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Proceedings of the Chemical Society, Vol. 18, No. 247 |
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Proceedings of the Chemical Society, London,
Volume 18,
Issue 247,
1902,
Page 39-50
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摘要:
Tssued 28/2/02 PROCEEDINGS OF THE CHEMICAL SOCIETY. EDITED BY THE SECRETARIES. Vol. 18. No. 247. February 19th, 1902. Prof. J. EMERSON Sc.D,, V.P.R.S,,REYNOLDS, President, in the Chair. Messrs. E. A. Lewis, R.A. Berry, H. W. Cromther and H. 0. Jones were formally admitted Fellows of the Society. Certificates were read for the first time in favour of Messrs : Bergtheil, Cyril, Checkley, Red Hill, Surrey. Boardman, Ernest, 41, Knowsley Road, Smithilis, Bolton. Davis, Charles Benson, 218, West 134th Street, New York, U.S.A. Hopwood, Arthur, 49, Stanley Street, Tunstall. Roberts, Jonathan Hugh, Oban Gwys, Swansea. Trimen, Stephen Herbert, 61, St. John’s Park, N. Tunnicliffe, William Wright, Newhall, Burton-on-Trent, Wain, William Charles, Mercantile Explosive Dept .,Sydney, N.S.W. It was announced that the following changes in the Officers and Council were proposed by the Council : As Vice-presidents : Prof. Meldola, F.R.S., and Prof. Frankland, F.R.S., vice Mr. Groves, F.R.S., and Prof. Purdie, F.R.S. As Foreign Secretary ;Prof. W. Ramsay, F.R.S., vice Prof. Meldola, F.R.S. As Ordinary Members of Council: Nr, J. E. Marsh, Dr. J. A. Voelcker, Dr. A. Harden, and Dr. Lewkowitsch, vice Mr. Fenton, F.R.S., Mr. Howard, Mr. Pope, and Dr. Crossley. Mi-.A. C. Chapman, Dr. Hewitt, and Dr. Thorne were appointed to audit the Society’s accounts. 40 A Ballot for the Election of Fellows was held and the following were subsequently declared duly elected : Keith Benhani Benhani. Mr.Holdsworth Hurtly, D.Sc. Walter Geoffrey Black. William Brannan Jackson. Harry Burrows, Ph.D. David S. Smith Jardin. T. K. Buxy, M.A. Selwyn Philip James Lavelle. Frederick E. Catchpole, B.Sc. Harry Lucas. Matthew Bradbury Challen. Ernest Bowman Ludlam, B.Sc. Kenneth Macomb Chance, B. A. John Ross Mackenzie. William Clifford. William Maitland, E.Sc. James Ward Daniels. Francis Martin. Frederick Davis, B. Sc. Francis Hylton Molesworth. Evelyn Andros De la Rue, B.A. Alfred Holley Mundey. v\Tilliam Dennis. Allan Ogilvie. John Kemp Smith Dixon. Sydney Glyde Stephen Panisset. Charles DorEe, M.A. William Charles Ross. Lewis Eynon. Ncvil Vincent Sidgwick, M.A., D.Sc. Alfred Vincent Elsden. Frank Sturdy Sinnatt. Eughe Arthur Fasnacht.Robert Eley Blake Smith, B. Sc. Frederick Ferrand. JTilliam Southworth. John Oliver Ferrier. Francis Bernard Stead, B. A. Clarence J. Green, B.Sc. James Swain. Paul Haas, 13.Sc., Ph. D. Lyon Viccars Turner. Noel Heaton, RSc. Arthur James Webb, B.A. Eugene Edwin Hennesey, B.A., B.Sc. Charles Edward Womersley. George Frederick Holdcroft. Of the following papers, those marked * were read : *24. The union of hydrogen and oxygen.” By H.B.Baker. Experiments have been made during the last ten years by H. B. Dixon, Victor Meyer, and by the author, with the object of seeing if the presence of moisture had any influence on the union of hydrogen and oxygen. These experiments have led to negative results. By the use of a new method of preparing very pure hydrogen and oxygen, namely, by the electrolysis of a solution of very pure barium hydroxide, the author has succeeded in preparing these gases so pure and dry that tubes containing them can be heated to redness without union of the gases, whilst tubes containing the undried gases, heated side by side with the dried tubes, readily explode.On the introduction of a small quantity of distilled water into the dried tubes, explosion follows at once. In gases which had been allowed to stand for two days only in contact with distilled phosphorus pentoxide, only a slow combination took place, so slowly that in one case ten minutes’ heating in the flame of a Bunsen 41 burner caused the union of only one-third of the partially dried gases.It seems therefore that water is not the only determining factor in the explosion of the heated mixture. In order to see if a still higher