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Proceedings of the Chemical Society, Vol. 6, No. 78 |
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Proceedings of the Chemical Society, London,
Volume 6,
Issue 78,
1890,
Page 19-28
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摘要:
Issiced / 1890 PROCEEDINGS OF THE CHEMICAL SOCIETY. No. 78. Session 1889-90. February 20th, 1890. Dr. W. J. Russell, F.R.S., President, in the Chair. Messrs. Frank H. Mason, A. H. McConnell, Edward Russell, John Wade and S. Russell Wells, were formally admitted Fellows of the Society. It was announced that the following changes in the Council list were proposed by the Council :-As Vice-Presidents: Professors Crum Brown, F.R.S., and W. N. Hartley, F.R.S. ; vice Prof. McLeod, F.R.S., and Nr. Ludwig Mond. As Members of CounciZ: Messrs. Henry Bassett, C. F. Cross, Professor R. Meldoln, F.R.S., and Mr. M. M. P. Muir ; vice Professors A. H. Church, F.R.S., and F. Clowes, Mr. C. W. Heaton, and Dr. H. F. Morley. Messrs. Bernard Dyer, R. H. Davies and R.J. Friswell were appointed by the meeting to audit the Treasurer’s accounts. Certificat,es were read for the first time-in favour of Messrs. William Frederick Laycock, Ph.D., 2, Park Street, Dewsbury ; Arthur Sheridan Lea, Caius College, Cambridge ; George Miiller, 125, Mercer Street, Jersey City, N. Jersey, U.S.A.;E. H. Neville, M.A., Sidney College, Cambridge; Ernest George Scott, Mayer Hall, near Birkenhead ; Willie Brewin Shuttlewood, Hong Rong ; Frederick Richard M. Stone, 64: Thomas Street, Merthyr. The following papers were read :-10. “The behaviour of the more stable oxides at high tempera- tures.” By G. H. Bailey, D.Sc., Ph.D., and W. B. Hopkins. The authors chiefly devote attention in this notice to oxide of copper.Previous experimenters had obtained cuprous oxide by 20 heating the oxide to redness. From the results obtained by the authors, it appears that at higher temperatures oxygen is given off, and that an oxide having the composition Cu30is formed. This is insoluble in mineral acids and even in boiling aqua regia; it can, however, be changed into a soluble form by fusion with caustic potash, from which it separates on treatment with water. The oxides of lead and tin seem to behave like that of copper at high tempera- tures. 11. “The inhence of different oxides on the decomposition of potassium chlorate.” By G. J. Fowler, BLSc., and J. Grant. The object of the experiments has been to systematically examine the influence of the chief metallic oxides and certain unstable salts on the decomposition of potassium chlorate.Upwards of a hundred experiments have been made, the most ,significant of which are recorded in the paper. In each case, the temperature at which oxygen is evolved, the amoiint.of chlorine given off and the com-position of the residue after heating have been determined. The variation of the results according to the acid or basic character of the oxide added, its physical condition and the relative masses of the oxide and chlorate has been recorded. The results obtained may be summarised as follows :-(1.) Acid oxides, such as Vz06,WO, and U308,cause the evolution of oxygen at a reduced temperature ; a metavanadate, tungstate or uranate being formed. Chlorine is evolved in these cases in large quantity, but the whole of the oxygen of the chlorate is not evolved, as the compound of K20with the oxide is not decomposed either by heat or by chlorine: $Kclo, + 2V205= 2K20V20,+ 2CI2 + 502.(2.) Alumina probably acts similarly but less energetically, the attraction between the K20and A1,0, not being so great. (3.) In the case of chromium sesquioxide, the oxygen is evolved at a reduced temperature, accompanied by chlorine. The decomposition may be supposed to be brought about by the affinity of the Cr203 for 0 and the affinity of the Cr03 thus formed for K20, but all the oxygen of t’he chlorate is not evolved, since 8KC103 + 2Cr2O3= 4KzCr04 + 4C1, + yo2. (4.) In the case of the sesquioxides of iron, cobalt and nickcl, cupric oxide and manganese dioxide, oxygen is evolved at a compara- tively low temperature accompanied by only a little chlorine ; the oxide is left but little altered at the end of the experiment.Accepting McLeod’s theory of the action of manganese dioxide (Chem. 8oc. Trans., 1889, 184), which is fully in harmony with the results of the experiments under consideration, it would seem that 21 manganese dioxide first acts by reason of its affinity for oxygen and the affinity of the higher oxide thus formed for K,O. The perman- ganate first formed, however, is unstable (here there is a difference between the oxides of this class and those of the preceding), and is resolved into K:,MnO4 + MnO, + 0,. The K2Mn04 is decomposed by chlorine into KC1 and MnOz, which is thus regenerated.The addition of sodium carbonate retards the epolution