CO.CH,.CO*CH,*COOH, triacetic acid. C H3*CO*CH2*COOH, diacetic acid.CH,.COOH, acetic acid. 115 At that time no acid corresponding to triacetic acid was known. Since then the author has, however, been able to obtain the lactone of this acid by the action of 90 per cent. sulphuric acid on dehydracetic acid at a temperat,ure of 130-135" C. :-CSHSOI + HZO = CgHCO3 t-CZH402. It crystallises from watter in fine needles, p.p. 18;;--189" (coi-r.). The properties of this new lactone resemble those of dehydracetic a.cid It docs not form a sta,ble ammonium salt, for, on evaporation of a solution of the acid in ammonia over sulphuric acid in vacuo, a certain quantity of the acid results. When boiled with acids or water it yields carbon dioxide and acetFl acetone, resembling dehydracetic acid and diacetic acid in this respect :-CH3* C 0.CH,*CO*CH,*COOH = CO, + CH3CO*CH,CO*CH:p CH3*CO.CHZ*COOH= CO, + CH,CO*CH,.When warmed with strong solution of caustic soda, acetone and acetic acid are produced. With bromine a mono-substituted bromine derivative is formed (m. p. 200-205") :-CgH603 f Br, = C,H,BrO, + EBr. Iftreated with hydroxylamine an hydroxime is formed, crystal- lisirig in long needles, m. p. 230-231" (corr.). Aid finally, if the ammonium salt is heated a nitrogen compound is produced, which is either a pyridine or pyrrol derivative, as it does not give any ammonia when heated with caustic soda :-CgHGO3 + NH3 = CgHiNO, + HZO. The investigation of this new compound is not yet completed. 31. " The refractive power of certain organic compmnds at different temperatures." By W.H. Perkin, Ph.D., F.R.S. Having found that the magnetic relations of substances, when examined at temperatures wide apart, showed that certain variations took place after allowing for change of density, experiments having been made by the authors in reference to the refractive power of liquids under similar circumstances. After describing the apparatus used, results are given showing that the specific refractive energy of the substances examined is not constant for all temperatures. The experiments were made at temperatures from about 14 to 92, and for the lines A, C, D, and F,the differences obtained wei-e calculated for a variation of loo", so tha,t comparison could be more easily made, and are as follows :-PA-1 PA -1 tl * cl p.Aniline .............. 0.00310 0.2897 Toluene .............. 0 00329 0.291 0 Hept ane .............. 0.0029 1 0.2914 Dimethyl anilino. ....... 0*0025:3 O*:3057 Phenyl iodide .......... 0-00214 0.4378 Octyl iodide ........... 0.00190 0.4549 Cinnaniic ether. ........ 0.00324 0.7080 Methyleno iodide ....... 0.00401 0.8685 By ww.paring the lincs A :nicl F it was also found that tlie disper- sion was slightly diminished by rise of temperature. When calcu- lated by Loi-entz's formula, the numbers gave higher results for high temperatures than for lower ones, showing the formula, is not suitable for the calculation of experiments made at high temperatures.Ketteler's experiments with water, alcohol, and carbon disulphide are also referred to. The influence of heat, therefore, affects both the refractive power as well as the magnetic rotatory power of substances ; the result, however, are not corr-parable as to the extent of change. D1SCUSSION. Dr. GLADSTOXEremarked that in the original paper by Mi*. Dale and himself, published in 1863, they had, as the result of an exumi-nation of 23 different liquicls, comc to the conclusion that r-1 ~ d was " nearly a const:uit " at all temperatures. T'hcy had tested this for the theoretical limit of the spectrum according to Cauchj's formula, as well as for the lines A and €3. Laiidolt and Wullner seem to have expected that the slight differences recorded were due to experimental error, but on carefully repeating the experiinerits they arrived at a similar result.Dufet, in 1885, published an elaborate paper, in which he proved that the general law was not absolutely true, but a near approximation. Nasini and Bernheimer, in 1884, published very careful qbservations both on saturated and unsatu-rated compounds, dea,ling both with the specific refiTaction and dis-persion ; while Weegman and others have also contributed material to the general investigation of the subject. Dr. Perkin's cxperiments were particularly valuable on account of 117 the indications tliey give that the rate of change of specific refraction is greater at high than at low temperatures, and as they afforded clearer proof tlian has heen hitherto given that the specific disper- sion does decrease with the temperature.If it should be found to be a general fact that the change is proportionaliy