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Proceedings of the Chemical Society, Vol. 6, No. 85 |
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Proceedings of the Chemical Society, London,
Volume 6,
Issue 85,
1890,
Page 95-106
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摘要:
Issued 17 /6/1890. PROCEEDINGS OF THE CHEMICAL SOCIETY. No. 85. Session 1890-91. June 5th, 1890. Dr. W, J. Russell, F.R.S., President, in the Chair. Messrs. W. B. Shuttlewood and H. R. Kenwood were formally admitted Fellows of thc Society. Certificates were read for the first time in favour of Measrs. Charles Edwin Day, 1,Merchiston Bank Terrace, Edinburgh ; Robert Frost, St. James’s Chambers, Duke Street, S.W. ; George German, Hunt-ingdon House, Ashby de la Zouch; Colin Gordon, Millwall Club, West Ferry Road, Millwall, E.; Frank Haydon, Ettrick, Putney Common, S.W. ; Arthur E. Palmer, Ashley Mount, Tettenhall, Wol-verhampton ; Thomas Parkes, Grammar School, Stamford ; Edward Cox Seaton, 35, George St,reet, Hanover Square, W. ; James Mitchell Wilson, Hall Gate, Doncaster.The following papers were read :-45. “The production of pure metallic copper in acrystalline con- dition.” By C. C. Duncan, King’s College, London. The method of precipitating copper oxide from a boiling solution of copper sulphate with potassium hydroxide and then reducing in electrolytic hydrogen having been found unsatisfactory, as the last traces of sulphur could no$ be washed away, experiments were made on the reduction of the sulphate by Ginc, To a solution containing several grams of purified sulphate made acid with hydrochloric acid, metallic zinc (cohtaining only a trace of lead) was added in small fragments. Dark, spongy looking copper at once separated, and this soon protected the zinc from the action of the acid; consequently the copper was very slowly deposited: it was found to be in the form of feathery, dendritic crystals.A portion of the crystalline copper, well washed with dilute hydrochloric acid and distilled wa,ter, was dissolved in strong nitric acid free from sulphur, the solution was diluted and barium nitrate added; no precipitate of any kind formed, even after standing 48 hours, showing the absence of sulphur. To discover whether the metallic copper contained zinc, two of the finest crystals (about 8 mm. long) were again well washed and dried in hydrogen. These crystals were then fixed in an ordinary spark- stand and the spark from a 2-inch Apps’ coil, with a Leyden jar of 1quart capacity in the circuit, was passed between them, and the light from the copper terminals was analysed by one of Browning’s two-prism spectroscopes.The spectrum given by the copper was compared with that of zinc, None of the lines of zinc coincided with those given by the copper; it was therefore assumed that zinc was absent. The bright lines given by the copper crystals agreed with those described by Thalkn (“ MBmoire sur la dhtermination des longueurs d’onde des raies m6talliques.” Act. Nova bpsaZ., iii, 6, 1868, 29). The spark and lines were extremely bright and no faint lines were fo be seen (except the usual air-lines), showing the absence of any nietallic impurity Microscopic examination proved the dendritic crystals to be built up of octahedrons. A5 the production of these crystals was quite accidental, experiments were made with different strengths of copper sulphate solutions, with and without free acid, in order to reproduce them.In the literature relating to the reduction of metallic copper from its salts by means of metallic zinc, there is no mention whether the copper so reduced is in the Crystalline state, except in a paper by Dr. Gladstone and Mr. Tribe (PYOC.Boy. Soc., 20, 1872, 219), who mention the deposition of metallic copper in a crystalline condition, but they make no remark on the purity or size of the crystals so formed. In another paper, “ On the Cryst#allisation of Silver, Gold and other Metals” (Proc. Boy. Institute, 6, E72, 428), Dr. Gladstone again refers to crystalline copper in the following terms :-“Copper salts give round nodules which have no crystalline appearance when deposited from moderately weak solutions, but a very strong solution of the chloride-about 40 per cent.