of oxygen, probably because the manganate is thereby rendered more stable. The action of the other oxides (cf. Spring and Pi-ost) of this class can, it is believed, be explained in a similar manner to that of manganese dioxide. (5.) The monoxides of barium, calcium and lead cause no evolu- tion of oxygen when heated with chlorate, but the latter breaks up below its normal temperature of decomposition, potassium chloride and a peroxide being formed. Here the affinity of the oxide for oxygen induces change. (6.) On the other hand, potassium chlorate may act as a reducing agent in the presence of such oxides as silver oxide and the per- oxides of barium and lead, a perchlorate being formed.No oxygen is evolved. Here the change is brought about by the affinity of the chlorate for oxygen. In the case of the oxides of calcium, barium and lead, the extent to which the chlorate is oxidised evidently depends on the relative masses of the interacting substances. (7.) Water of hydration appears to diminish the activity of an oxide, owing doubtless to the absorption of heat necessary for its conversion into steam. (8.) The physical condition of the oxide is of influence. Copper oxide prepared in the dry way is almost inactive. (9.) Certain substances, although apparently they undergo no chemical change, assist the decomposition, e.g., powdered glass, sand and kaolin.(10.) Oxides such as those of zinc and magnesium are inactive. DISCUSSION. br. HonmimoN said that he had noticed that all the chlorine wits expelled from potassium chlorate by heating it with either uranic or tungstic or vanadic oxide-was this because these oxides expel the chlorine from chlorides? In the case of stannic oxide, everything depended on the state of the oxide: the native form had no action, but metastannic acid expelled chlorine. Professor MCLEODthought that the decomposition of potassium chlorate was promoted in some cases by a mere action of presence similar to that which charcoal exercises on the boiling of water: for 22 instance, platinum black appeared to act in this way, and probably basic oxides exercised a, similar influence.Professor RAMSAY expressed the opinion that in some cases the oxides were converted into corresponding chlorates : that copper oxide, for instance, became conveTted into copper chlorate, which was thereupon resolved into copper oxide and an unstable oxide of chlor-ine ; it was desirable from this point of view to study the behaviour of various chlorates. Professor THORPEsaid that much had aheacly been done in the direction suggested by Professor Ramsay ; but difficulty arose as many chlorates were hydrated salts which decomposed during dehy- dration. After calling attention to Teed’s and Frankland and Ding- f all's experiments, he said there was no evidence that when, for example, manganese dioxide was used manganese chlorate was formed.Mr. Eccles had several years ago made experiments in his laboratory to test this point, and had found that no alkali was formed when manganese dioxide was used, as must have been the case if any chlorate of the oxide were produced. The non-production of per-chlorate was the most remarkable feature of the change in presence of manganese dioxide (cf. C‘hem. SOC.Jourrz., lS76, 856). In reply to a remark by Professor Ramsay, Professor MCLEODsaitl that the formation of permanganate accounted for the fact that no alkali was obtained, although chlorine was given off. 12. “ The interaction of hypochlorites and ammonium salts. Ammonium hypochlorite.” By C. F. Cross and K. J. Bevan. No mention is made of ammonium hypochlorite in the later text- books and dictionaries ; in the last edition of &eZi?z (vol.2, 479), however, there is a short paragraph headed “Ammonium hypo- chlorite?” in which its probable existence is spoken of on the authority of Sclionbein. This chemist observed that a pungent odour is developed when ammonia is added to chlorine-water, and that the liquid exhibits bleaching powers and the property of decomposing hydrogen peroxide with liberation of oxygen : hence it was supposed that the destructive action of chlorine on ammonia is preceded by the formation of ammonium hypochlorite. The authors have recently had occasioii to study the subject more closely. On treating a dilute solution of bleaching powder with the equivalent quantity of an ammonium salt, no sensible loss of “ avail-able chlorine” takes place provided interaction occur at a, low temperature (loG).The pungent odour already mentioned as noticed by Schonbein suggested that the resulting compound was volatile, and, therefore, in order to obtain evidence as to its composition, a current of air was passed through the solution and subsequently through water and through a solution of potassium iodide acidified with normal acid ; eventually the liberated iodine was titrated with thiosulphate and the excess