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Abstracts of the Proceedings of the Chemical Society, Vol. 4, No. 47 |
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Proceedings of the Chemical Society, London,
Volume 4,
Issue 47,
1888,
Page 7-16
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摘要:
ABSTRACTS OF THE PROCEEDINGS OF THE CHEMICAL SOCIETY. No. 47. Session 1887-88. February ‘Lnd, 1888. Mr. William Crookes, F.R.S., President, in the Chair. Certificates were read for the first time in favour of Messrs. Thomas Ashcroft Ellwood, 46, St. Mary’s Terrace, Paddington ; James H. Gardiner, 6, Bloemfontine Avenue, Uxbridge Road, W.; Charles E. Munroe, Newport, Rhode Island, U.S.A. ; Herbert Trewby, Langford Lodge, Clapham Park, S.W. ; Thomas Edward Towerson, care of Messrs. R. Hammond and Co., Bilbao, Spain. Professors Geuther, Ladenburg, Landolt, Nilson, Van’t Hoff, Wislicenus and M. Lecoq de Boisbaudran were elected Foreign Members of the Society. The following were elected Fellows of the Society :-Messrs. Edward Arthur Andrews, Samuel Banner, Arthur G.Bloxam, Peter Coulson Bunn, F. Barker Cooke, Albert W. Day, Philip A. Estcourt, William Cay Forsyth, Agnew Griffith, Lewis Walter Hawkins, John B. Kirk- land, Thomas A. Lawson, Ph.D., Frank E. Lease, Stevenson J. C. G. Macadam, Edmund G. McBrctney, W. Sedgwick Saunders, Frederick W. Shaw, Sidney Skinner, B.A., Charles F. Townsend, Alfred Edwin Tutton. The following lecture was delivered :-5. “ The Range of Molecular Forces.” By A. W. Rucker, M.A., F.R.S. In discussing the range of molecular forces it is convenient to adhere to the language of the theory of action at a distance, though with full expectation that it will ultimately be replaced by another, such as the vortex-atom theory of Sir W. Thomson, or the granular theory of Professor Osborne Reynolds, which involves only action in proximity.If we do this, however, it, must be admitted that the law of mole-ciilar action may be very complicated. It may be granted that we naturally look for simplicity in our fundamental assumptions, but it is certain that we have h priori no more right to expect simplicity in the results of the action of a medium than simplicity in its constitu-tion, and that the two are not necessarily obtained together. The largest values of the magnitude of the radius of molecular action which have been published have been deduced from observa- t<ions on the condensation of gases and vapours on the surfaces of solids. Estimates on this basis made by Miiller-Erzbach (Exiier’s Rep., 1885, 21, 409) and Kayser (Wied.Ann., 1881, 14, 450) have ranged between 1500 and 3000 micromillimetres* (p.~).Such observ- ations are open to many objections. Bunsen (Wied., 1885, 24, 335) has shown that CO, will not condense on glass unless a film of water be previously formed. Warburg and Ihmori (Wied., 1886, 27, 481, and W-ied., 1887. 31, 1006) adduce reasons for believing that the vater film is largely due to uncombined or loosely combined alkalis on the surface. On clean unvarnished metals, washed glass and quartz, the thickness of the water film which can be removed by dry air without heating does not exceed 12 .u.,u. A striking ex-cepttion is agate, on which films 1640 p,p. ttiick are stated to have been formed. As this substance, however, is composed of alternate layers of quartz and a porous impure opal the basis for an accurate calculation does not exist.On the whole, it seems that no definite conclusions as to the mag-nitude of the radius of molecular action (p) can at present be drawn from these experiments. Quincke (Pogg. Ann,., 1869, 137, 402), as is well known, by measur-ing the capillary elevation of liquids between glass plat,es coated with thin wedged-shaped films, found p = 50 p.p. Plateau (Xtatiqzce des Liquides, 1873, 1, 210) showed that the surface-tension of a soap-bubble, which thinned until its thickness was 118 p.,u., was unaltered. He concluded that p < .59 p.p. Max-well (Ency. Brit., Ed. ix, Art. “ Capillary Action ”), however, though by a confessedly imperfect theory, shows that the surface- tension may not change until the thickness of the film = p.Hence Plateau’s result may mean only that p < 118 p.p. Reinold and Riicker (Phil. Tq-ans.,177, Part ii, 1886,627) have proved that the surface-tension does not alter by 