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Abstracts of the Proceedings of the Chemical Society, Vol. 4, No. 48 |
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Proceedings of the Chemical Society, London,
Volume 4,
Issue 48,
1888,
Page 17-26
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摘要:
ABSTRACTS OF THE PROCEEDINGS OF THB CHEMICAL SOCIETY. No. 48. Session 1887-88. February 16th, 1888. Mr. William Crookes, F.R.S., President, in the Chair. Messrs. T. A. Lawson and Edward A. Andrews were formally admitted Fellows of the Society. Certificates were read for the first time in favour of Messrs. Alfred Chiddey, Mount Costigan Smelting Works, Tuena, New South Wales ; Harold Nicolai Faber, 56, Dalberg Road, Brixton ; James Hart, 131, Embden Street, Manchester ; C. Millard King, 63, Frorne Park Road, Hornsey, N. ; Vivian Byam Lewes, 18,Park Row, Green- wich, S.E. ; Frederick Grevile Ruddock, Wilderspool Road, Warring- ton ; H. Belcher Thornton, 11, Esk Terrace, Whitley, Yorkshire ; Edward Arthur Wates, 4, Princes Road, Lewisham, S.E. It was announced that the following changes in the Council List were proposed by the Council :-As Vice-Presidents, Professors Carey Foster and Mallet, vice Pro-fessors Dewar and Tilden.As Menzbers of Cou~zcil,Profeseors Dunstan, Heaton and Purdie and Dr. Plimpton, vice Messrs. Carteighe, Messel, Newlands and Stevenson, Professors Dunstan and Heaton and Dr. Rideal were appointed by the meeting to audit the Treasurer’s accounts. The following were elected Fellows of the Society :-Messrs. Henry Dudley Bevridge, Thomas Fraser Barbour, William H. Barraclough, Alfred Edward Carey, Lewis Smith Cocking, W. Hepworth-Collins, Astley Cooper, John TI.J. Dagger, Benjamin H. Gerrans, Christopher James, Charles R. Lafosse, J. Lewkowitsch, Frederick K.S. Lowindes, Thomm Maben, James Mayne, Otto Werbeck, Clifford Richardson, Angus Smith, Sam Smith, Robert Mason Sumner, Arthur J. C. Waterland; John Cuthbert Welch, Emil A. Werner. The following papers were read :-11. “ Chemical investigation of Wackenroder’s solution and ex-planation of the formation of its constituents.” By Professor Debus, Ph.D. F.R.S. “ Wackenroder’s ” solution is the solution formed by the action of sulphuretted hydrogen on an aqueous solution of sulphurous acid t,illthe sulphurous acid is decomposed. The compounds repre- sented by the formulze MZS306,M&06, M1S506and MzS60s,in which M stands for hydrogen or a monovalent metal, are called “ Polythio-nates.” The term “acid” is reserved by the author for the so-called anhydrides.The formula SO, stands for sulphurous acid, and H2S03for dihydric sulphite; S405for tetrathionic acid, and H,S406for hydric or dihydric tetrathionate. Wackenroder’s solution contains, according to our best authors, sulphur in suspension and pentathionic acid in solution. Pure pentathionic acid has never been prepared. The attempts to make salts of the acid also failed. In consequence, Spring a few years ago denied the existence of pentathionic acid, which he declared to be a solution of sulphur in hydric tetrathionate, not in atomic propor- tions, but of the same description as the solution of sulphur in carbonic sulphide. To test the correctness of Spring’s assertion, the author suggested to Mr. Lewes some experiments with Wackenroder’s solution ; and Mr.Lewes prepared nearly pure potassic and baric penta-thionate. These salts, however, could not be recrystallised from water, but split up in tetrathionates and sulphur: K2S506= K,S,06 + S. Spring, therefore, would not admit that they were pentathio- nates, but regards them as mixtures of tetrathionates and sulphur. In order to remove all doubts about the existence or non-existence of pentathionates, and also to explain some reactions of more than ordinary interest which the author had occasion to observe, whilst Ah. Lewes was carrying out his work, he undertook the experimental investigation described in the paper. The results briefly stated, are as follows : The filtered Wackenroder solution contains- (a.) Sulphur in suspension in very minute drops.(6.) A new allotropic nzodification of sulphur in simple solution, and in t7ae colloidal condition. This new form of sulphur, Sulphur 6, separates on evaporation of Wackenroder’s solution as a yellow, viscous, semi-fluid mass, partially soluble in much water. It resembles, in some respects, silica as set free from soluble silicates by strong acids. 