temperature would bring about the union, coils of very pure silver wire were heated by an electric current in the dried mixture, when it was found that the silver could be heated to its melting point without causing union. Experiments have also been made with the object of finding out if the moist gases were measurably dissociated whilst the dry gases were not. By a device of Professor Edward Morley’s, used for another purpose, gases were sealed up in tubes in which a contraction of less than 1/7000th of their volume could be detected. The gases were dried before their introduction into the tubes by simply passing them through a phosphorus pentoxide tube.They were then left in contact with the pentoxide for six months. No contraction, even to the small extent above noted, could be observed. The gases tested thus were hydrogen, oxygen, nitrogen, air, and a mixture of hydrogen and oxygen. These tubes were kept in a dark room during the whole period. It was found that a moist mixture of hydrogen and oxygen united slowly in sunlight, which may perhaps account for some previous failures to get the gases dry enough not to unite. In the first series of experiments above described, the mixed gases mere kept in darkness during their contact with the phosphorus pentoxide, lest the action of the drying agent should not be sufficiently rapid to cope with the water being produced by their union.*25. (( Enzyme action.” By A. J. Brown. The author has already shown (Trans., 1892, 61, 380) that in alcoholic fermentation a constant weight of sugar is decomposed in unit time by a constant amount of yeast in solutions of equal volume containing different amounts of sugar, and has called attention to the fact that in this respect the action of fermentation differs essentialIy from that of inversion, which, according to C. O’Sullivan and Tompson (Trans., 1890, 57, 865), follows the law of mass action. At the time the author described his work, the phenomenon of fermentation was believed to be a life function inseparable from the living cell, and therefore it did not appear remarkable that the order of progression of its action should differ from that of inversion; but since Buchner has shown that fermentation, like inversion, is an enzyme action, this point of difference required further investigation as the simple mass action of invertase demonstrated by O’Sullivan and Tompson is often regarded as typical of all forms of enzyme action.The author has examined the action of invertase on cane sugar, and 42 finds that the velocity of its action differs essentially from that of a mass action, and resembles that of fermentation. The velocity of its action represented graphically approximates a straight line when not influenced by the accumulation of inversion products. The retarding influence of inversion products occasions the curve found by O'Sullivan and Tompson, and these authors were mistaken in regarding the curve as the logarithmic curve of mass action.In a true mass action the value K, derived from the expression K= 1 log -,for any point 1 -x of the action is a constant, but this is not the case in inversion changes in which the products of inversion accumulate. On the con- trary, for such changes the value 2R is nearly constant when derived from the expression, recently suggested by Henri (Compt. rend., 1901, 133,89l), 2K= -1 log 1-X' -an expression differing essentially from e that representing the progress of a mass action, But although the action of inversion does not follow the law of mass action, it cannot be independent of mass influence, and there- fore the effect of mass during inversion change must be restricted by some other influence.This influence the author believes to be due to the existence of time as a factor in the complex changes which probably accompany inversion. In any simple chemical change the influence of mass regulates the number of molecular contacts between acting and reacting molecules in unit time; but if a time factor enters into a molecular reaction there must be a point beyond which the number of molecular changes cannot increase owing to the restriction of time in