greater in saturated than in unsaturated compounds, and still greater in such bodies as cinnamic ether, another connection will have been established between this phenomenon and what we already know of refraction, dispersion and magnetic rotation. The observation that the values decrease as the temperature rises if calculated by the old formula, while they increase as calculated from Lorentz's formula, seemed to be an argument in favour of the older formula; RS the hotter liquid is approaching the con-dition of a gas, and it is well known that the refraction of a substance is somewhat smaller in the gaseous than in the liquid state.Professor THORPEsaid that it would be specially important to study the influence of temperature on refractive power in the case of liquids, such as acetic acid, which were believed to undergo mole-cular change ; and it would also be interesting to know what was the behaviour of the phosphorus compounds, as the optical properties of many of these were most anomalous. Mr. HIBBERL'thought that the superiority of the formula~ over Lorentz's formula brought out by Dr. Perkin was an important resnlt. 32. "Note on a volatile compound of iron and carbonic oxide." By Ludwig Mond, F.R.S., wid F. Quincke, Ph. D. 'l'he authors describe experiments from which they conclude that iron forms a volatile compound with carbonic oxide of the formula Fe(CO)4 corresponding to that of nickel.Very finely divided iron --obtained by reducing iron oxalate by hydrogen at a temperature but little exceeding 400" and allowing it to cool to SO" in hydrogen-when heated in an atniospherc of carbonic oxide, gave a gas which burnt with a yellow flame ; and 011passing the gas through a,heated tube rz mirror of iron was formed at between 200" and 350", while at higher temperatures black flakes of iron and carbon were deposited. Only about 2 grams of iron, however, WRS volat'ilised after six weeks treatment of 12 grams of the metal ; it was necessary every five or six hours to interrupt the operation and to reheat the iron to 400" in hydrogen during about 20 minutes.When passing carbonic oxide at the rate of about 2+ litres per hour, not more than 0.01 gram of iron mas volatilised, corresponding to less than 2 C.C. of the compound Pe(CO)&in a litre of gas. Thc authors haye effected an analysis of the compound by passing the mixtuve of gases into mineral oil boiling between 250" and 300", and heating the solutioit so obtained to 180"; iron free from carbon is then deposited and carbonic oxide gas is evolved. Five analyses are quoted, the results of which give a ratio of Fe: CO varying only from 1:4-03to 1 :4.264. DISCUSSION. Dr. ARMSTRONGsaid that the authors' discovery was even more in- teresting than that of the nickel compound which they had previously described in conjunction with Dr.Langer, on account of the explana- tion which it might be held to afford of the permeability of iron by carbonic oxide at high temperatures, as well as of the production of steel by the cementation process, phenomena to which Graham bad drawn attention. Just as platinum was permeable by hydrogen and silver by oxygen aC high temperatures, so iron was permeable by carbonic oxide: it might be supposed in each case, because a dis-sociable compound of the metal with the gas was formed. Professor THORPE,after referring to the value of authors' observation as shedding light on the production of steel by the cementation pro-cess, stated that in studying, in conjunction with MI-. Ellis, the inter- action of nitrogen peroxide and carbonic oxide under the influence of finely divided platinum, he had recently had occasion to observe that platinum had the property of causing the separation of carbon from carbonic oxide.Mr. MOND,in reply, said that, although the application of their discovery in the directions indicated had not escaped their notice, they had refrained from discussing such matters, as the compound was only obtained at low temperatures. Dr. ARMSTRONGsaid that this might well be the case; but, as Mr. Mond and Dr. Quincke had established the all-important fact thatl iron had a specific affinity for carbonic oxide, the argument he had used would apply, although the compound might not be sufK-ciently shable at high temperatures to exist alone.33. "The formation of salt,s--a contribution to the theory of electrolysis, and of the nature of chemical change in the case of non-electrolytes." By Henry E. Armstrong. The author draws attention to the recent researches of Claisen, W. Wislicenus and others, which clearly show that ethereal salts, such as ethylic acetate, form compounds with sodium ethylate, and