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Abstracts of the Proceedings of the Chemical Society, Vol. 3, No. 43 |
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Proceedings of the Chemical Society, London,
Volume 3,
Issue 43,
1887,
Page 117-124
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摘要:
ABSTRACTS OF THE PROCEEDINGS OF THE CHEMICAL SOCIETY. No. 43. Session 1887-88. November 17th, 1887. Mr. William Crookes, F.R.S., President, in the Chair. Messrs. Edwin J. Ball and David Lloyd Howard were formally admitted Fellows of the Society. Certificates were read for the first time in favour of Messrs. Peter Coulson Burn, Junr., King’s Lynn, Norfolk ; F. Barker Cooke, 40, Wilson Road, Camberwell, S.E.; Agnew Griffith, Daisy Mount, Blundell Sands, Liverpool ; Frank Edward Lease, Cdedonia Estate, Province Willesley, Straits Settlements ; Edniund George McBretney , 25, Denton Terrace, Castleford, Yorks. ; W. Sedgwick Saunders, M.D., 13, Queen Street, Cheapside, E.C. The following papers were read :-81. “Zinc-copper and Tin-copper Alloys.” By A.P. Laurie. The author finds that if the zinc plate of a Daniel1 cell be replaced by acompound plate formed by joining copper and zinc, the cell has the same electromotive force as one in which zinc alone is used ; this is true even though the zinc surface be only mlmth part of the copper surface. If the zinc plate be replaced by copper-zinc alloys, no deflection of the electrometer is observed as long as the alloy con- tains less than 67 per cent. of zinc; at this point, however, a big deflection, practically equivalent to that given by zinc, is suddenly obtained. This result, in the author’s opinion, may be taken as evi- dence of t’he existelice of a compound of the two metals of the formula CuZn2. Alloys containing a greater proportion of zinc behave like zinc aloxe.Similarly in the case of tin-copper alloys, a sudden rise of electromotive force is observed when the proportion of tin in the alloy exceeds that which would be contained in a compound of the formula Cu,Sn. This result is in harmony with the evidence already obtained by observations of the density and thermal and electrical conductivity of the copper-tin alloys. If an alloy contaiiiing a larger percentage of tin than Cu,Sn, in a state of fine division, be placed in a copper cup and used in place of the zinc in a cuprous chloride cell, the excess of tin is gradually eaten out, leaving approxi- mately the alloy Cu,Sn ; this alloy undergoes no change if the circuit be kept closed. DISCUSSION. Dr.WRIGHT,after asking whether the author had made any experi-ments with ternary alloys, referred to observations which he had had occasion to make on lead-zinc-tin alloys. It is well known that lead and zinc will not permanently mix, bat that on cooling the lead separates with a little zinc and the zinc with a little lead: he had found that tin behaved itself indifferently to the two metals, dividing itself between them; but the zinc appeared to be able to take up more lead, and the lead more zinc, in presence of the tin. Mr. BALLsaid that under Professor Robert Austen’s direction he had made experiments on the eEect of melting’ lead-a metal which does not alloy with copper-with copper-tin alloys ; it was found, how- ever, that the lead had no influence, the copper-tin alloy separating out unmixed.Professor RAMSAYsuggested the application of the author’s method to lead-tin alloys, which appeared to be but “ solidified solutions.” The PRESIDENTdrew attention to the fact that amalgams presented many peculiarities. Thus iron, antimony, sodium, silver and gold will dissolve in mercury ; but if antimony amalgam be mixed with sodium amalgam the antimony is thrown out-iron also. 82. “ The Halogen Substituted Derivatives of Benzalrnalonic Acid.” By C. &I.Stuart, M.A. The author describes the preparation of orthochlorobenzaldehyde, orthobromobenzaldehyde and orthiodobenzaldehyde, and their tram- formation into the corresponding halogen substituted benzalmalonic acids ; and the decompositions which these acids and o-methoxy- benzalmalonic acid undergo when boiled with water : on the one hand (Eq.I), into benzaldehyde and malonic acid; and, on the other (Eq. It),into carbon dioxide and cinnamic acid (see accompanying table ; comp. Trans., 1886, 357). On reduction, orthonitrobenzal- malonic acid yields the cnrhost~rilcarbox~lic acid described by Fried-lander and Gohring. 