-yields with zinc first a black, thick growth, then arborescent fringes of red metal, terminating in crystals of very appreciable size.” In all the experiments made by the author with acid and neutral copper solutions, dendritic crystals of copper were found which could 97 be seen with the unaided eye ; they were small in the case of neutral, and large in the case of acid solutions.The following tables give the quantity of copper sulphate, water and hydrochloric acid (rel. den. 1.15’2)used in the different experiments, and the results :-Water. Acid.Results. --__--- I 0 Copper was at once reduced in, spongy state and then in minute dendritic 11 and 111 crystals just yisible to the unaided eye. The spongy copper proved to be composed of octahedrons under the microscope. The crystals did not increase in size on standing. Same as I. IV 10 0.0. The dendritic crystals produced were larger than any of those in I, I1 and 111. v 10 C.C. Same as IV. VI VII 100 C.C. BOO C.C. Crystals of copper which were slightly larger than those produced in V. Dendritic crystals of copper were pro-duced, several of which were 10 mm. in length. Sulphur was detected in these crystals, and in most other crys- tals which had been reduced in a solution %hi& Was very strongly acid.No zinc was detected by the spectro- Z’III 100 C.C. scope.The crystals produced were only very slightly larger than those in VII, but - - more numerous. As sulphur had been detected in several of the crystals deposited from the copper sulphate solutions, a few experiments were made with copper chloride free from sulphate (see table, p. 98). Crystalline copper is said to have been obtained by using iron and aluminium as reducing agents. Thus Gore, in his text-book of “Electro-Metallurgy,” pp. 203-204, refers to the use of iron in recovering copper from large deposits of the Tharsis and Rio Tinto mines in Spain. The copper is dissolved by means of hydrochloric acid, and the liquid is run into large vats filled with scrap iron.In a short time all the copper is reduced in the form of feathery crystals upon the iron. The process is described by P. Argall and G. A. Kinahan in the Sci. Proc. Roy. Dublin. SOC.,N.S., 3, 1883, 502-328, and on p. 399 the production of crystalline copper is mentioned. No reference is made to the purity or size of the crystals. 98 -Water. Acid. Results. I 400 C.C. 0 Small dendritic crystals of copper were quickly produced. On standing the crystals increased slightly in size. I1 0 Nunierous small dendritic ciytals with ,J several about 7 mm. long. No im-purity detected. 111 7, 20 C.C. Two or three crystals about 11 mm. long with the usual mass of smaller crystals. No impurities were detected. IV 97 20 C.C.Four or five crystals 12 mum long with the usual mass of smaller crystalsNo impurity detected. V GOO C.C. 40 C.C. This solution gave the finest crop of dendritic crystals yet pmdnced. One crystal measured 15 mm., and its lateral branches were composed of clumps of crystals. The crystals were erect, and had a beautiful metdlic appearance. Several of the crystals were from 5-8 mm. in length, two or three 12-13 mm., and only a little spongy copper was to be seen. No impurity could be detected. The pure crystalline copper is in-soluble in pure nitric acid (free froni nitrous acid). See Veley (Proc.Roy. SOC., 1890). The reduotion of oopper from its sulphate by the aid of aluminium is mentioned in “ Watts’ Dictionary of Chemistry,” 2nd Sup., 1875, p.383, in a passage which is extracted from Cossa (Nuovo Cimento [el, 3, 75. The crystals of copper are described as follows:-“Aluminium foil immersed in a solution of sulphate or nitrate of copper is not acted upon at once, but after two days the foil becomes covered with crystals consisting partly of dendrites, but for the most part of well-defined octahedrons.” It was found that if the solution of the copper sulphate is neutral, only octahedrons are produced ; but that if an acid is present, dendrites are produced. Sulphyr was the only impurity detected. “ Copper is immediately reduced by aluminium from a solution of cupric chloride, and likewise, though more slowly, from the acetate.” It is not mentioned whether the copper is deposited in the crystalline or amorphous state, but the autbor has found on experimenting with these substances that dendritic cryst,als of copper arc produced in both cases.No impurity could be detected. Magnesium was found to reduce copper from a solution of copper sulphate in very small quantities, the copper being formed in small patches composed of dendrites and octahedrons. Magnesiiim added 99 to a solution of copper chloride caused an evolution of gas, throwing down a green precipitate, and at the same time reducing the copper in the spongy state. The well-washed copper contained magnesium. In a note by M. A. Commaille "On the Action of Magnesium on Neutral Metallic Salts " in the Chem. News,14, 188, it is mentioned "that copper sulphate gives with magnesium the metal (copper), the hydrated peroxide and a green subsalt.With the chloride no metal (copper) is precipitated, but a deposit of Brunswick green." In experiments made by the author with the chloride, copper was reduced in appreciable quantity, but in an entirely amorphous state. 