to the bearing which these results have on the theory of the formation of salts generally. It may be supposed that in all cases the acid and the "base " in the first instance combine, and tlint the salt is formed 119 by subeqnent interactions mithin the molecule. In like manner, acids form dissociable compouds with water, and it is by the occurrence of chwge within such systems under tihe influence of an electro- motive force that, electrolysis is effected.In those cases in which the compound is highly unstable and prone to dissociate, the opportunity for change to take place within the system is but slight, and consequently the acid is a weak one, and its solution of relatively low conducting power. In the case of lion-clecti~olytes, tlie occurrence of change may, in like manner., be supposed to occur within complex systems formed by the union of th c interacting substances-sys tern s which are comparable with those formed by the union of acid and " base." 34. "Dibenzyl ketone." By Sydney Young, D.Sc., Professor of Chemistry, University College, 131*istol. Dibenzyl ketone was prepared by Popow (Cer., 6, 550) by the action of heat on calcium phcnylacetate.The author finds that when the calcium salt, dried at 130", is hea,ted in a hard glass tnbe in a combustion furnace, the yield is very poor, even when the temperature is kept as low as possible, and when a current of dry carbon dioxide is passed through the tube. After laborious purification of the product, not more than 27 per cent. of the theoretical amount of pure ketone was obtained. The action of heat on the calcium salt was then more carefully studiei, and it was found that the decomposition begins a@ about 360", and is very rapid at 445",the boiling point of sulphur. A considerable quantity of calcium phenylacetate was then heated by means of the vapour of boiling sulphv in a special apparatus described fully in the paper.More than 50 per cent. of the theo-retical was obtained by crystallisation of the crude product from small quantities of ether, and by fractiouation and subsequent re- crystallisation of the yesidues, the total yield of pure ketone was increased to 76.G per cent. Pure dibenzyl ketone melts at 33.0", and boils at 330.55" under norma1 pressure. 35. "The vapour. pressures of dibenzyl ketone." By Sydney Young, L).Sc., Professor of Chemistry, University College, Bristol. Constant temperatures above 280", the boiling point of bromo-naphthalene, may be obtained by means of the vapour of mercury boiling under known pressure, but there are serious objections to this substance. Renzophenone gives very good results according to Crafts (Amel-. J.Sci.. 5, No. 5), but the boiling point, 306", is not sufficiently far removed from that of bromonaphthdene to give a good range of temperature. Dibenzyl ketone boils at 330.55", and although it suffers a slight amount of decomposition on long continued boiling, the temperature of tlie vapour is not perceptibly affected. The ketone may also be readily purified by recrystallisa-tion from small quantities of ether. The vapour pressures from 230" to 280" were determined in a modified distillation bulb, the temperature being measured with a mercuria1 thermometer standardised by means of bromonaphtEia1ene. At higher temperatures a mercury vapour pressure thermometer was employed, and the ketone was boiled in a wide glass tube, enlarged into a bulb at it's lower end.Four series of determinations were made with very concordant result's. The logarithms of the pressure were mapped against the tempera- ture, and the constants for Biot's forniula (logp = a & bzL)were calculated from the values at 230", 280" and 330". Prom these constants the vapour pressures were calculatecl at cnch 10"from 230" to 330", and for each degree from 280" to 330". The results are tabulated in the paper.. 36. " The vapour pressures of mercury." By Sydney Young, D.Sc., Professor of Chemistray, University College, Bristol. In vol. 49, pp. 37-50, of the Transactions, a11 account wxs given by Dr. Ramsay and the author of determinations of tjhe vapoL1.r pres-sures of mercury at several widely different temperatures, and tables of vapour pressure, based gnthese results, were added. The Eiigliest temperature at which obserrations were made was that of thc vapour of sulphur boiling under atmospheric pressuye, and in calculating the results the boiling point of sulphur given by Regnsult was taken as correct. From a recent rescarch by Callendax and Grifliths (Phil.Tmns., 182, A, 119) it appears, howevey, that Regnault overestimated this temperature by nearly 4",and the vapour pressures of mercury at high tempei*atures