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Abstracts of the Proceedings of the Chemical Society, Vol. 2, No. 20 |
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Proceedings of the Chemical Society, London,
Volume 2,
Issue 20,
1886,
Page 171-178
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摘要:
ABSTRACTS OF THE PROCEEDINGS OF THE CHEMICAL SOCIETY. No. 20. Session 1885-86. March 18th, 1886. Dr. Hugo Miiller, F.R.S., President, in the Chair. Messrs. A. Dresel, Albert Ivatt and Edward Willmore were forinally admitted Fellows of the Society. Certificates were read for the first time in favour of Messrs. Cosmo Innes Burton, 11, Upper Phillimore Gardens, W. ; Arthur William Clayden, North Lodge, Bath College, Bath ; Christopher Hodgson, 144,Blake Street, Barrow-in-Furness ; John William King, St. George’s Hospital, W. ; Henry Oliver Minty, 731, Wandsworth Road, S.W. ; Richard Eloydd Whiteley, UniversiCy College, Not$ingham. The following papers were read :-30. “Note on the Combustion of Cyanogen.” By Harold B. Dixon, M.A. A few years ago, on discovering that a spark might be sent through a, well-dried mixture of carbonic oxide and oxygen without causing explosion, the author madB several experiments on well-dried cyanogen and oxygen.These experiments seemed to shaw that cyanogen, like carbonic oxide, would not explode when dry. On returning to this investigation last autumn, the author discovered that the non-explo- &on of cyanogen previously observed was due not to the absence of moisture, but to the insufficient temperature of the spark. A spark 1mm. long from a, Voss m8ohine may be passed through a mixture of cyanogen and oxygen without, causing exploslion or any appreciable decomposition of the cyanogen. A mixture of the gases dried by standing in contact with anhydrous phosphoric oxide for two mouths exploded with violence when a strong spark was passed through it.A similar mixture which had stood in oontact with a stick of potash also exploded violently. 172 It was found that the initial rate of explosiou of carbonic oxide and oxygen increased rapidly with the amount of aqueous vapour present in the mixture ; similar experiments made with cyanogen and oxygen showed that the initial rate of explosion diminished on adding aqueous vapour. It seems evident, therefore, that the explosion of cyanogen and oxygen does not depend upon the presence of water, which merely acts as a diluent in the mixture. The author has shown that when a platinum wire is raised to red- ness in a well-dried mixture of carbonic oxide and oxygen, the wire glows intensely for a short time, and that complete combination takes place between the carbonic oxide and oxygen without visible flame.A precisely similar phenomenon is observed when a platinum wire is raised to full redness in cyanogen and oxygen: the wire glows brightly and the cyanogen is oxidised to carbon dioxide. The tube is filled with orange vapour both when the oxygen is present in excess and in defect, but to a smaller extent in the latter case. No flame is visible round the glowing coil of wire. When the wire is only raised to dull redness no action seems to take place; on breaking the circuit the wire cools immediately; but when once the action has begnn, the wire continues glowing half a minute after the circuit is broken.DISCUSSION. The PRESIDENTremarked that it appeared t'o him that the cause of this remarkable behaviour of cyanogen just brought under the notice of the Society depended probably not 80 much on the greater heat effect of the larger or rather the longer spark as on its greater potential energy, which starts the explosive wave, for it is generally supposed that the degree of temperature in a small spark is much the same as that of a larger one of tlhe same electromotive force. Dr. ARMSTRONGsaid that the study of the behaviour of mixtures of cyanogen and oxygen in comparison with that of mixtures of carbonic oxide and oxygen, was of peculiar interest, as cyanogen was one of the few gases which decomposed with evolution of heat. It was well known that a certain minimum electromotive force was required to electrolyse liquids, and to effect.the electrolysis of gases a minimum -relatively very high-electromotive force was doubtless also reqiired I an explanation of Mr. Dixon's observations might perhaps be based upon this circumstance. 