of acid was determined in the same solu- tion by means of normal alkali. The iodine liberated was taken as equivalent to the chlorine, and the amount of acid saturated as equivalent to ammonia ; the results obtained were- (1.) C1 = 0.0365 NH, = 0*0090 2.06 :I (2.) C1 = 0.0316 NH4 = 0.0081 1.98 : 1.These correspond with the formula NH,OCl, in which the ratio of oxidising chlorine to ammonium is that of 2C1: NH,. Further evidence as to the compcsition of the compound was obtained by extracting the aqueous solution with ether, and after diluting the extract with alcohol adding potassium iodide and the necessary quantity of thio- sulphate : the resulting mixture was neutral. The compound was also volatilised by means of a current of air, which was then washed and passed into a solution of sodium sulphite ; the oxidation of the sulphite was the only change observed, the solution remaining neutral, whereas had no ammonia been present it would necessarily have been acid.The evidence of the formation and existence of ammonium hypo- chlorite in solution would seem, therefore, to be complete ; the isolation of such a compound, however, would necessarily be attended with cdnsiderable difficulty, and all attempts in this direction have hitherto failed to give a result. At ordinary temperatures solutions prepared as described contain- ing from 1to 2 gi ams Cl Fer 100 lose oxidising chlorine comparatively rapidly: thus one containing 1.6 grams per 100 immediately after preparation contained after filtering and standing 2 hours 0.12 gram ; after 48 hours 0.06, and after 72 hours 0.04. The ammonia product presents curious anomalies in oxidising pro-perties in comparison with other hypochlorites : thus it is without, action on many colourinp matters, e.g., those of the vegetable fibre; a solution tinged with a drop of a solution of indigo sulphonate retains its colour for some hours, although it at once liberates iodine from potassium iodide ; and it does not peroxidise hydrated lead oxide, nor does it oxidise potassium ferrocyanide in presence of acetic acid.But it' oxidises sulphites and arsenites, and its effect on anjline sfilts is identical with that of ordinary hypochlori tes. The coinpound is easily formed Inp the electrolysis of arnmoninln chloride solutions. I) ISCI JS~IOP;. said that a €ew months ago he also had nt-Professor RAMSAT tcrnpted to prepre ammoniuni llgpochlorite, ant1 had f'ouzltl th:lt OIL 24 adding ammonia to hypochlorous acid nitrogen was not given off.It was to be noted that the formula of ammonium hypochlorite was equivalent to that of hydroxplamine hydrochloride. In answer to Professor Dunstan, Mr. CROSS said that the addition of acid did not alter the properties of the liquid as an oxidising agent. Dr. ARMSTRONGsuggested that probably the authors were dealing with a chlorinated derivative of ammonia, e.g., NH,C1: Gattermann's experiments show that such compounds are more stable than is usually supposed. 13. " The action of phosphoric anhydride on stearic acid." By F. Stanley Kipping, Ph.D., D.Sc., Heriot Watt College. It is stated in both editions of Beilstein that when stearic acid ie heated with phosphoric anhydride it yields a compound of the formula ClaHarO, melting at 54-56', insoluble in potash.As the formation of a compound so related to the acid in this manner appeared remarkable, being I believe, without a parallel, I have re-examined the subject, and am led to give a brief account of my results in order to reserve the study of this and similar changes. If stearic acid be heated at about 200" in an oil-bath, and about an equal weight of phosphoric anhydride be added in small portions at a time, the whole beiug well stirred, a considerable quantity of gas is evolved and a black, tarry mass is obtained. The mixture is allowed to cool, then stirred with water and the whole boiled for some time With a large excess of moderately concentrated potash in order to remove the phosphoric acid.A dark-brown, almost black oil collects on the surface and, on cooling, solidifies to a soft, waxy cake ; this product is separated from the alkaline solution, washed with water, transferred to a flask and repeatedly extracted with boil- ing dilute alcohol. The alcoholic extracts deposit, on cooling, a yellowish, flocculent substrance, and there remains in the flask a dark- brown, waxy mass which is very sparingly soluble in dilute alcohol ; this residue is being investigated. The compound which separates from the alcoholic solution can be obtained in a colourless condition by repeatedly recrystalljsing it from alcohol and ether. It crystallises in colourless, waxy, microscopic plates, and is only sparingly soluble in cold ether and alcohol, but much more readily in the warm solvents and in benzene ; it seems to be insoluble in hot potash or in ammonia.When heated slowly in acapillary tube