therefore require correction. Messrs. Callendar and Griffit hs have also redetermined the boiliiig point of mercury by means of their platinum tliermonieter, and the temperature they have observed is about 1.5"lower t)haii that given in the tables of Ramsay and Young.Two additional observations of the vapour pressures of mercury at 183*75"and 236.9"have been made, and froni the previous results by €Lamsay and Young (corrected at the highest temperature for tlie alteration in the boiling point of sulphur), the boiling point of 121 mevxi-y given by Calleudar and Griffiths, and the values at 183.73" and 236.9",the vapour pressures of mercury at each 10" from 180"to 480°, and for each degree from 330" to 360" have been recalcuiated, and the tabulated results, with an account of the method of calculation, are given in the paper. ADDITIONS TO THE LTBRARY. I. Doizatiorzs. Coal and mhak we get from it, by R.Meldola. London 1891. From the Publishers. Colour Measurement and Mixture, by W. de W. Abaey. London 1591. From the Publishers. R8eportof the Sixtieth Meeting of the British Association for the Advancement of Science, held at Leeds in September, 1890. London 1891. From the Association- The Chemistry of Illuminating Gas, by N. H. Huinphrys. Lor don 189i. From the Author. California State Mining Bureau: Tenth Annual Report of the State Mineralogist (W. Irelan, Jr.) for the year ending December 1, 1890. Sacramento 1890. From the Bureau. IT. 131~€'u1. cha se. Handbuch der Elektrochemie und Metallui-gie, von F. Vogel und A. Riissing. Stuttgart 1891. A History of Chemistry from Earliest Times to the Present Day, by E.Meyer. Translated hy G. JlcGoman. London 1891. Tm Virus, par S. Arloing. Paris 1891. EXTRAORDINARY GENERAL MEETING. June 25th, 1891. Professor Crum Brown, President, in the Chair, The request of certain Fellows to the President to summon an Ext,raordinary General Meeting of the Socieiy and the notice con- vening the meeting were read, and on the motion of the President it was agreed that the proposals submitted for amending and altering the bye-laws should be taken as read, printed copies having been circulated among the Fellows. The President suggested that the most convenient course would be for the Fellows at whose request the meeting had been called to 122 explain and justify in general terms their proposals, and to leave the discussion of details to a later period.Mr. James Wilson, however, urged that, as specific resolutions had been submitted, the several bye-laws should be separately considered, and the President having agreed bhat this course would be in accordance with his ruling if the motion were confined in each case to an affirmation of the principle, Mr. Wilson moved : “ That Bye-law I be altered in the sense indi- cated by the clauses already in the haiids of the b’el10ws.~~ He then indicated, with special reference to Clause 3, the reasons which, in the opinion of the memoi~ialists, rendered such alterations desirable. The motion was seconded by Dr. Tccd. Professor Tilden, in his capacity as President of the Institute of Chemistry, strongly deprecated the proposal that Fellowship of the Chemical Society should be wgarded as a professiorial qualification. Mr.Cnrteighe then mored the following amendment :-“That this meeting decliiies to pledge itself to any amendment or niodification of the bye-laws which has not been approved and recommended to the Fellows for adoption by the Council.” Sir F. A. Abel seconded the amendment. Mr. Cassal, Mr. Lloyd and nr. Newton addressed the nieeting in support of the original motion. MY. Warington, Mr. Page, Dr. Odliiig and Mr. Friswell spoke in favour of the amendment. Mi.. Clayton spoke in answer to objections made by Mi-. Page to the use of the letters F.C.S., &c., nndey certain circumstances. Mr. Goffin also spoke. Mr. Lloyd and Dr. Teed having been aominated tellers for the original motion, and Messrs. Groves and Warington for the amend- ment, the meeting then divided. The votes recorded were- For tlie amendment. ............ 137 Against ,, ............. 47 Majority for the amendment ...... 90 Professor Odling then took the Chair, and declarecl the following resolution carried :-“ That this meeting declines to pledge itself to any amendment or modification of the bye-laws which has not been approved and recommended to the Fellows for adoption by the Coanuil.” On tlie proposal of Dr. Teed, seconded by Mi,. Carteighe, a vote of thanks to the President for his conduct, in the Chair was carried.
ISSN:0369-8718
DOI:10.1039/PL8910700113
出版商:RSC
年代:1891
数据来源: RSC
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