the action, and this point will be determined by the relative frequency of molecular contact and the relative length of the time interval of molecular change. There is good reason to believe that during the inversion of sucrose, this sugar enters into molecular combination with invertase previous to change, which presupposes a complex change and the existence of a time factor of some magnitude. Under these con-ditions it therefore appears more probable that this factor limits the effect of mass action in inversion changes in solutions of ordinary concentration.But if this is so, there must be a point of dilution in cane sugar solutions when invertase, acting in the dilute solutions, should exhibit an order of change in conformity with simple mass action. The author shows by direct experiment that this point is reached in a solution containing about 1 per cent. of cane sugar, so far confirming the conclusion that a time factor accompanying molecular change limits the action of inversion in all but very dilute solutions of cane sugar.The action of alcoholic fermentation follows the same order of 43 progression as that of inversion, and the work of Kastle and Loeven- hart (Amer. Chem. Journ., 1900, 24, 491) indicates that the action of lipase progresses in the same manner,-it therefore appears probable that both these enzyme actions are regulated, like inversion, by a time factor. With regard to the actions of such enzymes as diastase, glucase, and peptase there is not at present sufficient evidence on which to base an opinion. *26. “On the velocity of hydrolysis of starch by diastase with some remarks on enzyme action.” By H. T. Brown and T.A. Glendinning. The rate of change during the hydrolysis of starch by diastase does not conform to the simple logarithmic law of a unimolecular reaction. Throughout the hydrolysis there is a steady augmentation of the coefficient of velocity ;in other words, within any given time interval there iis more of the residual substance hydrolysed than there should be according to the logarithmic formula. The results are in the wrong direction to be accounted for by a gradual accumulation of the products of change with a consequent tendency to chemical reversion, nor can they be explained by the intermediate products of change exhibiting a differential resistance to hydrolysis. If the time curres expressing the rate of hydrolysis of a 3 per cent. solution of soluble starch are critically examined, ib is found that up to a hydrolysis of 30 to 40 per cent.the amount of transforma- tionis very nearly a linear function of the time. A further analysis of the curve shows that the remainder is approximately logarithmic. In all essentials, the progress of the hydrolysis of starch coincides with that of the inversion of cane-sugar by invertase, as shown by Adrian Brown in the previous paper. The rate of hydrolysis also conforms closely with the empirical formula of Henri for the inversion of cane sugar. The authors are inclined to adopt a somewhat different explanation of the time curves of hydrolysis from that suggested by Adrian Brown, and one which does not postulate any difference in the time intervals between the successive stages of the reaction other than those due to variations in the respective masses of the reacting substances existing in unit volume.This hypothesis has been fully elaborated, and an attempt is also made to link the phenomena of enzyme hydrolysis with those of acid hydrolysis, the water ions, or the active dissociated water molecules, being in both cases regarded as the true hydrolysts. *27. Polymerisation products from diazoacetic ester.” By 0, Silberrad, Ph.D. In this research, which is a continuation of work already published (Hantzsch and Silberrad, Ber., 1900, 33,58),the polymers of diazo-acetamide are dealt with. The investigation has led to the discovery of a third series of polymeric products from diazoacetic ester, of which the most stable representative appears to be the amide.This compound, which was formerly known as ‘‘ pseudodiazoacetamide, C3HN4(NH),(C10WH,),,”is now shown to be imidoazoacetamide, NH:C(CONH,) *N:N.C(CONH,)NH. Its