0.5 per cent., when the film is so thin as to show the black of the first order of Newton’s * Tlic micromillimetre is thc millionth of a millimetre. colours. This appears at first sight, at variance with Quincke’s result, but their observations are really in remarkable accord with his. The black and coloured parts of a film are separated by B sharp line, which proves a discontinuity in the thickness (PYOC.Roy. Xoc., 1887,No. 182,340).The colours, which correspond to certain thicknesses, which may be called tlhe unstable range of thickness, are always missing. The black part of the film has been proved by Reinold and Rucker (Phil.Trans., Part 11,1883,645) to be of a uniform thickness, which diffeis but little from 12 pp. Sir William Thomnon (PYOC.Royal Institution)and these observers independently amived at the conclu- sion that these curious phenomena are clue to the fact that the surlace- tension diminishes to a minimum, and then increases again when the thickness is somewhat >12 p.p. The colours of the film prove that the upper limit of the range of unstable thickness is between 96 and 45 p.p. Quincke’s result indi- cates that it lies between 100 p.p.and 50 ,u.p., according as we adopt Plateau’s or Maxwell’s views.These calculations are therefore in complete accord. Quincke’s result is not an isolated fact, but is supported by observations on soap films. The statement that 50 p.p. and the radius of molecular action are of the mme order of magnitude may now perhaps rank as an ascertained fact. Another method of investigating the radius of molecular action is based on the phenomena of electrolytic polarisation, by observing the change in the difference of potsntial between a metal and a liquid in which it is immemed, when a gas or metal is deposited on it by electrolysis. In the former case we do not know the density of the gas, in the latter Oberbeck (Wied., 1887, 31, 337) concludes that a plate of platinum is completely polarised by a film of another metal of from 3 to 1p.p.in thickness. The metliod of experiment is, however, open to objections which are indicated by Oberbeck himself. Measurements of the thickness of the double electric layer of Helmholtz, which is closely related to the distance between two con- secutive layers of molecules, have been made by Lippmann (Compt. red, 1882,95, 687), and Oberbeck and Falck (Wid.,1884, 21, 157). The values they give vary between 1and 0.02 p.p. Wiener (Wied., 1887, 31, 624) has studied the alteration in the phase of light reflected from very thin silver plates deposited on mica. He finds that the effect begins to alter when the thickness is reduced to 12 p.,u., and that it was possible to detect a silver film the thickness of which did not exceed 0.2 p.p.The diameter of a molecule is a conventional term for the mean distance of the centres of two molecules during an encounter. It may therefore be different in the liquid and gaseous stat,es. Sir William Thomson (Natural Philosq~hy:Thomson and Tait, Part 11,295, 1883), 10 as the result of his celebrated discussion of this point, concludes that the mean distances between the centres of molecules in liquids (supposed arranged uniformly) is between 0.07 and 0.02 p.,~.,and that the latter quantity is an inferior limit to the diameter of a gaseous molecule. The diameters of molecules (a) may be calculated if we know the mean free path (L), and the so-called condensation coefficient (u), which is the volume of the molecules contained in a unit volume of the gas.Loschmidt (Xitzungsber. Wien. Akad. Jluth. Classe, 52, abt. 2), and 0. Meyer (Die Kinetische TlAeorie der Case, 225, 1887) have calcu- lated d on the assumption that the molecules in a liquid practically fill the whole space it occupies. Exner (Rep. der Physik, 21, 226, 1885), using a formula given by Clausius, 'u = (K -l)/(K + 2), when K is the specific inductive capacity, and which may be replaced by u = (n' -l)/(nz+ a), when n is the refractive index, finds values of d about five times smaller. Three independent methods of calculating the diameter of a gaseous hydrogen molecule lead to results between 0.14 and 0.11 p.p. The most reliable conclusions which have been reached as to molecular magnitudes may be summed up in the following table, which is reproduced from a diagram exhibited during the lecture.Superior limit to p.. ...................... Plateau.1.18 (Maxwel!) . 