31. " Note on the Constitution of the Naphthalene-derivatives." By R. Meldola. Haring been unable to attend the meeting of the Society when 111..St,allard read his paper on the bromophthslic acids published in the current number of the Jonrnd (p. 187), I may take this oppor- tunity of pointing out that the new proofs advanced by him in favour of the constitution CO,H : CO,H : BY= 1: 2 : 3 for the hromophthalic acid of m.p. 174-176" appear to me to be perfectly conclusive. The same conclusion has, in fact, been simultaneously arrived at by Guareschi (Atti cl. R. Accat?. d. Fci. d. Toriiz.0, vol. xxi, January 24th, 1886),who has obtained a ehlorophthalic acid of m. p. 124" (anhydride, m. p. 124-125.5") by the oxidation of pi-dichlornaphthalene. The constitution of this chlorophthalic acid is analogous to that of the hromophthalic acid obtained by Smith, Guareschi and myself, and the isomeric acid of Alan, which has the constitution CO,H : CO,H : C1 = 1: 2 : 4, and melts at a lower temperature (148' according to AlAn ; 130-134" according to Kriiger). In accordance with this evidence, it becomes necessary to modify the formula, of Guareschi's nitrobromonaphthalene (m.p. 122.5") as proposed by Mr. Stallard, and as the discoverer has himself painted out in the paper referred to. The formula given bp me in my last paper (Trans., 1885, 515) for the dibromonaphthylamine of m. p. 105" must also be corrected, and I may here point ont that the constitution of this substance and of its derived di- and tri-bromonaphthalenea can be now defihitely established. The corrected formub will be- DibromonaphthylamineI m. p. 105', Br : Br : NH, = 1': 1: 3 Dibromonaphthalene, m. p. 74",Br : Br = 1: 1' Tribromonaphthalene, m. p. llOo, Rr : Br : Br = 1: 1': 3. The alternative formula Br : Br : NH, = 1':4 : 2 for the dibromo- naphthylamine is excluded because it does not give y-dibromonaph- thalene on displacing the NH,-group by H.The dibromonaphthylamine of m. p. 101-102" (Trans., 1885, 514) must accordingly have Lhe covstitution XH, : Br : Br = 1: 3 : 3' or 1 : 3 : 2', but there is at present no evidence to deoide which of these formulae is correct. That the second Br-atom does not occupy an a-position in the unsubstituted nucleus appears from the fact that I failed to obtain the 1: 2 : 3 bromophthalic acid from it by oxidation. Further, as this dibromonaphthylamine gave only a slight trace of phthalic acid when oxidieed, it would appear that the second Br-atom does not enter the substituted nucleus. Unfortunately, I: have not enough of the dibromonaphthylamine left to repeat the oxidation experiment, but I find on reference to my laboratory notes that the oxidation was twice performed with different preparations and with the same result in each case. The minute quantity of phthalic acid formed certainly does not appear to me sufficient to establish the formula Br : Br : NH, = 3 : 2 : 1,which is the only other one admissible (Trans., 1885, 514).174 The chief discrepancy at present remaining to be cleared up is the apparent identity of the two dibromonaphthalenes of m. p. 74". I have re-examined the specimens in my possession, and as far as melting point and crystalline form can be trusted as indications of identity, these two dibromonaphthalenes are certainly indistinguishable from one another; nevertheless they may be isomeric, as I have already pointed out (Trans., 1885, p.516) that naphthalene derivatives which are known to be isomeric may have the same crystalline form and melting point, The question can only be decided by a further study of the derivatives of the dibromonaphthalenes in question, but I regret that the quantity at my dispogal is much too small t.0 enable me at present to extend the research in this direction. The bromo- phthalic acid used by H. v. Pechmann (Ber., 12, 2126) may have been the meta-compound, the production of erytlhroxyanthraquinone from the corresponding bromobenzoglbenzoic acid being due to intra- molecular migration to the orthoaposition on fusion with alkali. I may take the present opportunity of pointing out that the di- bromonsphthalene (m.p. 68") obtained by Canzoneri (Oazxetta, 12, 424) from smith'^ monobromo /3-naphthol, is in all probability identical with the orthodibromonaphthalene described in a former paper (Trans., 1883, 5). It has been argued that the investigations of Beilstein and Kurbatow (Annulen, 202,228) show that Psdinitronaphthalene (map, 176") has both N02-groups in the same benzene-ring, mosr, probably in the meta-position (Jacobson, Inaug. Diss., 1882, 37). If so, Y-dichloronaphthalene (m. p. 83"), obtained by Atterberg (Ber., 0, 1730) by the action of PC16 upon this dinitronaphthalene, is analogous to the metadibromonaphthalene (m, p. 64") described by rue in 1879 (Ber., 12, 1962). DISCUSSION. Dr, ARMSTRONGsaid that as regards the constittition of p-dinitro-naphthalene, the production from it of dinitrophthalic acid (Beilstein and Kurbatow) by the action of nitric acid in sealed tubes, was not satisfactory evidence ; and Jmobson7s contention that