46. "The action of ethylic oxalate on camphor." By J. Bishop Tingle, Ph.D. The author finds that camphor and eth.ylic oxalate in presence of CH2 +metallic sodium interact according to the equation CeH14< Ico qH.CO*CO,C,H, + C2H,0H, forming CJ&,Oa C 0.C 02C2H,= CBH,, <co ethylic camphoroayZate. This is an oily liquid, which decomposes on distillat ion ; on hydrolysis it is converted into cumphoroxylic acid, which crystallises in rhombic plates melting at 88" C.On reducing this acid with sodium amalgam, a &!actone of the formula-CH*CH(OH)*? 0 is obtained, melting at 75-76". EthylicCsH,,<~ 0-camphoroxylate and phenylhydrazine interact to form a mortophenyZ-hydrazone, which crystallises in white needles melting at 187-188" c. By the action of hydroxylamine a compound is formed which melts at 193" and will be further investigated, On heating ethylic camphoroxy late with aniline to 165", ozanilide is produced. 47. "The oxidation of turpentine in sunlight." By Henry E. Armstrong. It was pointed out by Sobrero in 1851 (C. R., 33,66) that when turpentine is exposed to light in presence of moisture and oxygen a crystalline substance is formed which has the composition represented by the formula CloH1,02 ; and that this substance is decomposed when boiled with dilute sulphuric acid, an oil being formed which has a powerful odour recalling both that of camphor and that of turpentine.The author's attention became directed to this substance about 12 years ago in the course of his studies of the terpenes and camphor, and in most years since, during the summer, he has carried 100 on experiments on the oxidation of CloHIshydrocarbons in sunlight, and has been able to confirm Sobrero's statements in every particular. As the crystalline product in question has not yet been named, it is proposed to term it-at all events, provisionally and until its constitution is determined-sobreroZ. Sobrerol is readily soluble in alcohol, and crystallises from this solvent usually in large, flexible, monosymmetric prisms having a peculiar hour-glass structure inside and showing hemihedrism.It is slightly eoluble in water, benzene, chloroform and petroleum spirit ; the aqueous solution has a bitter taste. It melts at about 150". The results obtained on analysis (carbon, 70.57 and 70.49 per cent.; hydrogen, 10.71 and 10.7'4 per cent.) show that, as Sobrero states, it has the formula CloH1,02= Cl0H,,+ H202,and there can be very little doubt that it is a glycol ; but, owing to its extreme sensitiveness to the action of acids, it is difficult to prove this by the ordinary methods. Sobrerol i8 optically active in a high degree, the apparent specific rotatory power of tho products from French turpentine in a 5 per cent.solution in alcohol (B. P.) being slightly above 150". Sobrerol from American turpentine (from Savannah) was found to have about the same rotatory power, but in the opposite direction. The optical similarity of the two products is noteworthy, inasmuch as the American has less than half the rotatory power of French turpentine. It would seem that only the terpenes proper, and not the citrenes, &c. (cf. Chern. 8oc. Trans., 1879, 734; J. SOC.Ghem. Ind., 1882, 478) form sobrerol. To ascertain whether this be the case, and what are the crystallographic and optical relationship of the products obtained from terpenes from different sources, the author is engaged in conjunction with Mr.W. J. Pope-to whom he is indebted for assistance in the research-in studying the behaviour of pure C1,H,,hydrocarbons of all kinds. When boiled with dilute snlphuric acid, sobrerol is readily converted into the oil referred to by Sohrero; the product is undoubtedly identical mth the isomeride of camphor which Wallach and Otto have obtained by treating turpentine with nitrous acid (AnmaZert, 253, 249), and which they have provisionally named pinoZ; as the compound is not an oZ, i.e., an alcohol, it may be suggested that it might appropriately be termed sobrerone. The product from sobrerol begins to boil at 150-160"? but passes over almost entirely at about 183",leaving a. small amount of a viscid oil ; it readily combines with bromine, forming a dibromide (bromine found 50.78 per cent.) which crystallises very beautifully in forms of the rhombic system, the lengths of the axes being in the ratio a : b : c = 0.5696 : 1:1.5553, dimensions which almost absolutely agree with those quoted by Wallach and Otto, viz., a : b : c = 0.5700': 1': 1.5553.The di- 101 bromide was found to melt at 93.5”, 94O being the