19 (c.) Traces of trithionic acid. (d.) Hydric tetrathionate. (e.) Hydric, pentathionate. (f.) A polythionate with more sulphur than pentathionates contain, probably hydric hexathionate. Pure potassic and cupric pontathionates were prepared from Wackenroder’s solution, and the reactions of the polythionates care-fully investigated.The most interesting of these reactions are the spontaneous changes of the polyt7~ionates in aqueous solutions ;they are indicated by the equations- -(a*)KzS5Os -K(aS106 +s Pot. pentathionate. Pot. tetrat,hionate. (b.) 2(KZS*O,) = KzS3Os + ~t(,SDa. Pot. tetrathionate. Pot. trithionate. Pot. pentathionate. (c.) 2(K2S3O6) = K2S406 + KzSOa + SO, Pot. trithionate. Pot. tetrathionate. Reactions (a)and (b) occur reciprocally in either direction with equal facility. From these reactions important conclusions can be drawn with regard to molecular and atomic motion in liquids. The penta- thionates resemble persulphide of hydrogen, and are, like ozone and peroxide of hydrogen, endothermic compounds. The similarities which exist, from a chemical point of view, between the polythionates on the one hand and ozone and peroxide of hydrogen on the other, are applied in the paper to explain some of the chief properties of ozone and peroxide of hydrogen.In the second part of the paper the action of sulphuretted hydro- gen and sulphurous acid respectively on the hydrogen salts of the polythionic acids are fully investigated. It is proved that the penta- thionic acid of Wackenroder’s solution is chiefly derived from the condensation of bhiosulphuric acid, thus :-5 (SzO,) --2( s505) Thiosulphuric acid. Pentathionic acid. A2(S,O5) + 2H2O -~H,s,o~ Hydric pentathionate. The final products of the action of sulphuretted hydrogen on liydric tetra- or hydric penta-thionat’e are water and sulphur.The statement of the text-books that siilphuretted hydrogen and sulphur- 20 ous acid produce water and sulphur, is, therefore, correct in so far as the final products are concerned. The polythionates are intermediate products. Sulphurous acid and potassium thiosulphate or sulphurous acid and the chlorides of sulphur, produce salts of the polythionic acids. The third part of the paper is devoted to the discussion of the formulee of the polythionates. It is shown that the following formula: are the most correct expressions of our experience :-K*SO,*() KS*SO,*(! KO.SO,*S KO*S0,-S Pot. trithionate. Pot. tetrathionate. KS,.SO,*O KS3-S0,*P KO-SO,.S KO-SO,.S Pot. pentathionate. Pot. hexathionate. 12. (‘Potilizin’s Law of Mutual Displacement of Chlorine and Bromine.” By T.E. Thorpe, F.R.S., and J. W. Rodger. On heating bromine with an equivalent quantity of an anhydrous metallic chloride in a sealed glass tube free from air at the temperature of the melting point of zinc, Potilizin found that the amount of chlorine displaced by bromine was greater the higher the atomic weight of the metal in the chloride. Experiments were made with the chlorides of Rodium, potassium, silver, calcium, strontium, barium, lead and mercury. Potilizin further fouiid that if A be the atomic weight of the metal, p the percentage of chlorine displaced from its chloride Awhen treated as above, and E its valeacy, the formula PB2= a constant, held good in the case of lithium, sodium, potassium, silver, calcium, strontium, barium, lead, mercury, bismuth, tin and iron.He considered the quant’ity of chlorine displaced to depend on the atomic weight, valency and temperature. Arranging the metals in accordance with the periodic law in vertical series, the chlorine dis-Aplaced was as the atomic weight, -being a constant for each P series. Berthelot pointed out that displacement of chlorine by bromine was only possible if the heat of formation of BrCl was greater than the heat absorbed in the direct substitution. Such displacemeiits might, he thought, take place at temperatures at which the chloride was dissociated, so that the bromine would be able to unite with the free metal. He repeated Potilizin’s experiments but found no action up to 400”.Yotilizin in answer to Berthelot repeated his previous 21 experiments, and further varied the mass of the bromine employed. He used sealed vacuous tubes, heating them at 400-515” or at 300--31.5°, aiid found that the chlorine displaced varied with the mass of the bromine, but at a given limit increase in the amount of bromine or of the temperature did not affect the quantity of chlorine displaced. He pointed out that the interaction mas not in entire accordance with Berthelot’s principle of mztximum work, but that it depended partly on this principle