119 Boiled for 1hour. Boiled for 15 minutes. Decomposition according Decomposition according to to Eq.I. Eq. 11. Total. Eq.I. Ey.11. Total. --.___ Benzalmalonic acid. .... . . . . . 85 ‘8 10-8 96.6 57 ‘8 1-41 59 -2 84 *4 10 -6 95 -0 58.3 1.25 59.5 Orthonitrobenzalmalonic acid . 24.5 5.7 30.2 s.70 1.* 18 9 -88 23 *6 6.5 30.1 8 *71 1-25 9.96 I24 -4 6‘4 30*8 -__ Orthochlorobenzalmalonic acid 65 *I7 8 ‘40 73 -57 30 *8 3.36 34‘16 64 -35 9.64 73 *99 30 -8 3 ‘47 34‘27 Orthobromobenzalmalonic acid 66 -0 10-6 76.6 33 -0 3 *22 36 ‘22 67 *6 10.2 77-8 32.3 2 -84 35-14! Orthiodobenzalmdonic acid .. 67-6 9.09 76 %9 33 .o 3*5 36 -5 65 *7 10.09 75 -79 31 -9 3.0 34.9 Orthomethoxybenz almalonic acid.. .............. ..... 78 -1 8 -16 S6 *2 45 -9 2 -72 48 -62 76.4 9 ’27 85 *6 44 ’0 2 ‘04 46.04 83. “Note on a Modification of Traube’s Capillarimeter.” By H. S. Elworthy. The author describes a modification of Traube’s instrument for determining f use1 oil in spirit by measuring t,he capillary depression, the essential feature being that the tube is fixed at an angle approaching the horizontal instead of vertical. In Traube’s instru- ment a pure 20 per cent.(by volume) spirit is said to rise 50 mm.; but in the author’s modification the rise is 173 mm., and 1per cent;. of fuse1 oil produces a depression of 25 mm. instead of only 7 mm. 84. “ The Formation of Hyponitrites : a Reply.” By Edward Divers, M.D., F.X.S. The paper on the “Formation of Hyponitrites,” by Professor Dunstan and Mr. Dymond (Trans., 1887, 646), whicli I received a few days ago, contains some references to papers by Mr. Haga and myself, and by me alone, which are erroneous, and place us in a false’ position. (1.) In the section headed “Discussion of Results,” p. 656, the authors say: ‘‘ We are unable to confirm the statement made by Divers and Haga that ferrous hydroxide in presence of alkali does not form hyponitrite from nitric oxide ? ” Such a statement has not been made by us.All that we have said on this subject occurs in two lines near the end of a short paper describing the formation of hypo-nitrite from nitric oxide by acting on it with potassium stannite, in reference to the only experiment we have made with ferrous hydroxide and nitric oxide, one in which we employed st’rongsolution of potassium hydroxide with the ferrous hydroxide. Our words were (Trans., 1885, 364) : “Neither hydroxylamine nor hyponitrite could be detected as products cf this reaction.” The authorfi record their repetition of this experiment, with results the same as ours (p. 649), and have thus actually confirmed our only statement in the matter.The authors signally confirm also our other experience with ferrous hydroxide, in failing, like us, by ZOWL’Sprocess, to reduce nitrites and nitrates to hyponitrites. (2.) The authors find thaf I regard “ the formation of hyponitrites as due to the direct withdrawal of oxygen from the nitrite or nitrate by the metal” (p. 657), and give as references my first paper on ‘‘Hyponitrites ” (Yroc. Boy. Xoc.., 1871), and subsequent communica- tions, more particularly that “ On the Production of Hydroxylamine from Nitric Acid,” presented to this Society. For the very sufficient reason, however, that I have as yet formed no clear notion of the constitution of hyponitrites, I have never offered any formal theory of their formation, unless it be the very one offered by the authors themselves, incideiitally given in my discussion of the reduction of nitric acid by metals (see below).Nowhere otherwise in that paper, nor at all in any other communication, have I treated of the theory of the formation of hyponitrites, so far as I can find. In my first paper occurs only the equation-NO,Ka + 2Na = NONa + Na,O, and the bare statement that the sodium reduces the nitrite. The autthors were, therefore, hardly in the position to state that I regard its formation as due to the direct withdrawal of oxygen, the word withdrawal italicised, in order plainly to make a contrast to their supposition that first sodium nitrite directly combines