melting point given by Wallach and Otto. The formation of sobrerone from sobrerol is of interest as serving to explain its formation by Wallach and Otto’s method: very probably sobrerol is first produced, ahd is at once acted on by the acid. Sobrerol is probably always ‘the initial product of oxidation of turpentine.It may be expected that sobrerone will be found among the oxygenated constituents of some essential oils, and it is proposed to search for it. If, as appears probable, sobrerol be a glycol, the formation of sobrerone from it is analogous to that of pinacolin from pinacone ; but, in this latter case, an isomeric change takes place, pinacolin being a ketone, CMe,*CO*CH,, and not the oxide corresponding to pimcone. Wallach and Otto’s observations, however, show that sobrerone is not a keto-compound. It would, therefore, appear to follow that sobrerone is an oxide formed by withdrawal of the elements of a, water molecule from two hydroxyls attached tb contiguous carbon atoms. 48. The structure of cycloid hydrocarbons.” By Henry E. Armstrong.The appearance of Bamberger’s remarkable papers (AnNalem, 257, 1 ; Ber., 1890, 1124), in which formule are pmposed for naphthalene, anthracene, &c.: apparently analogous to that suggested by v. Baeyer and the author for benzene, renders it desirable that the cases in which this formula is applicable should be carefully considered, espe- cially as the somewhat novel ccnceptions which the author would associate with this symbol tend to limit the extension of the hypo- thesis. Althoiigh superior to all other symbolic expressions in almost every respect, Kekulk’s formula is, nevertheless, admittedly open to the objections (1)that it apparently involves the existence of two ortho- and two met,a- di-derivatives ; and (2) that it represents benzene as containing three pairs of carbon-atoms in the condition of those in ethylene.The centric formula was developed to meet these objections. It represents benzene as a sjmmetrical configuration, and is sugges- tive of only three di-derivatives. The six affinities which in Kekule’s symbol act in pairs, as in ethylene, are assumed actually to neutralise each other milch as t.he affinities do in paraffins, but without con: stituting cross linkages within the ring as represented in the Claus formula, for example : the behaviour of the hydroterepthalic acids, of quinone and of anthracene, and, among others, Kekule’s researchm on the constitilltion of pyridine, of which he recently gave an account 102 in Berlin, affording, in the author’s opinion, abundant evidence of the non-existence of such cross linkages.The conception in his mind, to which, however, expression has not hitherto been given, has always been that the centric affinities act within a cycle rather than merely towards the centre in the manner pictured, and that there are peculia- rities in the carbon-atom which render such a form of action possible : benzene, according to this view, may be represented by a double ring, in fact. It would appear that when an additive compound is formed the inner cycle of affinity suffers disruption, and, such a cycle being no longer possible, the contiguous carbon-atoms to which nothing has become attached of necessity acquire the ethylenic or unsaturated condition. An extension of the hypothesis to naphthalene was suggested in September last year in a paper read at the British Association meet- ing at NewcastJe (B.A. Report, 1889, 175). The following is the symbol there proposed :-a This symbol again involves the admission of the unusual concep- tion that an affinity can act in two directions ( cf. PhiZ. Mug., June, 1888), the two carbon-atoms common to the two nuclei being repre- sented as exerting an influence in both nuclei. In this case also the ‘‘ centric ” affinities are regarded as acting within a cycle composed, however, of 10 carbon-atoms; but no separation of the central carbon-atoms, such as Bamberger suggests, is supposed to have taken place. It becomes possible in this hypothesis, in a measure, to under- stand that a radicle in the one nucleus should, as is known to be the case, exercise an influence on a radiole in the other nucleus, It appears to have hitherto been supposed that anthracene has a, symmetrical structure : the author contends, however, that this is not the case, and that it is to be represented by the formula H C H wherein C is the centric nucleus of benzene ; buk anthraquinone -which, strictly speaking, is derived from dihydroanthracene and not 103 from anthracene-is symmetrical and contains two centric benzene nuclei, thus :-co The behaviour of anthracene and anthraquinone appears to be entirely