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Abstracts of the Proceedings of the Chemical Society, Vol. 2, No. 19 |
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Proceedings of the Chemical Society, London,
Volume 2,
Issue 19,
1886,
Page 161-170
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摘要:
ABSTRACTS OF THE PROCEEDINGS OF THE CHEMICAL SOCIETY. No. 19. Session 1885-86. March 4th, 1886. Dr. Hugo Muller, F.R.S., President, in the Chair. Certificates were read for the first time in favour of Messrs. Carl Bennert, Ph.D., Blaydon, near Newcastle ; Edwin Ebenezer Burnett, 118, Huddleston Road; Arthur Robert Ling, 14, Woburn Place, Russell Square, W.C. ; Prank Morel, Aldersgate Chemical Works, Southall ; Dr. Robson Roose, 45, Hill Street, Berkeley Square, W. The following were elected Fellows of the Society :-Messrs. James Henry Allan, Henry I(.G. Bamber, Leopold Mandeville Deane, Preo Loll Dey, Adolph Dresel, Herbert Samuel El worthy, John William Ellis, Caleb Ferrey, M.B., B.Sc., James Arthur Forrnoy, Francis W. L. Glenfield, Bertram Harvey Hart, Andrew Henderson, George Thomas Holloway, Arthur Percy Hoskine, William tang, Jun., Arthur Pillans Laurie, Peter MacEwan, Walter Newton, Eugene Obach, Oliver Qaibell, James Galbraith Ross, Richard Spencer, Arthur John Starey, Francis Xapier Sutton, Charles Metford Thomp- son, Julius Wertheimer, Sidney Williamson, Edward Willmore, William T.Wright and Brougham Young. 19. “ A New Element : Germanium.” By Clemens W-inkler. The author, in a, letter addressed to the Society, dated Freiburg, Saxony, February 21st, 1886, states that he has discovered in the mineral Argyrodite a new non-metallic element, closely related to arsenic and antimony, and that he has named it Germanium. Argyrodite is a new mineral discovered at Freiburg by A.Weisbach, consisting of silver, sulphur and germanium. 20. “The Influence of Temperature on the Heat of Chemical Combination.” By S. U. Pickering. A large number of experinients have been made by the author, with the view of ascertaining whether the heat of combination is inde- pendent of temperature, or whether, if not, the variations are of a regular nature. According to Kopp's determinations of specific heats, the heat of combination of solids should be uninfluenced by tempera- ture, but the methods available for ascertaining specific heats would be too imperfect to show any alterations in the heat of combination unless these were very great. The particular cases selected were the heat of hydration of z1 salt and the heat of formation of double salts.The sulphates were the salts chosen. Every means was adopted for rendering the experiments as precise as possible ; the temperatures employed were confined within the ordinary range of atmospheric temperatures; as many as seven different thermometers were used, the more delicate of which read to less than 1/3000" C., and a method was devised whereby the same portion of any instrument was used for every experiment with any particular substance, whatever the temperature might be. The pro- portion of salt to water taken was 1:400 formula weights with the single sulphates, and 1:800 with the double sulphates. Hydrates irz XoZutiom-The results when plotted as curves exhibit very remarkable features. In no case is the heat of dissolution of any of the salts represented by a straight line nor even by a single curve, but consists of a series of curves more or less regular in their nature. Hydrated potassium magnesium sulphate exhibits the greatest number of such changes ; a straight line may be drawn so as to touch or nearly touch the portions of the curves at 2*5", 7-5", 15" and 22.5" C., the portions intermediate between these points corresponding about 100 calories above this straight line.Hydrated magnesium sulphate exhibits similar peculiarities, but fewer in number, the points of minimum heat evolution being about 3", 14" and 22" C. With hydrated copper sulphate the heat of dissolution appears to be repre- sented by a series of straight lines rather than curves.Hydrated potassium copper sulphate presents the appearance of one curve, broken only by a deep indentation extending from 12.5" to 15". With hydrated sodium sulphate there is a depression between 5.5" and 10.5", the heat of dissolution above this point being probably represented by a straight or nearly straight line. The curves of the anhydrous salts generally exhibit peculiarities resembling those of the corresponding hydrated salts, but not always. With potassium sulphate there is a break at 14", a similar one occurs with lithium sulphate, but in the case of sodium sulphate such a break