96-45 Range of unstable thickness begins.. Reinold and ........i Riicker. 59 Superior limit to p.. ........................ Plateau. 50 Magnitude of p ............................ Quincke. Reinold and 12 Range of unstable thickness ends ..........{ Itiicker. 12 Action of silver plate on phase of reflected Wiener.light alters ............................ 1 10.5 Thickness of permanent water film on glass at Bunsen.23°C.. ................................ l-4-3 Mean distance between centres of molecules in 0.Meyer.gases at 760 mm. and 0°C................1 3-1 Thickness of metal films which polarise plati-1 nuin .................................. .J Oberbeck. Lippmann and 1-0.02 Thickness of electric double layer .......... Oberbeck. 0 *2 Smallest appreciable thickncss of silrer film .... Miiener. Exner. 0'14-0 '11 Diameter of gaseous hydrogen molecule.. .... i 0. Meyer. Van der Waals. 0* 07-0 * 02 Maan distmce between centres of liquid mole- W. Thomson.cules.. ............................... I 0.02 Inferior limit. to diameter of gaseoua molecule ., W. Thornson. 11 6. " A New Method of obtaining Monohydrazides of a-Diketones." By Francis R. Japp, F.R.S., and Felix Klingemann, Ph.D. Nitrous acid interacts with ethylic methacetoacetate, forming etbylic isonitrosopropionate, and m-ith methacetoacetic acid forming isonitroso-ethyl-methyl ketone.The authors recently showed (Proc., 1887, 140) that in the first of these reactions the nitrous acid may be replaced by diazo-salts, in which case an ethylic phenylhydrazine- pyruvate is obtained. They now find that the analogy between nitrous acid and diazo-salts extends also to the second reaction. Byacting on sodium methacetoacetate with diazobenzene chloride they have prepared v. Pechmann's monohydraside diacety1:- Ac*CH(CH,)*CO,Ka 4-C,H,.N,Cl = CH,*CO*C*CH,+ GO, + NaCl N.NHC,H, The compound crystallised in short needles, melting at 133", which agrees with v. Pechmann's determination. With phenylhydrazine it yields a compound melting at 243", identical with v.Pechmann's dihydrazide of diacetyl (m. p. 240" ; v. Pechmann). The authors intend to extend this reaction to other alkyl-aceto- acetic acids. 7. "The Formation of Dihydrazides of a-Diketones." By Francis R. Japp, F.R.S., and Felix Klingemann, Ph.D. The authors find that the compound CIGHIPP\TP!which they obtained by heating phenylhydrazinepyruvic (benzene-azopropionic) acid, aiid which is formed according to the equation 2C,H,,N,0z = C16HltrN4+ 2C02 + H, (Sw.,20,2943), is identical with the dihydrazide of diacetyl, since prepared by V. Pechmann (see preceding note). Its formation from phenylh ydrazine-pyruvic acid may be represented thus-CH,-C :(N2HGfiH5)*COGB-CH3*C: (N2H*CfiH5) 4-Hz'CH,.C :(N,E*C,H,)*~COO~E€~ CH:,*C (N,H.C,H,) +-The authors have prepared the corresponding compounds from the tolylhydrazine-pyruvic acids, and are engaged in comparing them with those obtainable from diacetyl and the tolylhydrazines. 8." The Action of Phenylhydrazine on an Unsaturated -/-Diketone." By Francis R. Japp, F.R.S., and G. N. Huntly. The saturated ydiketones, such as acetonyl-acetone, are known to interact with 2 mol. proportions of phenylhydrazine to form colour- 12 less dihydrazides : the authors find that an unsaturated 7-diketone- anhydracetophenonebenzil-behaves differently, thus : Ph*CO*CPh:CH*CO*Ph+ CGH:j*NH*NH,= C2sH2,NZ + H2O + 0, the reduction involved in the pyocess being probably effected at the expense of a second molecule of phenylhydrazine.The compound C28H22N2forms canary- y ellow need1 es, melting with decomposition at 231”, very sparingly soluble in all the ordinary organic menstrua of low boiling point. The authors regard it as a closed-chain compound, possibly with two nitrogen-atoms in the ring. 9. “The supposed Identit’y of Rutin and Quercitin.” By E. Schunclr, Ph.D., Y.R.S. Rutin, a crystalline yellow colouring matter contained in the leaves of garden rue (Ruta grnveoZena), was discovered by Weiss, and sub-sequently examined by Borntrager ; Iny Rochleder and Hlasimstz, who obtained it from capers, the flower buds of Cappa& spinosn; by Stein, who found it in Chinese yellow berries, the flower buds of Sophora japorLica; and by the author himself, who extracted it from the leaves of PoZygonum