constitution has been estab- lished chiefly by a comparative study of the action of reagents on this compound and on its isomerides in the other two series of polymeric derivatives of diazoacetamide, namely, the C-and N-dihydroteti*axine-dicas.boxyZamides, the latter of which has been prepared for the first time. Of the reactions studied, that with alkalis may be taken as characteristic. In the case of the C-and N-dihydrotetrazine-dicarboxylamides saponification occurs in a perfectly normal manner ; neither substance shows any inclination to form salts as imidoazo- acetamide does.In the presence of mercury, however, X-dihydro- tetrazinedicsrboxylamide forms a compound of such stability that prolonged boiling with concentrated sodium hydroxide entirely fails to saponify the amide. With pseudodiazoacetamide an imido-salt of the amide is first produced, as, for example, the ammonium salt NH:C(CONH,)N:N*C(CONH,)N(NH4). It was the analysis of these salts which first showed the compound to be a dimolecular polymer of diazoacetamide. Secondary reactions subsequently occur thus (1) Baryta water on warming produces barium imidoazoacetate g*C(NH)CO, (2) The prolonged action of aqueous ammonia at N *C(NH)COz>Ba.NHordinary temperatures gives rise to isodiazoacetarnide, CONH,*C< IN together with a small quantity of diazoacetamide. The constitution of the former was deduced chiefly from its action on benzaldehyde, with which it forms benzalazine, N,(CHC,H,),. (3) Concentrated sodium hydroxide at 100’ gives rise to bisdiazoacetic acid, CO,H*CH<:~:>CH*CO,H. The action of nitric oxide is also wcrthy of note as by its means either triazole nitrate, CH<z!?E%>CH (a derivative of N-di- - 45 /O\N-Nhydrotetrazine), or bisazoxyacetic acid, CO,H.CH<N-N>CH*CO,H \O' (a derivative of C-dihydrotetrazine), can be obtained at will. 28. Condensation of phenols with esters of unsaturated acids. Part VII." By S. Ruhemann. Benzo-1 :4-pyrone (chromone) and its homologues have basic pro- perties ; they dissolve in hydrochloric acid to form hydrochlorides, and these solutions yield platinichlorides ; but the salts are unstable and are decomposed by water with re-formation of the benzopyrones.The author having been unable to obtain hydroxybenzo-1 :4-pyrones from the dihydric phenols, has attempted to prepare them by starting from their mono-ethers, and from guaiacol and ethyl chlorofumarate has obtained ethyl guaiacoxyfumarate, (1)(CH,O)*C,H,$*C( CO,E t):CH*CO,Et, a yellow oil, b. p. 212-213O (at 15 mm.) and the corresponding acid (m. p. 138' with decomposition); on treatment of this acid with strong sulphuric acid a compound was obtained which is most prob- ably methoxybenzo-1 :4-pgronecarboxylic acid.This the author in- tends to transform into 0-hydroxybenzo-1 :4-pyrone. It was further shown that the action of ethyl chlorofamarate on a-naphthol differs from the behaviour of the ester towards P-naph- thol, for whilst with the latter it yields ethyl P-naphthoxyfumarats, C,,H70*C(C0,Et):CH*C0,Et,a yellow, fluorescent oil, b. p. 240-242' (pressure 12 mm.), which on hydrolysis is transformed into the corre- sponding acid, yellowish plates, m. p. 236' with decomposition, it reacts with a-naphthol to form in addition to a small quantity of ethyl a-naphthoxyfumarate, two substances which belong to a new class of compounds. One has the formula C,,H,,O,, and crystal- lises in yellow needles, m. p. 146-147'; the other has the formula C24H1204,it forms orange needles which do not melt at 335O, are in- soluble in the ordinary solvents, but dissolve in boiling nitro-benzene.The first compound is regarded as a derivative of the '-/ bH,, called ncqAtharone, and as having the con-\-/' stitution /\-’\--c()/ \C:CH*C02Et, ethyl naphtharonylacetate, \-/whilst the compound C24H,20, is represented by the formula /-\-/-‘\\-/ cO\C:C/co-\\o--/-\ / and termed bisnaphtharongl./ \--/\-/ \-/Reasons for assigning these constitutions, and the description of some derivatives of these compounds, were given by the author. 