is absent. The curves of these three salts do not show any marked resemblance. The increase in the heat of dissolution of a salt which thus takes place at oertain temperatures, can only be attributed, in the author's opinion, to the formation of some new and higher hydrate.That an increase of temperature should favour the formation of such is not considered extraordinary, when it is remembered that the tempera- tures at which the observations were made are comparatively low, and that with sodium sulphate, where we have other reasons for considering a high temperature would favour the dissociation of the salt from its water, no such increase takes place after 10.5",a much lower temperature than in any other case. No special changes were noticed at 4"C., the temperature of the maximum density of water. The author considers that the heat of formation of these higher hydrates is probably not an inconsiderable quantity in comparison to that of the known hydrates of the salt, but it is impossible to deter-mine its exact value in any special case.The occurrence of these successive changes in the constitution of a salt in solution will involve successive variations in the specific heat of their solution; the temperature of the latter, therefore, will rise under the influence of a, constant source of heat, not in a, regular but in an undulatory manner. Water of Crystallisation.-A comparison of the heat of dissolution of the same salt in the hydrated and anhydrous condition gives the heat of formation of the solid hydrated salt. When the various values obtained for this at different temperatures are represented diagrammatically, they form a series of curves showing that the heat of this combination is not a constant quantity.With magnesium sulphate the heat of hydration increases from 13,100 cal. at 3" to 13,300 cal. at 23",there being a small but questionable break at 14"C. With copper sulphate the variation is much more marked; the line forms one curve from 2" to 9", another from 9" to 17", after which it again rises, attaining the value of 11,320 cal. at 23", whereas at 2" it was only 10,780 cal. The heat of hydration of the double salts shows similar irregularities as well as a similar tendency to increase with the temperature. With sodium sulphate only is a decrease in value ob-served as the temperature rises, this decrease beginning at about 15", after experiencing some remarkable fluctuations at lower temperatures.These fluctuations in the heat of hydration of a salt the author attributes to intramolecular rearrangements ; changes of a nature similar to those which cause the same substance, sometimes even when an element, to exhibit different physical and chemical properties. The general tendency towards an increase in the heat of combination as the temperature rises is in accordance with what has already been observed in other cases. Prom these variations in the heat of hydration it follows that the specific heat of a,solid hydrated salt will be subject to small variations, as in the case of its solution, and also that it will not be exactly equal 164 to the sum of the specific heats of the anhydrous salt and water, but generally slightly less.It is observed that the temperature at which the heat of hydrat,ion of a solid salt is a minimum corresponds to an increased heat in the dissolution of the hydrated salt, as if the possibility of a higher hydrate being formed were due to there being less energy expended in retaining the water already combined, DoubZe8aZts.-The heat of formation of thedoublesalts, MgS04,K2SOA and CuS04,R2SO4,in the solid and anhydrous condition, was cal-culated from the data already alluded bo. This quantity appears to vary also with the temperature ; with both salts it attains a minimum at about 14",the extreme variation with the copper compound being as much as 640 cal., from -240 cal.to f 400 cal. One of the most remarkable features in the variation of this quantity is that an in- crease in it occurs at those temperatures which are marked by a decrease in the heat of combination of the same double salt with its water of crystallisation, thus bearing out the conclusions previously drawn from a comparison of this latter quantity with the heat of dissolution, as to there being some principle of intramolecular corn- pensation, whereby an increase in the energy of combination between any two portions of a molecule can take place only at the expense of the energy between these and the other portions. 