fagopyrunz, the common buck-wheat.By most of these chemists it was held to be a distinct substance. The experiments of Hlasiwetz, however, seemed to prove that it was identical with quercitrin, and this view appears to have been generally adopted. Quercitrin having within the last few years been examined by Liebermann and others, and its true composition having been ascertained, while rutin, so far as the author knows, has not recently been made the subject of investigation, it was thought that it might be of interest again to compare tho two substances, and, if found to be distinct, to ascertain wherein the difference consists. The quercitrin employed by the author was obtained from quercitroii bark, and was found to have the properties and composition assigned to it by Liebermann and Hamburger.The rutin was derived from buck-wheat leaves, and though it had been in the author’s collection for many years had undergone no perceptible change, A comparative examiriation of the two substances led to the conclu- sion that they are indeed extremely similar, but that they difler essentially as regards some of their properties ; they also differ in composition. Rutin yields with acids the same products of decomposition as quercetrin, viz., quercetin and isodulcite, but not in the same relative proportion ; it gives less quercetin and more isodulcite. The analyses of rutin agree with tlie formula CiLH5,0,,, that of quercetrin being C,sH,,020. The process of decomposition with acid# would be repre- sented by the equation- 13 C42050H25 + ~HzO= CZ.,Hl6Oll + 3C6HI4069 ECence it would appear that rutin is derived from 1 mol.of quercetin and 3 mols. of isodulcite, and quercitrin from only 2 mols. of the latter and 1 of the former. 10. "The Composition of Bird-lime." By E. Divers, M.D., F.R.S,, and M. Kawakita, M.E., F.C.S. Bird-lime from Ilex aqu~foliunzwas investigated a few years ago by J. Personne, who found in it, besides vegetable &blb?-is and water, calcium oxalate, caoutchouc and ethereal salts of a solid, crystalline alcohol, C25H440,m. p. 175", with undetermined fatty acids, The authors had partly examined Japanese bird-lime before Personne published his results, and were induced to continue their work after-wards by finding that their observations, to some extent, differed from and went beyond his.Indeed, their work renders it probable that Japanese bird-lime, prepared as it is, mt from I. aqzcifoZium, but from I. integra, is different in some respects in composition from European bird-lime. They find the fatty acids of the ethereal salts to be palmitic acid, and, in very small quantity, a semi-solid acid, the calcium salt of which is soluble in ether and in alcohol. They have obtained two very similar alcohols by hjdrolysis, one differing only slightly from Personne's ilicic ako7~ol,which they ha\-e named ilicylic alcohol, and have found from closely concordant analyses to have the composition! C22H380; and another, which they have namcd mochyZic alcohol, from mochi, the Japanese word for (bird-)lime, or glutinous matter, and which agrees closely in composition with the formula C26H460.The melting point of this alcohol is 234" C., and that of ilicylic alcohol, 112".The two alcohols are separated from each other and from a resinoid body, C26H440,by a tedious process of fractional dissolution with spirit of varying strengths. The resinoid body is readily soluble in spirit as weak as 80 per cent., mochylic alcohol in that of 95 per cent. or stronger, and ilicylic alcohol in that: of 85-90 per cent. or stronger. The resinoid body (m. p. 110") volatilises above 360", apparently but little changed, ilicylic and mochylic alcohols, without change in a vacuum, at about their respective melting points.Heated with palmitic acid, the two alcohols are converted into compounds just like purified bird-lime. Caoutchouc is also present in Japanese bird-lime to the extent of about 6 per cent. ; but only minute qunnti- ties of oxalates. By destructive distillation, bird-lime yields much palmitic acid and a thick, oily, hydrocarbon, C26H44, besides fluorescent and more carbonaceous hydrocarbons, very little gas, and very little 14 carbonised residue. The authors consi dor bird-lime to be closely allied to the waxes in chemical constitution. ADDITIONS TO THE LIBRARY. I. Donations. Etudes