Liebermsnn and Dittler's nitro-x-naphthol (m.pi 138') could not well be an ortho; derivative because the amidonaphthol prepared from it did not furnish a quinone on oxidation was equally unsatisfactory as being negative evidence ; there was no obvious flaw in Atterberg's argument that y-dichloronaphthalene is an a-a-derivative (Watts' Dictionary, vol. viii, Pt. 11, pa 1376). The argument from analogy is apt to break down on comparing bendene with naphthalene, as two new come into force in the case of naphthalene, namely, the tendency for substitution to take plaoe in both "rings," and the marked tendency to forfi a-derivatives. The formula given by 175 Professor Meldola to the dibromonaphthylamine melting at 1,01-102” must be accepted with reserve on this latter account.32. “Action of Ammonia on Chromyl Dichloride.” By Samuel Eideal, B.Sc. Dry ammonia gives with chromyl dichloride ammonium chloride, nitrogen and brown oxide of chromium, the reaction being expressed by the equation: 3Cr02C12+ 8NH3 = 6NHIC1 + N, + Cr20a*Cr0,. No addition products or chromammonium bases are formed when the vapour of chromyl dichloride burns in an atmosphere of dry ammonia, under the ordinary temperature and presaure. This explanation of the reaction agrees with the observation a+‘Persoz that 20.98 parts of chromyl dichloride absorb 79.1 parts of ammonia.33. .‘Note on the Estimation of Resin in Soaps.” By C. R. Alder Wright, D.Sc., F,R.S., and C. Thompson, F.C.S. We have had occasion to make a number of experiments with various of the methods hitherto proposed for the determination of resin in soaps, with the general result of finding that one and all leave much to be desired in the way of accuracy. Sutherland’s process (oxidation by nitric acid) in Some instances gave fair results; but this occurs mostly through the balancing of two opposite sources of error, viz., incomplete removal of resin by oxidation-tending to iiicrease the percentage of fatty acid found; and oxidation of true fatty acids-tending t,o decrease it, Treatment of aqueous soap solution by various processes intended to throw out of solution true soaps of fatty acids leaving dissolved resinates did not answer at all well in our hands: sometimes fatty soaps were retained in solution, and resinates were often mechanically carried out of solution along with the fatty soaps, and no certainty of complete separation was ever attainable.On the whole, the process recommended by Gladding (Chem. Xews, April 14, 1882) seemed to give figures most in accordance with the truth, provided the nature df the fatty matt’ers contained in the soap examined were approximately known so as to permit of the application of a correction-factor variable to some extent with this nature. The method consists in separating the fat acids, dissolving about 0.5 gram in 95 per cent.alcohol, neutralising with saturated alcoholic potash, then adding a few additional drops and boiling to saponify any small quantity of glyceride present (through imper- fection in manufacture, &c.) ; after cooling, ether is added to 100 c.c., and finely powdered neutral silver nitrate, and the whole well agitated: finally a known fract’ion of the ethereal solution oP 176 silver resinate, &c., is treated with hydrochloric acid, and the liberated resin, &c., weighed after evaporation of the ether. Accord-ing to Gladding (who, however, only quotes a very small number of test experiments), 100 C.C. of alcoholic ether dissolves 23.5 mgrms. of oleic acid, when '' pure fat acid " (mixture of stearic and oleic ?) is thus treated ; and this correction-factor he found to be applicable with accuracy when Castille soap, linseed oil soap arid soaps containing knowxi amounts of resin were examined.Our experience, however, is that 23.5 mgrms. (representing 4.: per cent. on 0.5 gram fatty acids and resin) is a correction-factor by no means universally applicable. With pure stearic or oleic acid it is much too large: with acids from castor-oil far too small; with various mixtures it is not far from the truth. Thus the values given in the table were obtained as the result of a large number of observa-tions which, moreover, did not always show a high degree of con-cordance, notmithstanding all the care taken to avoid sources of error ; partly no doubt tlhis is-due to the circumstance that different specimeiis of oils, &c., were employed in the production of the soaps treated.The temperature was throughout nnt far from 18"C., but was not kept absolutely uniform; which circumstance may again partly account for apparent irregularity in the solubility of the silver salts. Although Gladding's correction of 23-5mgrms. is not strictly applicable in all cases, yet the figures in the table indicate that it is not far from the truth in at least a number of instances of mixtures likely to occur in actual manufacture : in such cases a tolerably fair approximation to the truth is attainable by assuming that the weight of the resin apparently found in 0 5 gram of fatty acids should be diminished by some 25 mgrms., or what is the same thing, that the percentage of resin found in the total fatty acids, &c., is 5 per cent.too high. But this correction cannot be regarded as applicable universally. 