29. “The chemical change produced by the immersion of lead in distilled water.” By F. Clowes, D.Sc. The author finds when very pure lead and ordinary distilled water Were employed that much of the lead which underwent change passed into solution most probably as hydroxide, and was removable to a large extent from solution by passage through filter paper, from which it could again be entirely extracted by cold acetic acid.The compound of lead which remained undissolved by the water was found to have the formula 3PbC0,,PbH202. In order to ascertain the respective parts played by atmospheric oxygen and carbon dioxide in solution, distilled water freed from dissolved gases by boiling was employed. When such water was placed in contact with lead in a vacuum or in an atmosphere of hydrogen, action only took place to the extent of 0.3 part of lead per million of water.When the water employed had been boiled in glass vessels and again exposed to air it never regained its full activity. This inhibitive effect varied with different glass vessels, being most marked in those kinds of glass which gave most dissolved matter to the water; contact of cold water and glass did not produce this effect, which was eliminated, however, in the experiments, the results of which are given below, by boiling the water employed in copper vessels. The average results, expressed as percentages of lead in terms of the water employed, are shown in the following table : 24 hours. 48 hours. 72 hours. Oxygen alone ................................. 0.013 0.023 0.029 Carbon dioxide alone ........................ 0.005 0.008 0.017 Equal volumes of carbon dioxide and oxygen ....................................... 0.003 0.003 0.003 Eight volumes of oxygen to one volume of carbon dioxide ...........................0.015 0.018 - 47 This shows clearly that oxygen is the principal and primary agent, and that carbon dioxide exerts a restraining action in proportion to the volume present. It was found that carbon dioxide acted similarly in preventing solution of litharge. The first action of aerated water apparently consists in oxidation and formation of hydroxide, which is precipitated as hydroxycarbonate by the carbon dioxide. The action is prevented or retarded by the presence of carbon dioxide in the initial stages. Total immersion of the lead also retards the action in presence of air, although the final result is the same whether the lead be wholly or only partially immersed in the water.Of the substances which prevent this action, sulphuric acid and soluble sulphates are most effective, soluble carbonates are less so, whilst calcium hydroxide is still less so, but when present in larger quantity actually promotes the action. 30. The bases contained in Scottish shale oil. Part I.” By F: C. Garrett and J. A. Smythe. The authors are continuing the examination of the bases contained in the Broxburn shale oil, of which a short account has been already given (Proc., 1900, 16,190) and have completed tho investigation of the portion boiling below 164’. The following bases have been isolated and identified : Pyridine, b.p. 115-116’ (in very small quantity). a-Picoline, b. p. 129.5’ (bar. 763 mm.). ay-Dimethyl pyridine, b. p. 159-159-5’. 99apl-,? b. p. 154-155’. t aa-,, ,, b. p. 142.5’ (bar. 760 mm.). aya’-Trimethyl pyridine, b. p. 170.5’ (bar. 760 mm.). ap’-Dimethyl pydine is a colourless liquid with a strong pyridine- like odour; it gives a picrate, m. p. 151-152’; a gold compound, m. p. 156-157’ ;a platinichloride containing 2 molecules of water and melting (when anhydrous) at 238’ with decomposition; and a mercuri-chloride (CrH,,HCI,6HgCI,) in very small, heavy crystals, m. p. 1639 31. “Note on ‘liquid nitrogen peroxide as a solvent.’ ” By P. F. Frankland, F.R.S.,and R. C. Farmer, Ph.D. In the authors’ recent communication on liquid nitrogen peroxide as a solvent ” (Trans.,1901, ’79,1356), they inadvertently omitted to men- tion the previous work of Bruni and Berti (Gccxx.chim. .Ii!tlZ., 1900, 30,ii, 151), of which they mere not cognisant at the time. 48 It is fortunate that, whilst the two papers deal to some extent with the same subject, the experimental results do not to any great extent overlap, but rather supplement each other. Bruni and Berti concerned themselves principally with cryoscopic measurements, and thus extended the still earlier work of Ramsay (Trans., 1890, 57, 590), whereas the authors have investigated the electric conductivity and ebullioscopic behaviour of the solutions of a considerable number of different substances in the liquid peroxide, be- sides making a somewhat extensive examination of the action of the latter on a number of other substances, organic and inorganic.The crgoscopic and ebullioscopic determinations agree in showing that the liquid peroxide is in many cases a powerfully associating solvent, and it is noteworthy that Bruni and Berti found acetic acid to be associated to triple molecules at the freezing point of the solvent, whilst the authors’ measurements at the boiling point of the latter only revealed an association to double molecules. The authors desire herewith to express their regret that the important work of these authors had escaped their attention, ADDITIONS TO THE LIBRARY. I. By Donation. Ditte, Alfred. Introduction ii l’htude des metaux.Pp. 488. Paris 1902. From the Author. White, Edmund, and John Humphrey, Pharmacopedia, a commentary on the British Pharmacopceia, 1898. Pp. 696. 111. London 1901. From the Authors. 11. Pccmplzleis. Richards, Theodore William. The relation of the taste of acids to their degree of dissociation. 11. (From The Joumal of Physicd Chemistry, vol. iv, No. 3, March, p. 207.) From the Author. Richards, Theodore William. Suggestion concerning the nornen-cIature of heat capacity. (From the Proceedings of the Americniz Academy of Arts and Sciences, vol. xxxvi, No. 18, January, 1901.) Prom the Author. Richards, Theodore William. The possible significance of changing 49 atomic volume, (From the Proceedings oj the Anze&an Academy Arts and Sciences, vol. xxxvii, No.1,June, 1901.) Prom the Author Richards, Theodore William. The significance of changing atomic volume. 11. The probable source of the heat of chemical combination, and a new atomic hypothesis. (From the Pvoceedings of the American Academy of Arts chnd Sciences, vol. xxxvii, No. 15, February, 1902.) From the Author, Richards, Theodore William. Modification of Hempel’s gas appar -atus. (From the Proceedings of t?Le American Academy of Arts and Xciences, vol. xxxvii, No. 10, November, 1901.) From the Author. Richards, Theodore William, and Frank Roy Fraprie. The solu- bility of manganous sulphate. (From the Proceedings of the American Academy of Arts and Sciences, vol. xxxvi, No. 28, April, 1901.) From the Authors.Richards, Theodore William, and Ebenezer Henry Archibald. The decomposition of mercurou8 chloride by dissolved chlorides : a contri-bhtion to the study of concentrated solutions. (From the Y?*oceedings of the American Academy of Arts and sciences, vol. xxxvii, No. 13, January, 1902.) From the Authors. Richards, Theodore William, Charles F. McCaff rey, and Harold Bisbee. The occlusion of magnesic oxalate by calcic oxalate, and the solubility of calcic oxalate. (From the Proceedings of the American Academy of Arts and ,Sciences, vol. xxxvi, No. 22, April, 1901.) From the Authors. Richards, Theodore William, and Ben jsmin Shores Merigold. A new investigation concerning the atomic weight of uranium. (From the Proceedings of the American Acadenap of Avts and Sciences, vol.xxxvij, No. 14, February, 1902.) From the Authors. 50 At the next meeting, on Thursday, March 6th, at 8 p.m., the following papers will be communicated : “The slow oxidation of methane at low temperatures.” By W. A. Bone and R. Y. Wheeler. (‘Isomeric additive compounds of dibenzyl ketone and deoxybenzoin with benzalp-toluidine, m-nitrobenzalaniline and benzal-via-nitraniline. Part 111.” By F. E. Francis. ‘(Mesoxalic semi-aldehyde.” By H. J. H. Fenton and J. H. Ryffel.‘‘ .~-il-Nitrobenzoylcamphor.” By N,0. Forster and Miss F. M. G. Micklethwait. ‘(Picrimidothiocarbonic esters.” By J. C. Crocker. ‘(The identity of osyritin and myrticolorin.” By A. G. Perkin. RICHARD CLAY AYD SONS, LIMITED, LONDON AND BUNOAT.
ISSN:0369-8718
DOI:10.1039/PL9021800039
出版商:RSC
年代:1902
数据来源: RSC
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