it begins to soften at 73" and melts completely at 75-76", or about 3" higher than stearic acid. On combustion, 0.1420 gram gave 0.4316 gram CO, and 0.1771 gram HzO. 25 C18H340. c18H3602. c35H700-Found. C = 81.20 76-27 83.00 82.88 per cent. H= 12.78 12.68 13.83 13.85 ,, 0 = 6.02 11.05 3.17 3.27 ,, The results show clearly that the compound is not simply un-changed stearic acid, a fact which is further proved by the higher melting point, and that it has not the composition Cl8H34Ois apparent from the high percentage of hydrogen which it contains.The results of the analysis agree very closely with the formula C3&00, and the experiment described below confirms this conclusion. It seems, then, that when stearic acid is heated with phosphoric anhydride, under the conditions described above, one of the products is stearone, and that action takes place according to the equation: 2Cl7H3,-COOH= (C,,H,,),CO + CO, + H,O. Quantitative experi- ments have not yet been made, but the yield appears to be as good, or better, than that obtained in preparing stearone by the distillation of salts of stearic acid. Stearone has been previously prepared by Heintz (Jahresb.,1855, 515, 516) by distilling stearie acid alone or with lime ; Heintz gives 87.8" as the melting point, whereas the compound obtained as described above melts at 75-76".The cause of this difference has not yet been ascertained, but it is probably due to the presence of impurities too small in quantity to have any effect on the analysis. The stearic acid employed melted at about 62" ; the experiments will be repeated with the pure acid. Stearonehydroxinw (C,,H,,),C:N*ON. A small quantity of the colourless, crystalline componiid (m.p. 75-76') was dissolved in warm alcohol and boiled for about three hours with excess of hy-droxylamine and a large excess of potash. On cooling the solution and adding water, a colourless, flocculent substance was precipitated ; the solution was filtered, the precipitate washed repeatedly, first with dilute hydrochloric acid and then with water, and dried on a porous plate. 0.2514 gram gave 6.6 C.C.of nitrogen at 755 mm. and 40", or 2-65' per cent. ; the theoretical percentage corresponding to the formula C,,H,,NO is 3.07 per cent. This Iiydroxime is a colouialess, seemingly amorphous compound readily soluble in benzene and warm alcohol, but insoluble in acids and in alkalis. When heated very slowly in a capillary tube, it begins to soften at about 53" and melts completely at 58-59'. It separat,es from alcohol as a powder which, when examined under the microscope, appears to be perfectly homo- geneous. 14. " Semithiocarbazides.'' By Augustus E. Dixon, M .D. Orthotoly223henylseinithiocarbuLide (from o-tolylthiocarbamide and 26 phenylhydrazine) forms vitreous prisms melting at 162-163".It is nearly insoluble in water ; soluble in alcohol, ether and chloroform. YhenyZorthotoZylsemithiocarbazide (from phenylthiocarbimide and o-tolylhydrazine) is isomeric with the preceding. It forms long, pearly-white prisms melting at 145-146" ; it is nearly insoluble in water, but dissolves freely in alcohol, ether and chloroform. 2Methylp~enyZsemn,ithiocal.baz.ideforms delicate, silky needles melting between 88" and 89". It is somewhat soluble in hot water; very soluble in alcohol and in chloroform. Et72ylorthotoZ~lsemithiocarbazide crystallises from alcohol, in which it is rather freely soluble, in fine, white needles possessing a faint pink tinge. It melts at 129-130"; is insoluble in cold water, but dissolves freely in ether and chloroform.All~lphenylsernithiocarbazide separates from benzene in tangled masses of silvery-white, flexible needles, which become highly electrical on friction ; it melts at 118-119" to a bluish-green liquid. It is soluble in ordinary solvents, but is precipitated from solution in benzene by light petroleum. Tbese compounds all give with concentrated sulphuric acid solutions varying in colour from greenish-blue to deep azure. They are desulphurised, either with great, difficulty, or not at all, by boiling alkaline lead tartrate ; but readily yield their sulphur to ammonincal silver nitrate. With CuS04 or Fe2C16they afford strongly-marked colour changes. The connexion between the solubility and fusibility of the several compounds is traced, and it is shown that, as a rule, Carnelley's prin- ciple holds good that the greater the solubility the lower is the melting point ; the author also suggests ail application of Carnelley's principle to connect the melting points with the molecular structure. 