des dissolutions aqueuses, fond6e sur les changements de leurs poids sphcifiques, par D.Mendeliief. St. Petersburg 1887. (In Russian.) Yrom the Author. Liquid Fuel. Its advantages for firing Steam Generators, by B. H. Thwaite. Liverpool 1887 (Pamphlet). From the Author. A Treatise of Chemistry, by H. E. Roscoe and C. Schorlemmer. Vol. 111,Organic, Part IT. London 1888. From the Authors, Notes on the Chemistry of Building Materials for Students of Con-struction, by A. J. Evans and A. Grenville. London 1887. From the Authors. Report on Indian Fibres and Fibrous Substances exhibited at the Colonial and Indian Exhibition, 1886, by C. F. Cross, E. J. Bevan, and C. M. King, in association with E. Joynson; with Notes of Methods of Treatment and Uses prevalent in India, by G.Watt. London 1887. From the Authors. Five-figure Logarithms, by C J. Woodward. London and Bir- mingham 1887. From the Author. Arithmetical Cheinistry: Par.ts I and 11, by C. J. Woodward, London and Birmingham. From the Author. The Mineral Resources of the United States for the Year 1886, by D. T. nay, U.S. Geological Surcey. Washington 1887. From the Survey. 11. By Purchase. Dix nnn&es dans l’histoire d’une th&orie, par J. H. Van’t Hoff. Rotterdam 1887. Technical School and College Building, by E. C. Robins. London 1887. Lectures on t,he Phjsiology of Plants, by J. v. Sachs. Translated by H. Marshall Ward. Oxford 1887. Food Adulteration and its Detection, by J. P. Battershall. New York and London 1887. A Chapter in the History of Meteorites, by the late W.Flight. London 1887. Leyons de physiologie exp6rimentale appliquC. i la mC.decine, par C. Bernard. 2 tomes. Paris 1855. 15 Lecons sur la physiologic? ct la pathologie du systeme nervonx, par C. Bernard. 2 tomes. Paris 1858. Legons sui-la propri6tAs physiologiqnes des liquides de l’organisme, par C. Bernard. 2 tomes. Paris 18.59. Introduction B 1’6tude de la m6decine expArimentale, par C. Bernard. Paris 1865. Legons sur les anesthesiques et sur l’asphyxie, par C. Bernard. Paris 1875. Legons sur la chaleur animale, sur les effets de la chaleur, et sur la fibre, par C. Bernard. Paris 1876. Legon8 sur le diabete et la glycogenbse animale, par C. Bernard. Paris 1877. Leqons de physiologie opAratoire, par C.Bernard. Paris 1879. Levons sur les ph6nomhnes de la vie communs aux animaux et aux v&g6taux,par C. Bernard. Tome I, ‘Lme ed. Paris 1885 ; tome 11. Paris 1879. Legons de pnthologie experimentales et leqons sur les propriAt6s de la moelle &pinhe, par C. Bernard. 2me ed. Paris 1880. Legons sur les effets des substances toxiques et mAdicamenteuses, par C. Bernard. Nouvean tirage. Paris 1883. L’ceuvre de Claude Bernard. Introduction, par M. Duval. Paris 1881. Die starke umbildende Fermente in den Pflanzen, von J. Bara-netzky. Leipzig 1878. Pharmaceutische Chemie, von F. A. Fluckiger, Zweite Auflage. 2 Bande. Berlin, 1888. Fortschritte der Electrotechnik. Vierteljahrige Berichte uber die neueren Erscheinungen auf dem Gesammtgebiete der angewandten Electricitatslehre rnit Einschluss des electrischen Nachrichten- iind Signal-wesen: Unter Mitwiykung von M.Kiliani and E. Pirani, herausgegeben von I(. Strecker. Erster Jahrgang : das Jahr 1887 ; erstes and zweites Heft. Berlin 1888. NOTICE TO AUTHORS OF PAPERS. To facilitate the preparation of the abstract accounts of the Pro- ceedings at the meetings of the Society, all authors are requested to furnish abstracts of their corrimiinications, and to send their papers so that they may be in the hands of the Secretaries, if possible, on the Monday before the day of meeting. Authors are also requested to write on their papers the address to which they wish proofs to be seh. 16 At the next meeting, on February 16th, there will be a ballot foF the election of Fellows, and the following papers will be read:- “An Analysis of Wackenroder’s Soluiion and an Explanation of the Formation of its proximate Constitnents,” by Prof. H. Debus, F.R.S. “Potilitzin’s Law of mutual Replacement of Bromine and Chlorine,” by Prof. Thorpe, F.R. S., and J. W. Rodger.‘‘ The Action of Phosphorus Pentachloride on Salicylaldehyde,” by C. M. Stuart. RAPKIYON AND 80N8, PRINTERS IN OBDINABY TO HER MAJEBTY, BT. MARTIN’S LANE.
ISSN:0369-8718
DOI:10.1039/PL8880400007
出版商:RSC
年代:1888
数据来源: RSC
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