21. " The Salts of Tetrethylphosphonium and their Decomposition by Heat." By Professor E. A. Letts and Norman Collie, Ph.D.The authors confirm Hofmann's statement that tetreth yZp7msp7zonimm hydroxide is resolved on heating into ethane and triethylphosphine oxide ; the change occurs quantitatively. The chloride, PEtf4C1,is resolved quantitatively into triethylphosphine hydrochloride and ethylene, On haating the carbonate they obtained t'riethylphosphine together with its oxide, and diethylketone, carbon dioxide and tetrane, whereas Hofmann and Cahonrs state that it yields triethylphosphine arid ethyl carbonate. The acid cadonate behaves similarly. The acetate appears to undergo two distinct changes, and to be resolved partly into triethylphosphine oxide and methylethylketone, and partly into triethylphosphine, carbon dioxide, ethylene and methane. The befizoate is decomposed in a similar manner, ethylphenylketone and benzene taking the place of ethylmethylketone and methane.The products of decomposition of the oxdate at 200-230" are hi-ethylphosphine and its oxide, ethylene, carbon monoxide and dioxide, and perhaps diethylketone. If the oxalate be heated to 160"with the minutest trace of sulphur, a deep indigo-blue colour becoming green and finally yellow is produced ; this reaction furnishes an excellent test for sulphur. The suZphate yields almost quantitative amounts of hriethylphosphine snlphide and oxide, together with charred products. A concentrated solution of the cyanide decomposes when heated, and yields triethylphosphine oxide, ethane and hydrogen cyanide ; a srxlall quantity of what appears to have been propionitrile was also obtained.The iodide decomposes in a complex manner and yields charred pro- ducts. 22. “The Formation of Acids from Aldehydes by the Action of Anhydrides and Salts, and the Formation of Ketones from the Com- pounds resulting from the union of Anhydrides and Salt’s.” By W. H. Perkin, Ph.D., F.R.S. The method of preparing unsaturated ‘acids from aldehydes dis- covered by the author has of late been the subject of much discussion, Fittig especially contending that condensation takes place between the aldehyde and the salt, and not, as the author supposes, between the aldehyde and the anhydride. Believing the arguments put for-ward by those who oppose this latter interpretation to be inconclusive, he has resumed the study of the subject ; the experiments are as yet incomplete, however, and only one observation bearing on the ques- tion is fully discussed in the pasper.The author has piieviously shown that when a mixture of isobutyric anhydride, sodium iso- butyrate and beriaaldehyde is heated, carbon dioxide and butenyl- benzene are produced; these result from the decomposition of phenyl-hydroxyisobutyric acid, which Fittig has proved to be the first product of the reaction. He now finds that on heating a mixture of benzaldehyde, isobutyric anhydride and an acetate, about 60 per cent. of the theoretical amounts of bu tenylbenzene and carbon dioxide are obtained ; whereas, on employing acetic anhydride and sodium iso- butyrate, cinnamic acid was obtained in considerable quantity, and less than half as much carbon dioxide and butenylbenxene as in the previous experiments.These results afford strong evidence that condensation hkes place between the aldehyde and the anhydride, and not between the aldehyde and the salt. The paper mainly consists of an account of the results obtained on heating anhydrides with their salts. On boiling a mixture of butyric anhydride and sodium butyritte, carbon dioxide is gradually evolved and dipropylketone is formed. Isobutyric anhydride and sodium iso- butyrate react in a similar manner. A mixture of sodium propionate with excess of propionic anhydride, heated in sealed tubes at 180-190”, yields carbon dioxide and diethylketone; and acetone is ob- tained in like manner from acetic anhydride and an acetate.The author belieires that the formation of the ketone depsnds on the inter- action of the salt and the anhydride, and that this is the case appears to be proved by the observation that methylpropylketone is obtained if a mixture of sodium acetate and butyric anhydride be heated. 23. "A New Method of Preparing Tin Tetrethide." By Professor E. A. Letts and Norman Collie, Ph.D. In preparing zinc ethide by Gladstone and Tribe's method, the authors obtained a liquid bye-product which they ultimately ascer-tained was tin tetrethide. Experiments were therefore made with zinc-tin alloys containing from 1to 50 per cent. of tin; the yield of tin tetrethide, calculated as percentage of tin converted, varied from 27-56 per cent., but in most of the experiments about 50 per cent.of the tin present was converted, whatever the composition of the alloy. The yield of tetrethide was almost proportional to the mass of tin in the alloy until it contaiiied one-third tin ; it then became almost inactive: and the time necessary to complete the reaction increased enormously. On adding powdered tin to the zinc-copper couple together with ethyl iodide, tin tetrethide was produced on heating ; and a similar result was obtained when zinc ethiodide was heated with powdered tin, but it was necessary to raise the tempera- ture to 160". Alloys of zinc with 20 per cent. antimony, aluminium, bismuth and lead, when heated with ethyl iodide, gave only zinc ethide. 