15."Note on the production of ozone by flames." By J. Tudor Cundall, B.Sc., University College, Cardiff. It is stated by L. Ilosvay de N. Ilosva (Ber. Befemte, 1889, 791 et sq.) that when the products of combustion of various kinds of flames are collected, they do not exhibit the smell and taste of ozone. This is confirmed by the results of some unpublished experiments made by the author in it similar manner in 1886. Recently, however, the author has found that the air aspirated through a tube (3 mm.in bore) whose mouth is fixed about 5 mm. above the tube, and 5 mm. away from the flame, of a Bunsen burner, both tastes and smells strongly of ozone. Similar results were obtained both from luminous and hydrogen flames. It was not found possible to confirm this fact by any other. test for 27 ozone, owing to the impossibility of finding any which was sufficiently sensitive which was not common to it and dilute nitrogen oxides. At first sight, it seemed that Houzeau’s papers (impregnated with red litmus and potassium iodide) would give the necessary distinction, as an acid gas could not be expected to give an alkaline product. Ilosva states, however, that aitrogen oxides turn these papers blue, and the author has confirmed this result.Papers impregnated with thallium hydroxide were employed with negative results, but, on testing them in a stream of ozonised oxygen from a Siemens tube, they were found to be far from sensitive. The same applies to an acidified solution of sulphanilic acid and as-napthylamine, which certainly gives a yellow colour with a fair amount of ozone, but this colour is completely masked by the rose-red produced by small traces of nitroge2 oxides which may be present simultaneously. The gas aspirated in this way both from coal gas and hydrogen flumes gave definite indications with mercury of the peculiar behaviour of ozone, but the quantity present was not sufficient to make the mercury adhere completely to its containing flask.In conclusion, the author agrees with Ilosva in so far that he regards the smell and taste of ozone as the only tests for it that are at all reliable when it is present only in traces, but differs from him as regards its formation in flames; although nitrogen oxides are undoubtedly formed in flames, yet at the same time ozone can be detected by aspirating the air surrounding the flame in such a manner as to get a minimum of the products of combustion and at as low a temperature as possible. ANNIVERSARY MEETING. The anniversary meeting will be held at Four o’cJocJG in, the After-noon of Thursday, March 27th next. It is arranged that, in the evening of the same day, the Fellows and their friends will dine together at the Whitehall Rooms, Hatel M6tropole (entrance in Whitehall Placej.Dinner will be on the table at seven for half-past seven o’clock. Fellows intending to be present are particularly requested to give notice by means of a post- card which they will receive for the purpose not later than Saturday, March 22nd. Price of dinner, including wine, One Guinea. It is proposed to hold a special meet’ing of the Society on Thursday, May 8th, for the exhibition of new interesting apparatus or specimens. Fellows who desire to exhibit objects are requested to communicat’e with the Secretaries. 28 At the meeting on March 20th, Professor Judd, F.R.S., will delivela a lecture on the evidence aeflorded by petrographical yesearch of the occurrence of chefnical change wader great pressures.At the next meeting, on Thursday, March 6th, the following candi- dates will be balloted for :-1. Anderson, Frederick Alfred, B.Sc., Lesney House, Erith, Kent. 2. Babington, Percival, Elmfield, Rotherham, Yorks. 3. Beardmore, G. R-~issell,M.D., Warwick House, Upper Street, Isling ton. 4. Berncastel, Richard, 38, Ventnor Villas, Brig11ton. 5. Blount, Bertram, 1,Broadway, Westminsher. 6. Blake, Robert Frederick, 37, Hartjington Street, Dublin Road, Belfast. 7. Bunting, Henry Herbert, 82, Netherwood Road, Kensington, W. 8. Burton, William, 18,Victoria, Street, Stoke-on-Trent. 9. Cobbold, Paul Alexander, Warwick School, Warwick.10. Dennant, John, Lyndhurst Crescent, Glenferrie, Melbourne 11. Gossling, Frank, Waldegrave Road, Teddington. 12. Jackson, John Charles, 51, Wellington Road, St. John’s Wood. 13. Lumsden, John S., 5, Paradise Road, Dundee. 14. Macintyre, Alfred E., Saint John, N.B., Canada. 15. Mills, Frederick, Bevnii Crescent, Stockton-oil-Tees. 16. Moore, Ira, Sntton, Crosshills, vid Keighley. 17. Myles, John, Butterburn Park, Hamilton. 18. Rothwell, Robert Richard, 82, Mawson Street, Ardwick Green, Manchester. 19. Sargeant, Edward, 75, Park Road, Bolton. 20. Valentin, Basil William, Acton Brewery, Birmingham, The following papers will be read:- “Crystalline products derived from various species of Citrus.” By Professor Tilden, F.R.S., and C. R. Beck. “ Reduction of a-Diketones.” By Dr. Japp, F.R.S., and Dr-. Klingemann. “ Studies on Isomeric change. Halogen-derivatives of quinone.” By A. R. Ling. HARRISON AND SONS, PRINTERS IN ORDINARY TO HER MAJESTY, ST. MARTIN’S LANE.
ISSN:0369-8718
DOI:10.1039/PL8900600019
出版商:RSC
年代:1890
数据来源: RSC
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