in accordance with these conclusions.Phenanthrene may be regarded as composed of two lateral (( centric ” nuclei, to which is conjoined a median nucleus in which the only two (‘available ” carbon-atoms are in the ethylenic condition.The behaviour of anthracene is more nearly that which it may be supposed the hypothetical hydrocarbon having the structure indi- cated by Kekul6’s benzene symbol would manifest. Pyrene, probably, is still more closely related to the ethylenic form of benzene, and has little, if any, resemblance to the centric form. Two formula may be assigned to this hydrocarbon- The first of these is the symbol of a phenanthrene derivative, but the behaviour of pyrene is so entirely unlike that of phsnanthrene that it may be regarded as out of the question ; the second would appear to be entirely in accordance with the results of Bamberger’s researches.It is contended that the formulae now siiggested serve to explain the exceptional physical properties of hydrocarbons such as anthra- cene and pyrene. DISCUSSION. Dr. JAPPdesired to know what precise mechanical conception Dr. Armstrong wished to express by the broken bonds in his centric formula. They appeared to denote attractive forces‘which stopped half-way-in other words, attractive forces which did not attract. In this way the centric formula would resolve itself into a benzene hexagon with triadic carbon. Professor RAMSAYsaid that he did not 0ee the necessity of substi-tuting an unusual conceptim for the one in common use, which, in his opinion, gave a sufficient and clear mental picture of the relations between benzenoid compounds.In the case of crotonio and isocro- tonic acids, an isomeric change is known whereby the position of the ‘(double bond ” is shifted. The difficulty in unreservedly accepting KekulB’s bznzene formula, caused by the fact that two ortho-com- pounds are unknown, while they are required by his conception, was, to some extent, removed by KekuG himself by his supposition that the double bonds were not stationary but were sometimes between carbon-atoms 1and 2, and sometimes between 2 and 3. In order to 1 explain the fact that a change from the symbol 11A1 to the sym- \/4 X bol (1/\11 is possible, it may be conceived that so long as no external ‘d influence is exerted on the benzene ring, it has the constitution sug-gested by KekulB.It is probable that two isomeric ortho-compounds are impossible, because, if formed by substitution of hydrogen-atoms 1 and 2, a change would take place whereby the double bond, con- necting 1with 2, would be dissolved and replaced by a single bond, while the double bonds would then exist between 1 and 6, 3 and 2 and 5 and 4. Or the contrary may be the case, and the single bond may be the more unstable form of uuion, in which case, if an ortbo- compound were formed between 2 and 3, the position of the bonds would also be reversed. The case of a change of position of double bonds in the crotonic acids renders this hypothesis not untenable. Mr. CROMPTONagreed with Professor R’amsay in his remarks, and thought that objections to the KekulA symbol,, based on the view that, because this symbol contained double bonds, benzene should behave as an olefinic compound, were unjustifiable. A double bond was nothing more than an incomplete representation, on paper, of an un- sat’urated condition or want of equilibrium in the molecule, a state of things that might be due to totally different and distinct causes in the two cases.The behaviour of benzene in this respect must, there- fore, differ from that of ethylene. The difference would have to be looked for in the different configurations of the molecules ; but it was just this point’ that received no representation, or only an inadequate one, in the plane formulae st present in use. The problem would, no doubt, only be finally solved when satisfactory space formulm for these compounds had been discovered. In reply to Dr.Japp, Dr. ARMSTHONGsaid that the broken bonds were intended to figure as resultants, much as the conjoiued effect of two forces acting from different directions was expressed by their resultant. Referring to Professor Ramsay’s remarks, he expressed the opinion that the isomerism of the crotonic acids was not suffi-ciently understood to serve as an argument in such a case. However 105 weli Lhe non-existence of isomeric ortho- and meta-derivatives might be accounted for by KekulB’s oscillation hypothesis, it was impossible in this way to explain the fact that benzene, on the whole, behaved as a saturated and not as an ethylenic compound ; there was also no reason to suppose, as Mr.Crompton had suggested, that “double bonds” in