24." Contributions to the History of Cyanuric Chloride." ByAlfred Senier, M.D. On heating together cyanuric chloride, C3N3C13, and sodium acetate in closed tubes at loo", sodium cyanurate, C3N303Na3, and acetyl chloride are produced, but interaction takes place only partially. Silver acetate is not attacked by the chloride ; and cyanuric acid and acetic anhydride do not act on each other. On heating sodium formate with cyanuric chloride, sodium cyanurate, carbonic oxide and hydrogen chloride are formed. Sodium benzoate and cyanuric chloride give benzoyl chloride and sodium cyanurate, 88 per cent. of the theoretical yield of the former being obtained. The action of cyanuric chloride on benzamide is similar to that of phosphorus penta- chloricle, and results in the formation of cyanuric acid, henzonitrile and hydrogen chloride.BenzoyZ cyanuyate, C3N3(C,H,O,),, is readily obtained on heating a mixture of benzoyl chloride and silver cyan- urate at 100";it is readily hydrolysed, if heated for a short time with Walterat loo", into benzoic and cyanuric acids. 167 25. “ The Action of Naphthylamine on Cyanuric Chloride.” ByHarold H. Fries. The author has succeeded in displacing the three chlorine-atoms in cyanuric chloride one by one by the group NH*C,,H,. The dichloride, C3N,C1,(NH*C,,H7), and the monochloride, C3N3C1(NH*CloH7)2, are obtained on mixing the proper quantities of cyanuric chloride and naphthylarnine, both dissolved in ether ; they crystallise from hot; alcohol in needles, the former melting at 149”, the latter at 215”.When either of these bodies is heated with the proper quantity of amine at loo”, nuphthyZmeZarnine,C3N3(NH*CIOH7)3,is formed ;it melts at 223”. 26. “Sulphine Salts containing the Ethylene Radicle. Part I. Diethylenesulphide-methyl-sulphineSalts.” By Orme Masson, M.A., D.Sc. Two substances of the empiric formula C,H,S have been described, one being an amorphous insoluble non-volatile compound, concerning whose constitution nothing is known; the other is crystalline, dis- solves in alcohol, ether and carbon disulphide, boils at 200°, and, as Husemann has shown, has a vapour-density corresponding to the formula (C7H4),S2.The author describes the preparation of this latter; he then discusses its constitution, showing that it is adequately represented by the formula S { E:}This sulphide unites directly with methyl iodide to form diethylene-A series of derivatives prepared from this iodide are described, vie.:-The iodide, C5HllS,I ; the tri-iodide, C5Hl,S213; the nitrate, ; the silver salt, C6Hl1S2NO3*AgNO,C5HllS2NO3 ; the sulphate, 2(C5H11Sz)2S04*7H20 ; t’he chloroplatinates, ; the chloride, C5H11SaC1 (CSH 1iS2CI),PtC1,, (C5H,iSzC1)43P t C14, (C6Hi,S,CI)PtCI4, CloH,,S,Pt,C19) ; the gold salt, C6HllS,C1*AuC13 ;; the mercury salt, CaHIIS2C1~HgC12 the hydroxide, C5EB,IS20H; a volatile oil, Cl2H7,S5. In their general characters the salts of the base resemble those of trimethyl-sulphine, but they differ in some important particulars, of which the following are the most striking:-1.There is much less tendency to form addition-products with the halogens. 2. The salts are decomposed by potash. 3. The hydroxide undergoes a peculiar decomposition, slowly when cold, rapidly on heating; the chief product of which is the oil CdLS5. 168 4. The compounds formed by the chloride with platinic chloride are peculiarly various, and are possessed of characteristic properties. 5. None of the salts examined, with the exception of the sulphate, are at all deliquescent. The constitution proposed by the author for this sulphine base represents it as trimethyl-sulphine in which two methyl-groups are displaced by the dyad (comparatively negative) group S(CZH4),.This view of their constitution affords an explanation of the first two of the above-mentioned characteristics of the base.. 27. “ Sulphine Salts containing the Ethylene Radicle. Part 11. On Dehn’s Reaction between Ethylene Bromide and Alkyl Sulphide.” By Orme Masson, &LA.,D.Sc. In 1865 Dehn published an account of the action of ethylene bromide on ethyl sulphide (Annulen, Suppl. IV, 83), which he summed up in the following scheme :-(1.) 