177 Fatty matters dissolved (as silver salt) in 100 C.C. of alcoholic ether. Nature of fatty niattera in soap examined. Maximnin. Minim urn. General average. --I--___-----mgrms. mgrms. mgrms.Pure stearic acid.. .................. 16 -0 8.0 11.6 oleic ), .................... 15 ‘0 0 .o 12.0 Nearly pure prtlmitic acid ............ 30 ’0 28.0 29 *1 Cotton-seed oil.. .................... 34 -0 20 *o 26 *9 Castor oil.. ........................ 62 ‘0 49 -0 53 -9 Cocoanut oil (fatty acids dried on water- bath) ........................... 17 -5 12 -0 14 -8 Cocoanut oil (fatty acids dried oTer H2S04) .........................23 ‘0 19 *o 21 -1 Stearic and oleic acids, in nearly equal proportions ...................... 22 -0 18*o 19-1 Stearic acid and cotton-seed oil, in nearly equal proportions ................. --25 -5 Oleic acid and cotton-seed oil, in nearly equal proportions ................. --24.5 Stearic acid and cocoanut oil (waterr bath), in nearly equal proportions ... --23 -4 Oleic acid and cocoanut oil (water-bath), in nearly equal proportions ......... --25 -6 A source of error that should not be overlooked is that the concentrated alcoholic potash used as directed by Gladding is liable on keeping to become dark-coloured, and in so doing to contain more or less notable amounts of resipoid matter (from action on the alcohol or impurities contained therein).Several milligrammes of incre-ment in the ether residue may readily be brought about by the use of such potash solution. Another source of error is the decomposition of certain of the insoluble silver salts of fatty acids by light, causing in some instances appreciable amounts of additional matter to become dissolved in the alaohdic ether. 34.“The Properties of the Nitrobenzalnialonic Acids.” By Charles M. Stuart, M.A. On boiling benzalmalonic acid, C,H,.CH C(COOH),, with water, it is resolved partly into benzaldehyde and rrialonic acid (l),and partly into cinnamic acid and carbon dioxide (2) ; the three nitro-derivatives behave similarly, the percentage amounts converted in accordance with the first and second modes of change being shown in the following Table.Boiled for 1hour. IBoiled for 15 min. I. 11. rotai. I. 11. Total. _1 --Benzalmaloiiic acid. ................ 85 -2 --57.8 1-41 59 '2 ,) ................. 85 -8 10*8 96 *.6 58'3 1-25 59 -59, ,, ................. 84 *4 10.6 95 -0 ---1) Paranitrobenzalmalonic acid ........ 80 *2 14 -8 95 '0 61-54 3-89 65 -4 >Y 77 *. *. *-'* 82.7 12 '4 95 -1 62 -64 3 -77 66 -4 Metanitrobenzalmalonio acid ........ 83 -1 10 -4 93 -5 61-3 fi-3 67 -6 --. . * -.. 79 *9 14.4 94 -3 62.5 5.8 68 -39% ). n Y? a. a*..** 79 -7 12*6 92 '3 Orthonitrobenaalmalonic acid ........24 -5 5 *'7 30-2 8.7 1-18 9*88 ,9 .f.**.*. 23 *6 6 -5 30 *1 8.71 1'25 9.9677 24.4 6 -4 30 *8 ---7* 77 ........ Bsnzalmdonic acid and its para- and meta-nitro-derivatives form additive compounds with bromine and with hydrogen bromide, which are decomposed by water. The ortho-nitro-derivative is converted both by the action of bromine and hydrogen bromide into a con-densation product which is not decomposed by water or alcohol. The author suggests that this behaviour may be regarded as an argument in favour of Kekul6's benzene formula. From cinnamic acid and malonic acid he has obtained a phenyl- butindicarboxylic acid, CsH5*CH:CH-CH:C(CO,H), ; this melts at 208", but is resolved into GO, and cinnamenylacrylic acid. Salicylic and ma'lonic acids give coumarincarboxylic acid ; this melts at 18'7" without decomposing, but is resolved at a higher temperature into CO, and coumarin. The Anniversary Meeting of the Society will take place on Tuesday, March 30th, at 8 P.M. At the next ordinary meeting, on Thursday, April lst, the following papers will be read :-''The Determination of Boiling Points." "The Action of a Red Heat on Chloroform." By Prof. Ramsay and Dr. Young. ''The Use of the Electric Light to Influence Chemical Change." By Dr. Armstrong. " Some Sulphur Compounds of Barium." By V. H. Veley. lihEXISON AND SONS,PRINTERS Ih' OXDINARY TO HER MAJESTY, ST.MAETIN'S LANI.
ISSN:0369-8718
DOI:10.1039/PL8860200171
出版商:RSC
年代:1886
数据来源: RSC
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