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Abstracts of the Proceedings of the Chemical Society, Vol. 4, No. 46 |
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Proceedings of the Chemical Society, London,
Volume 4,
Issue 46,
1888,
Page 1-5
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摘要:
ABSTRACTS OF THE PROCEEDINGS OF THE CHEMICAL SOCIETY. No. 46. Session 1887-88. January 19th, 1888. Mr. William Crookes, F.R.S., President, in the Chair. Mr. J. Garnett Heywood was formally admitted a Fellow of the Society. The President annoniiced that the Couiicil nominated as Foreign Members Professors Geuther, Ladenburg, Lnnclolt, Nilson, Van’t HOB, Wislicenus and Mons. Lecoq de Boisbaudran ; and that these would be balloted for at the next meeting. Certificates were read for the first time in favour of Messrs. William Herbert Barraclough, Westfield House, Thorpe Hesley, near Rotherham ; Thomas Fraser Rarbour, 16, Gladstone Terrace, Edin- burgh ; Henry Dudley Bcrridge, 203, Bellevue Road, Leeds ; Alfred Edward Carey, M.Inst.C.E., 9, Dean’s Yard, Westminster ; Lewis Smith Cocking, Martin Bank, Huddersfield ; Walter Hepworth Collins, 14, Bradford Chambers, Mawdsley Street, Bolton-le-Moors. Lancashire ; Astley Cooper., 66, Queen’s Road, Xeadingly ; John H.?J. Dagger, 3, West Bank Road, Edge Lane, Liverpool ; Benjamin Henry Gerraiis, .Jun., 47, Aubert Park, Highbury, N. ; Christopher James, Ida Villa, Swansea; J. Lewkowitsch, 6, Warwick Place, Leeds ; Charles Robert Lafosse, Knolls House, Hr. Broughtoui, Manchester ; Frederick K. S. Lowndes, 4,Plumstead Common Road, Woolwich ; Thomas Maben, 8, Eskdaill Terrace, Hawick ; James Mayne, 203, Oxford Street, Sjdney, New South Wales; Otto Over- beck, Wootton Bassett, Wilts ; Cliffold Richardson, Office of the Engineer Commissioner, Washinston, U.S.A.: Robert Mason Sumner, SO, Lord Street, Liverpool ; Sam. Smith, 30, Commercial Street, Batley, Yorkshire ; Angus Smith, 5, Antigua Street, Greenocli ; Arthur J. C. Waterland, Sidney Villa, South West Road, Leytonstone ; 2 John Cuthbert Welch; Emil A. Werner, 5, Church Avenue, Rath- mines, Dublin. The following papers were.read :-1. “Morindon.” By T. E. Thorpe, F.R.S., and W. J. Smith, M.B. The aiithors have confirmed the observations of Thorpe and Greenall (Chenz. Xoc. Trans., 1887, 52) on Morindon. Morindin, the active colouring matter of A’l, the root-bark of Morinda citrifok‘a, yields 48.4per cent. of moridon on hydrolysis. This latter subst)ance is not identical with alizarin, but has the composition CI5Hl0O5,and differs from all of the eight compounds of the same formula which are known at present.That morindon is a methylanthracene-derivative has been proved by distilling it with zinc-dust. The methylanthracene so obtained was oxidised by chromic acid to artthraquinonecarboxglic acid having all the properties described by Lieberniann. 2. “Manganese trioxide.” By T. E. Thorpe, F.R.S., and F. J. Hambly. The authoys have repeated the experiments of Pranke (Journ.j”;* Y~drt.Chemie, 1887) on the so-called volatile oxides of manganese. They have been unable to obtain any evidence of the existence of the blue gaseous manganese tetroxide. They find, however, that itiaiiganese trioxide exists and can be formed by the action of a solu- tion of potassium permnnganate in sulphuric acid on dry sodium carbonate.It is a reddish-pink amorphous solid, extremely delique- scent, and stable only at a low temperature. On heating it is at once decomposed into manganese dioxide and oxygen. Water decom- poses it into manganese dioxide and permanganic acid. 3. “Note on Chatard’s process for the estimation of small quantities of manganese.” By the same. The authors find that the inconvenience arising from the formation of lead carbonate in the titration of permanganic acid by ammonium oxalate may be obviated by addiug sulphuric acid when boiling with the lead dioxide and nitric acid without impairing the accuracy of the results. DISCUSSION. In reply to a questioii by the President, Mr. Hehner said that Chatard’s method was an extremely delicate om ; using it in the form of a colorimetric process, he had been able to detect manganese in R few mgrlzis.of steel containing only half a pel. cent. of manganese. Professor Thorpe, also in reply to the President, said that there was no reason to belicve that any volatile oxide of manganese existed. Chatard’s was essentially a minimetric method, and gave highly satisfactory results with very small quantities of manganese. 4.“ Contributions to the theory of the vitriol-chamber process.” By G. Lunge. The theory has been recently advanced by Raschig that the vitriol- chamber process involves the formation in the first instance from nitrous acid and sulphurous acid of dihydroxylaminesulphonic acid, which being acted on by nitrous acid yields sulphuric acid and nitric oxide ; this nitric oxide he considers is then reconverted into nitrous acid.This theory is regasded by the author as untenable on all points. It completely ignores the existence of nitrosyl sulphste (chamber- crystals) ; moreover, according to Raschig’s own investigation, the dihydroxylaminesulphonic acid, as it could not possibly meet at all points with nitrous acid, would yield N,O, of which a very large quantity would be found in the chambers, which is never the case ; lastly, nitric oxide, oxygen in excess and water do not yield nitrous acid but nitric acid. Raschig’s indirect proofs are equally unsatis- factory, and would at most only show that subsidiary reactions may take place to a small extent.A true theory of the