a ring would behave differently from those in an open chain : the whole of v. Baeyer’s recent work was in contradiction to any such assumption, and Thornsen’s and other observations left little doubt that in che formation of benzene there is a considerable “ outgoing of affiniby ” beyond that which takes place when ethylenic union is effected. He scarcely thought that the introduction of geometric considerations would materially advance the solution of the problem under discussion. Whatever the ultimate fate of his hypo- thesis, he was convinced that ;I settlement of many practical problems -those relating to laws of substitution and isomeric change, for example-required the knowledge of the inner structure of the cycloid hydrocarbons ; and such speculations, even if proved to be entirely false, at least served to suggest fresh lines of experimental iiiyuiry, and on this account were not only permissible but also desirable.49. “ Tertiary butyl mercaptan.” By Leonard Dobbin, Ph.D., Chemical Laboratory of the University of Edinburgh. The author finds that when tertiary butyl iodide is digested at a gentle heat with a suEcient quantity of zinc sulphide, an interaction takes place which results in the formation of tertiary butyl mercaptan. It is a colourless, extremely volatile liquid which boils at 65-66”, possessing an overpowering and disagreeable smell, recalling that of other mercaptans ; it solidifies in a freezing mixture of snow and salt to a white, semi-translucent mass ; it forms white, insoluble com- pounds with mercuric chloride and with silver nitrate.Products of higher boiling point are formed at the same time as the mercaptan ; these are believed to be tri-isobutylene, and probably also tertiary butyl sulphide. This part of the subject is under in-vestigation. 50. ‘G Desylacetophenone.” By Alex. Smith, B.Sc., Ph.D., Chemical Laboratory of the University of Edinburgh. The author finds that a dilute solution of potassium cyanide in alcohol and water acts in many cases as a condensing agent. Byboiling equimolecular proportions of benzoin and acetophenone in dilute alcohol with very little potassium cyanide, a condensation product, desyZacetophertone, is formed, CsH,*CO-CH(C,H,) (OH) + CH3*CO*C6H5= C,H,.Co*CH(C,H,).CH,.CO.CsH, + H20, which is the saturated coinpound corresponding to Jap p’s arihydracetophenone-benzil.It may be got perfectly purc and white by recrystallisation from acetic acid and alcohol. It melts at 126”. It is easily trans- formed into triphenyljhrfurane, triphenylpyrrole and triphenylthiophen, showing its constitution to be that given above. It forms a mono-and a di-hydroxinie ; by its interaction with one molecular proportion of phenylbydrazine, two molecular proportions of water being given off,an oiazine (pyridazine) is formed. This latter compound is con- verted by excess of phenylhydrazine into az’P-N-tetraphenylpyrrole.A large quant,ity of another substance having the formula C,,H,,O, is formed at the same time as the desylacetophenone. It would seem tbat the benzoin, or a part of it, acts as benzaldehyde, 3C6H6*COH+ CH,*CO*CsH, = CZgH2202 + 2Hz0. From acetone and benzoin the only substance isolable, if not, indeed the only one formed, is that corresponding to the last-mentioned pro-dixct from acetophenone. It has the formula C21H2002. The proper- ties and constitutions of these two substances are still under investi- gation ; as are also some other applications of the new interaction. At the next meeting, on June 19th, there will be a ballot for the fcllowing candidates :--1. Branson, Charles F., Kenly Lodge, Macaulay Road, Clapham Common.2. Edward, John Hutchison, 117, Stockport Road, Msnchester. 3. Hadam, Arthur R., Ph.D., 64, Rathgar Road, Dublin. 4.Jenkins, Wallis, 410, Glossop Road, Sheffield. 5. Johnson, John Robert, 16, Oxford Street, Liverpool. 6. Kelly, Patrick, 43, Lennox Street, Dublin. 7. McKillop, John, Pulan Brani, Singapore. 8. Parker, Thomas, M.I.C.E., W olverhampton. 9. Redding, Richard James, Royal Laboratory, Woolwich Arsenal. 10. Smith, Frederick, Johannesburg, Transvaal, South Africa. 11. Thornley, John Brooks, Ivanhoe Terrace, Ashby-de-la-Zouch. The following papers will be read :-“ Invertase, a contribution to the history of an unorganised fer- ment.” By C. O’Sullivan, F.R.S.,and I?, W. Tompson. “The action of carbonic oxide on nickel.” By Mr. Mond and Drs. Langer and Quincke. “The interaction of iodine, water and potassium chlorate.” ByH. Bassett. ~ABILISQNAWL) SONS, PHLNTGBS IN OBD:NARY TO HER XAJESTF, ST. MARTIT’S LANE.
ISSN:0369-8718
DOI:10.1039/PL8900600095
出版商:RSC
年代:1890
数据来源: RSC
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