2C2H4Brz+ 2(C,H,),S = (CZH4)&+ 4CzH5Br. (2.) CzH5Br + (C2H5)zS = (CzH,),S. (3.) C2H4Br2+ (CzH5),S= (Cz€15)z(CzH4)SviBrz. (4.) C2H4Brz+ CzH48 = (C2H4)2SViBi’2. The truth of equations (1) and (2) was well proved; that of (3) and (4)rested on rather doubtful evidence.(C,HJ SviBr2 and (C2H4),SViBr2If the compounds (C2H5), really exist’, they are unique specimens of a class of sulphinic salts, and are of considerable theoretic interest. An investigation, however, of the circumstances attending the formation of the salts to which Dehn attributed these formul~, of the properties of their platinum salts (as described by Dehnj, and of the anzlyses on which this theory was based, conclusively shows that Dehn was really dealing with salts aaalogous to those described by the author in Part I of this communi- cation. The author supports this conclusion by proving that sulphinc salts possessed of the required properties are actually formed when diethylene disulphide is heated with ethyl bromide and with ethylene bromide.He therefore substitutes the following equations for nehn’s third and fourth :-(3.) CzH,Br + (C,H4),Sz= C2H4)2S2(CzH5)Br. (4.) CZH~B~Z+ (CzHJZS2 = ((CzH,),Sz)2(C,H,)Brz. 28. “ The Identity of Certain Mixed Ethereal Oxalates.” By L. Gordon Paul. The author has compared the methylic ethylic oxalate obtained, 1, by adding the theoretical amount of CHs*OHto the chloride 169 COC1-COOEt, and 2, by adding the theoretical amount of C2Hb*OH to the chloride COC1-COOMe, and concludes that the two reactions furnish the same product. If an excess of alcohol be used, methylic oxalate in the one case, and ethylic oxalate in the other, is obtained in place of the mixed salt,; but whereas the displacement of ethyl by methyl takes place at once and is very complete, that of ethyl by methyl is much more gradual and less complete.Methylic oxalate may be converted into ethylic oxalate by heating it with methylic alcohol, and vice uersh. Methylic ethylic oxalate is converted by repeated distillation into a mixture of me thylic and ethylic oxalates. ADDITIONS TO THE LIBRARY. I. Donations. Third Snnual Report, 1881-82, of the Bureau of Ethnology of the Smithsonian Institution : by J. W. Powell, Director : Washington, 1884: from the Institution. Journal of the Iron and Steel Institute: No. 11, 1885: London, 1885 : from the Institute. Outlines of Organic Chemistry : by H. F. Morley : London, 1886 : from the Author. The Chemistry of the Coal-tar Colours: by R.Benedikt: trans- lated and edited, with additions, by E. Knecht : London, 1886: from the Publishers. An Introduction to Practical Organic Analysis: by G. E. R. Ellis : London, 1885 : from the Author. Rudiments of Chemistry : by Temple Orme : London, 1886 : from the Publishers. Annual Report for 1885 of the Comptroller of the Currency of the United States : Washington, 1885 : from the Comptroller, H. W. Cannon. Bulletin of the United States Geological Survey : New Series: NOS.7-14. 11. By Purchase. Micro-organisms and Disease; an Introduction to the Study of Specific Micro-organisms : by E. Klein : London, 1885. The Dyeing of Textile Fabrics : by J. J. Hummel : London, 1885. Sngar Growing and Refining: by C.G. W. Lock, G. W. Wiper, and R. H. Earland : London, 1885. A Treatise on the Principles of Chemistry: by M. M. P. Muir: London, 1884 (for Reference Library). Annuaire de 1’Observatoire de Montsouris pour l’an 1886: Paris, 1886. Papers of interest to Chemists recently read at Societies in the United Kingdom :-“Note on the Paper by Mr. J. W. Clark on the Determination of the Heat-Capacity of a Thermometer.” By A. W. Clayden. “ On Experimental Errors in Calorimetrical Work : and on Delicate Calorimetrical Thermometers.” By S. U. Pickering. Physical Society, January 23rd and February 13th. “ On Radiant Matter Spectroscopy. Note on the Earth Ya.” ByW. Crookes, F.R.S. “ Colour Photometry,” By Captain Abney, R.E., F.R.S., and Major-General Festing, R.E. Royal Society of London, February 25th and March 4th. “ On the Magnitude of the Mutual Attraction between two pieces of Matter at distances of less than 10 micro-millimBtres.” By Sir William Thomson. “ On Radiation from Snow.” By John Aitken. “ On the Change of Volume of a Salt when Dissolved in Water.” By J. H. Pollok. “ On Electrolytic Polarization,” By W. Peddie. “ On Thermometer Screens.” By J. Aitken. Royal Society of Edinburgh, March 1st. ~-EARRISON AND SONS, PRINTERS Ih’ORDINARY TO EEb MAJESTY, ST.MAXTIN’S LANE-
ISSN:0369-8718
DOI:10.1039/PL8860200161
出版商:RSC
年代:1886
数据来源: RSC
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