vitriol-chamber process must deal with the substances actually present and with reactions fully proTed to take place. It has been already foreshadowed by the author (Chew. Soc. Tram., 1885,470) in these words : “ It is not as hitherto generally assumed NO, but N203,which acts as carrier of the oxygen in the vitriol chamber, &c.” The principal reactions are :-2S0, + N,O, + 0, + H,O = 2SO,(OH)(ONO). BSO,(OH)(ONO) + H,O = 2SO,(OH), + NZO,?. These reactions are modified in the first part of the chambers by the excess of SO, ; in the last part sometimes by the complete absence of SO,; and in some places by an excess of water. No theory can be accepted which alssumes the formation of NO,, since this gas does not occur at all in normally working chambers, and since its formation is practically excluded by t’lie conditions which obtain in the end chambers.The question whether N,O, exists as a gas or not plays oiily a secondary part in this discussion ; but the phanomena occurring in the vitriol-chambers make it at least more probable that N,Os must exist as a gas for some time before it is dissociated. At all events the 4 gas present in the back chambers has a coinposition equivalent to N,O.,, and this 01-NO(0H) must be introduced into the reactions. Ths direct reactions : SO, + N,O, + H20= S0,(OH)2 + 2N0, and 4N0 + O2 = 2N203,cannot any longer be considered as important, since nitric oxide and oxygcn do not S;ielcl N,03 except in immecliate contact with sulphuric acid-when SOz(OH)(ONO) is formed ; apa1.t Erom this, NO, must be formed in dry places, or NO,H in the presence of water, but the presence oE SO, modifics evei-jthiiig.In the front chambers there is inncdi NO present along with N20,. NO is formed by a secondary reaction (denitratioii) from nitrosyl snlpliate: 2SO,(OH)(ON0) + SO, + 2H,O = SS04H2+ 2N0, and is principally absorbed by the dircct renction-4S0, + 4N0 + 302+ 2H,O = 4S02(OH)(ONO) ; none of it can pass into NOz, bnt some of it may pa,ss into NO,H, which is at once acted upon by SO,, and converted into nitrosyl sulphate. Thus the normal vitriol-chamber process is not as hitherto understood an alternation of reductions and oxidations, but it is a coi~de?zs~tionof nitrous acid, or of NO witlh SO, mid 0, to nitrosyl sulphatc, nncl a splitting up of the latter into salphuric: acid and N,O,.Abnormally, N20can be formed by the reduction of NO by SO,, but net according to Raschig’s theory. This reaction in properly working chambers does not exceed an extent of 0.5 pnrt of NaNOy on 10G of S. Much larger losses are sometimes caused by the abnormal formation of X02in the back chambers, which is due to an abnormally great supply of nitre. In this case the acid-forming process is finished too soon ; the N20, does not meet with any more SO,, and thus finds time to dissociate into NO and NO,. Another abnormality is caused by a deficiency of nitre, which leads to losses in the shape of N20,of NO, mcl of NOSH.Much importance is due to the fact that the normal working of the acid-forming process is a mass reaction, requiring a great excess of oxygen, without which the denitrating reactions, norudly prevailing in the front chamber, set in abnormally in the back chamber. This leads to an explanation of the fact why larger (:liamber-space and a more copious supply of nitre compensate each otlze~to a certain extent. nr. ALDER WR1C;IIT thought that an avgumcnt mignt perhaps be adduced in favour of the predominance of NO in tlic cmlicr cliaiiibers of a series as compared with Nz03,from the colour of the gases, the pale colour of which (as coiitimtetl with thc tint that would bc secii were all nitrous fumes prcsent ns nT,0,3)woulcl suggest that only a 5 sinall fraction of the gnses was in the higher state of oxidation.He was disposed to believe that in the chambers themselves suZplmy dioxide was capable of reducing higher oxides of nitrogen not only to NO but even to N,O and N,. This was generally considered to be brought about in the Glover tower in virtue of the higher tempera- ture, and also of the presence of AsaO, from pyrites ; but as nitrous fumes were known to be destroyed (presumably by reduction) when no Glover tower was used, and with brimstone acid where little or no arsenic was present, it appeared to him that some other source of such loss must be looked for, and that this was to be found in the power of sulphur dioxide to reduce oxides of nitrogen to nitrous oxide at a lower temperature than usually supposed possible.Professor RBIISAPsaid that Dr. Lunge’s remark that nitrous anhy- dride might act 2s such, or as a rnixtu1.e of nitric oxide and peroxide, is, so far as the last statement is concerned, in complete accordance with Professor Ramsay’s experience. A mixture of NO, and NO in the proportion necessary to form N203will act as such with such reagents as water or sulphuric acid. With regard to Dr. Wright’s remarks 011 the production of nitrous cxicle, Professor Ramsay had heard from alkali makers that when “things went wrong,” i.e., when excess of sulphur dioxide was present, such reduction does take place. 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 communications, and ta 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 add?-ess to zulzich they toish proofs to Dc sewi. At the next meeting, on February 2nd, a lecture will be delivered on “ The Range of Molecular Forces,” by Professor Riicker, M.A., I3.R.S. HARRISON AR’D SONS, PRINTERS IN OKDINAILYTO HW. MAJLSTY, ST M.ZRTIF’B LANE.
ISSN:0369-8718
DOI:10.1039/PL8880400001
出版商:RSC
年代:1888
数据来源: RSC
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