and also on the atomic weight, mass, valency and temperature of the interacting bodies. Berthelot attempted to reconcile Potilizin’s statements with his principle by assuming that intermediate compounds-metallic per-bromides and chlorobromides together with bromine chloride-were formed and dissociated.In the light of such a supposition he con- sidered the displacement of chlorine by bromine if the latter is present in excess, and the small displacements if the two are in equi- valent proportions, to be in accordance with the provisions of thermal chemistry. AIn answer, Potilizin stated that he verified t’he formula ---= a constant, in the case of 14 chlorides, also in the case of nickel and cobalt. He denied that intermediate compounds could exist at the tern- perature of the interaction, and thought the cause of the interaction must be sought for “in the intramolecular conditions of the bodies ; being probably dependent on the varying rates of the molecules.” No further work appears to have been done on the subject, and in order to test the validity of the law stated by Potilizin the following experiments were instituted :-An amount of bromine equivalent to about 1gram of anhydrous chloride was sealed off in a small glass bulb, and a quantity of the salt, exactly equivalent to the quantity of bromine taken, was weighed out into another bulb, and the two were placed in a piece of glass tubing closed at one end.At about 6 inches from the closed end the tube was thickened in the flame and dyawn out into a thick capillary. Beyond $his point it was drawn out and bent so as to be evacuated by the Sprengel pump. When the exhaustion was complete the tube was sealed up by directing a blowpipe flame on to its capillary portion; the point was then annealed and the tube allowed to cool.The bromine bulb was next broken and the chloride distributed as uniformly as possible over the inside of the tube, in order to expose it most advantageously to the action of the bromine. By means of an air-bath the tubes were heated to about the boiling point of mercury in some cases and to about 450” in others. After heating, the tubes were freed from any adherent oxide of iron due to contact with the iron tubes of the bath, by immersion in 22 warm chlorhydric acid, washed, dried, opened by means of a hot wire oc a piece of glazed paper, and heated at 120" till the free bromine was expelled and the weight constant.Lastly, the contents of the tubes were washed out and the empty tubes weighed. From the increase in weight of the chloride taken the amount of bromine sub-stituted and hence the chlorine displaced could be calculated. The results of the experiments carried out in this way are given in the subjoined table. Chlorides marked with the same letter mere heated simultaneously :-It will be seen that only on one occaion-in the case of silver chloride-was a number got in anything like agreement with the figures demanded by Potilizin's law. In all other cases, the amount of chlorine displaced was considerably less than that required by the law. The table, however, shows, that although the amount of chlorine dis- placed stands in no definite relation to the atomic weight of the metal in the chloride used, yet in all cases most chlorine is displaced from the chloride of highest molecular weight when several are heated simultaneously.Further, in all cases with the exception of silver chloride, the longer the time of heating, the more chlorine was substituted, and hence it might be thought that if the time of heating were sufficiently prolonged, a limit would be reached. On the other hand, in no instance was t.he amount of chlorine displaced in any one chloride proportional to the time of heating; even after heating sodium chloride for 120 hours scarcely half the quantity demanded by Potilizin's law was substituted. In the only case in which Potilizin gives definite data, viz., in the case of barium chloride, the percentage of chlorine displaced was 7.78 on heating from two to six hours at 400", whereas me obtained only 4.8 on heating for 17 hours at about 450".The authors consider that these observations altogether disprove the validity of Potilizin's law of displacement. Temperature Time of1 IChloride used. of bath. heating. replaced. 5.5(a) NaCl ............ about 350° 8 hours 0.5 (6) NaCl ............ 450 14 9, 5.51 INaCl ............ :: 450 120 ,, 2.6 (u)KC1 ............. about 350" 8 hours (b) KC1 .............I .. 450 (a) AgCl ............ about 350" 8 hours 450 14 7,(6) AgCl ............ :: 350AgCl ............I I 8 ..(c) SrClz ............I about 450' I 17 hours 1.3 I 5.2 (c) BaC1, ............ I about 450' I 17 hours 4.5 I 7.78 PbC12.. ..........I I I(c) about 450' 17 hours 5.0 12.4 1:3. "A Gasometric Method of Determining Nitrous Acid." ByPercy I?. Frankland, Ph.D., B.Sc., F.I.C. The method is based on the well-known interaction of urea and nitrous acid. The author evaporates a definite volume of the solution containing the nitrite to dryness in a small beaker on the water-bath, the residue is then dissolved in a few C.C. of hot distilled water, and trailsferred along with an excess of urea to a tube standing over mercury. Dilute snlphuric acid is then admitted, whereupon an evo- lution of nitrogen and carbonic anhydride takes place. The reaction is found to be complete in 15 minutes. An excess of a strong solu-tion of pure caustic soda having been admitted into the tube to absorb the carbonic anhydride, the residual nitrogen is transferred to a gas-apparatus and measured.The method was found to yield very satisfactory results. The method was also employed for determining nitrites in the pre- sence of nitrates and ammonia : the nitrate was destroyed by evaporat-ing one portion of such a mixture with excess of ammonium chloride, nnd the nitric acid in the residue was then determined by the mercury method ;whilst another portion was evaporated with an excess of pure caustic soda-to prevent the destruction of the nitrite by the ammonia present-and in the residue the nitrous acid was determined by the urea method.14." The Action of some Specific Micro-organisms on Nitric Acid." By Percy P. Frankland, Ph.D., B.Sc., F.I.C. The author has investigated the behaviour, when grown in nutritive 24 solutlions containing nitrates, of a number of micro-organisms obtained from air and water, and cultivated in a state of purity. Of 32 differ-ent forms so examined, 16 or 17 were found to reduce the nitrate to nitrite more or less completely, whilst the remainder were quite desti- tute of this power. The behaviour of the various organisms was not altered in this respect by excluding air from the solutions in which they were cultivated. In a number of cases the changes taking place in the condition of the nitrogen were followed quantitatively.In some cases ammonia made its appearance in the solutions, but by quantitative experiments it was found that this ammonia was due to the decomposition of peptone, which was the only other nitrogenous ingredient besides the nitrate in the cultivating medium employed. A number of special experiments were made with two micro-organisms, BaciZhs ramoms and B. pestifer, which powerfully reduce nitrates to nitrites, and which also give rise to the appearance of ammonia in the peptone-culture-fluid. In these experiments it was found that the nitrite produced in a given time was augmented by increasing the organic matter, peptone and sugar present in the solu- tion, and that the peptone was much more potent in effecting this increase than the sugar.It was further found that the ammonia generated in these experiments was increased by raising the proportion of peptone to sugar, and diminished by increasing the proportion of sugar to peptone. In nearly dl cases in which partial or total reduction of nitrate to nitrite had taken place, the sum of the nitrogen as nitrate and nitrite in the fermented solution was practically identical with the nitrate in the original unfermented solution ; whilst in those cases in which no reduction to nitrite took place, the nitrate in tohe solution remained practically unaffected by the growth of the micro-organisms. In one case, however, it was found that an organism, B. apuatilis, which does not reduce nitrates to nitrites, caused by its growth the disappearance of a considerable proportion of nitric nitrogen, the defi- ciency not being accounted for by the small proportion of ammonia which was generated in the solution.It is pointed out how this difference in reducing power may in certain cases be of great value in distinguishing between micro-organisms morphologically very similar. 15. “The Action of Phosphorus Pentachloride on Salicylaldehyde.” By Charles M. Stuart, M.A. The author fmds that phosphorus pentachloride converts salicyl- aldehyde into the phosphate of diclrlororthocresol, PO(O*C,H4.CHCI2),, and iiot into dichlororthocresol, as stated by Henry (Bey., 1869, 1%). Dichlororthocresylic phosphate is not altered by boiling with potassium hydroxide solution.By the action of phosphorus penta- chloride on orthomethoxybenzaldeliyde, orthomethoxybenzal chloride, C,H,(OCH3)*CH2C12,is obtained ; this is readily reconverted by the action of warm water into the aldehyde from which it was formed. 