with hydrogen.I have long ago expressed the latter view myself, but I should still express the wsult of the reaction by the above equation in my first paper. (3.) The authors further find me to suggest “ that a compound of the formula NaNONa, is formed by the substitution” (the italics again are theirs), “ of two atoms of sodium for one of oxygen in the nitrite NaNO, + 4Na = NaNONa, + Na,O” (p. 657). But at the place referred to (Trans., 1883, 458), there is only the equation -Zn(NO), + 4Zn = Zn2N202Ziii-2Zn0, together with words which have rightly led the authors to write 2Na for Zn, and halve the formula. Of the substitution of metal for oxygen there is neither word nor implication in my paper. 2n2N20,Zn, or Na,NONa, is clearly hydroxylamine with zinc or sodium in place of hydrogen, huh the authors have, by some strange error, written, three times over, as my formula, NaNONa,. Such an niijustifiable mode of writing may serve to illustrate the absurd view they attribute to me, that 131 two atoms of sodium are substituted for one of the atoms of the oxygen of the nitrite (!), but no such view is expressed or coun-tenanced in any paper of mine.The authors will, I am sure, agree with me that a position-formula, which contains two or more groups of atoms of the same element, does not preserve its meaning when rewritten with another arrangement of its symbols. (4.) Having shown the insufficiency of the views they attribute to me, incorrectly as I have just pointed out, the authors praceed to advance a view of their own, which is nevertheless to be found stated explicitly in that communication of mine to the Society, to which they principally refer.They say : “ The hypothesis we wish to suggest as at once the simplest and most in accordance with the facts, supposes that the sodium nitrite first directly combines with two atoms of hydrogen. The formula of the new compound will be Na-N :(OH),, or perhaps NaONHeOH. This substance will on the one hand split up into sodium liyponitrite and water, 2NaN(OH), = Na,N,O, + 2H,O, and on the other be acted on by hydrogen, yielding hydroxylamine and sodium hydroxide, NaN(OH), + H, =NH20H + NaOH. More hydrogen will yield ammonia . . .” (p. 657). Essentially all that is contained in the above extract is given by me in my paper on the “Production of Hydroxylamine from Nitric Acid” (43,443).I there suggest that nitrous acid “passes next to a transition-body capable of decomposing to hyponitrous acid, but readily passing on directly to hydroxylamine, thus : HNO, + H, = HN(OH), = HNO + OH,, or otherwise, HN(OH), + 2H = H,NOH+ OH,, a repetition of which action would give ammonia’’ (OF. cit., p. 462). I have much less confidence than the authors appear to have, as to the sufficiency of this view, which was indeed only expressed by me incidentally in connection with the reduction of nitric acid, and I should not have felt induced to assert my claim to it now, had the authors confined themselves to putting it forward as new, and not, with many references to my papers, erred in representing me as having advanced only other and extravagant views.85, “ Reply to the foregoing Note.” By W. R. Dunstan. 1. As regards the interaction of nitric oxide and ferrous hydroxide, the statement quoted by Dr. Divers in par. 1,is only a fair interpre- tation of his own words. If Dr. Divers believed that hyponitrite was formed, but could not be detected in presence of the excess of alkali (which we have shown to be the case), misunderstanding would have been avoided had he explicitly said so, although there would have been at that time au absence of experimental evidence for the 122 suggestion. This reference to Zorn’s process does not correctly represent our conclusion. We found, contrary to the experience of Divers and Haga, that hyponitrite can be formed from nitrite by a process which is substantially that proposed by Zorn.2. We certainly had gathered from Dr. Divers’ papers that he regarded the formation of hyponitrite from nitrite as the result of the direct withdrawal of oxygen by sodium, and not of the intervention of hydrogen. The habitual exclusion of water from his equations is in itself a sufficient justification for our statement. I fail to find in