16. ‘(Some interactions of Nitrogen C‘hloroph~sphuret.’~ By Ward Couldridge, B.A. The paper is chiefly devoted to the description of experimenta on tbe action of amines on nitrogen chlorophosphuret, P3N$!6, the com- pound which result’s on heating together phosphorus pentachloride and amrnonium chloride ; the small yield obtained by this process is attributed by the author to the formation of phospham, P3N3(NH),, by the action of ammonia on the chlorophosphuret. He finds that the compound P3N3(NH*CsH6),,which Hofniann prepared by treating the chlorophosphuret with aniline, is not altered by heating with muriatic acid at 150°,but that at 250” it is resolved into phosphoric acid, ammonium chloride and aniline chlorhydride. By the action of orthotoluidine, a compound of the formula P,N,(NH.C6H4*CH3), was obtained, and similar compounds were prepared from phenylhydrazinc and piperidine.Attempts to displace the chlorine by cyanogen were unsuccessful, and experiments with sodium and with zinc ethide also gave negative results. 17. “Action of Alcohols on ethereal salts in presence of small quantities of Sodic Alkylate.” By T. Purdie, Ph.D., B.Sc., Professor of Chemistry in the University of St. Andrews, and W. Marshall, B.Sc. The addition of a minute quantity of sodic alkylate to a mixture of an alcohol and an ethereal salt induces an extensive interchange of alkyl radicle between the two substances. The authors having examined the interaction in the case of a number of ethereal acetates and alcohols of the CnH2n+10Hseries, find that a much greater inter- change occurs when the alcohol of complex radicle acts on the ethereal salt of simple radicle than in the converse interaction.The numerical results obtained indicate that, excluding the met>hyl radicle, the affinity of the alkyl radicles for the hydroxyl-oxygen of the acid, as measured by the interaction under consideration, increases with increasing complexity of the alkyl radicle ; but that with regard to the methyl-radicle its affinity is greater than that of the ethyl and less than that of the amyl radicle. 18.“ Note on the densities of Cerium Sulphate Solutions.” By B. Brauner, Ph.D. The author has determined the densities of solutions of the anhy- drous and of the hydrated salt, and finds that the values are identical for solutions of equal concentration. ADDITIONS TO THE LIBRARY. I. Donations. Accidents in Mines, by F. A. Abel ; with an Abstract of the Discus- sion upon the Paper. London 1888. From the Author. Die chemische Krafte, von G. A. Hagemann ; aus dem Dtinischen ubersetzt, von T. Knudsen. Berlin 1888 (Pamphlet). From the Author. Des emplois chimiques du bois dans les arts et l’induetrie, par 0. Petit. Paris 1888.From the Publishers. Results of Experiments at Rothamsted on the Growth of Root-crops for many years in succession on the same Land, by J. H. Gil berf. Cirencester 1887. 11. By Purchase. The Theory and Use of a Physical Balance, by J. Walker. Oxford 1887. Modern Theories of Chemistry, by L. Meyer. Translated by P. P. Bedson and W. C. Williams. London 1888. A Text-book of Inorganic Chemistry, by V. v. Richter. Translated by E. F. Smith. 3rd edition. Philadelphia 1887. chemistry of the Carbon Compounds, or Organic Chemistry, by V. v. Richter. Translated by E. F. Smith. Philadelphia 1886. Lectures on Bacteria, by A. de Barry. Translated by H. E. F. Garnsoy ; revised by J. B. Balfour. Oxford 1887. The Principles of Theoretical Chemistry, with special reference to the Constitution of Chemical Compounds.Philadelphia and London 1887. A Treatise of Chemistry, by H. E. Roscoe and C. Schorlemmer, Vol. 111,Organic Chemistry, Part IV. London 1888. (For circula-tion.) A Treatise on Ore Deposits, by J. A. Phillips. London 1884. The Chemistry of Foods, with Microscopic Illustrations, by J. Bell. Part I. Tea, Coffee, Cocoa, Sugar, &c. London 1881. Part 11. Milk, Butter, Cheese, Cereal Foods, Prepared Starches, &c. London 1883. At the next meeting on March Znd, the following paper will be read :-“The origin of colour and the constitution of colouring matters generally :’’ by Professor Armstrong. HABRISON AND SONS, PRINTERS IN OXDINARY TO HER MAJESTY, ST.MARTIN’S LANE.
ISSN:0369-8718
DOI:10.1039/PL8880400017
出版商:RSC
年代:1888
数据来源: RSC
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