any of Dr. Divers’ papers an expression of the view that, in the forma- tion of sodium hyponitrite by the action of sodium on sodium nitrite, water is the necessary link in the series of interacting compounds, and that the hydrogen of this water first attaches itself to sodium nitrite.3. The ‘‘ absurd view ” that we had attributed to Dr. Divers has arisen from a misunderstanding of his formula Na2NONa, or, as we had written it, NaNONa,. The equation he gives certainly involves the substitution of sodium for oxygen, but Dr. Divers now explains that the resulting compound is to be regarded not as a sodium-derivative of sodium nitrite, but as a metallic derivatire of hydroxylamine. 4. I am surprised to find that Dr. Divers claims as his own the hypothesis we have suggested to account for the formation of hypo- nitrite and hydroxylamine from nitrites and nitric oxide. He admits that he has never fully discussed the general question. He has pro- posed a similar theory to account for certain decompositions of nitric acid by the tin-zinc metals, but he nowhere attempts to show that an analogous change takes place when sodium acts on dissolved sodium nitrite. Moreover, there is no recorded evidence that Dr.Divers had noticed the significance of the simultaneous formation of hyponitrite and hydroxylamine from sodium and sodium nitrite, and he certainly had not shown that the hydroxylamine was not derived from the hyponitrite ; on the contrary, he has suggested that hyponitrite does yield hydroxylamine when hydrogeniaed (Trans., 1885, 204). It may fairly be said that Dr. Divers was not even in possession of the facts which our hypothesis was devised to explain. My only object in writing this rejoinder is to point out the grounds for attributing to Dr.Divers the views to which he now takes exception. I am glad to firid that after all our interpretations of the facts do not appear to be so divergent as I had formerly supposed. 123 ADDITIONS TO THE LIBRARY. I. Donations. University College, Nottingham. Calendar for the Seventh Session, 1887-8. Nottingham. 1887. From the Council. The Chemistry of Nitrogen as disclosed in the Constitution of the Alkaloids, by A. B. Prescott. Salem. 1887. From the Author. Die Oberharzer Huttenprocesse zur Gewinnung von Sil ber, Kupfer, Rlei und arseniger Saure, mit besonderer Beriicksichtigung des Vorkommens und der Aufbereitung der Erze, von Bruno Kerl. Clausthal. 1860. From Mr. B. H. Brough. 11.By Purchase. Physico-Chemical Constants. Melting and Boiling Point Tables, by T. Carnelley. Vol. 11,4to. London. 1887. Agriculture in some of its Relations with. Chemistry, by F. H. Storer. 2 vols. London. 1887. The Owen’s College Course of Practical Organic Chemistry, by J. B. Cohen. London. 1887. Laws and Definitions connected with Chemistry and Heat, with explanatory Notes on Physical and Theoretical Chemistry, also Special Tests and Examples for Practical Analysis, by R. G. Durrant. London. 1887. Le potential thermodynamique et ses applications tl la mhcanique chimique et A l’etude des ph6nomhnes Blectriques, par P. Duhem. Paris. 1886. IAt the next meeting, on December lst, there will be ballot for tlie election of Fellows, and the following papers will be read :-“ The alleged Existence of a, Third Nitroethane.” By Professor Dunstan and T.S. Dymond. “ An Extension of Mendeleeff’s Theory of Solution.” By Holland Crompton. “ Note on Electrolytic Conduction and on Evidence of a Change in the Constitution of Water.” By Professor Armstrong. “Researches on the Laws of Substitution in the Naphthalene Series.” By Professor Armstrong. RESEARCH FUND. A meeting of the Research Fuiid Committee will be held in December. Fellows desiring grants are requested to make applica- tion before December 12th. NOTICE TO AUTHORS OF PAPERS. To facilitate the preparation of the abstract accounts of the Proceedings at the meetings of the Society, all authors are requested to furnish abshacts of their communications, 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 serct. -~ ~~~ ~ ~~ ~ I1ARRI6ON AND SONS, PHIXTBltd 1N OXDINARY TO I3ER MAJESTY, 6T.NABTIN’S LANE.
ISSN:0369-8718
DOI:10.1039/PL8870300117
出版商:RSC
年代:1887
数据来源: RSC
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