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Proceedings of the Chemical Society, Vol. 22, No. 310 |
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Proceedings of the Chemical Society, London,
Volume 22,
Issue 310,
1906,
Page 141-152
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摘要:
lssLced 30/5/0G PROCEEDINGS OF THE CHEMICAL SOCIETY. Vol. 22. No. 310. Thursday, May 17th, 1006, at 8.30 p.m. Professor R. MELDOLA, F.R.S., President, in the Chair. Messrs. E. Barrett, E. R. Uhrystall, J. L. Foucar, P. H. Marsden, H. Martin, J. T. Nance, W. D. Seaton, W. H. Simmons, D. Sommer-ville, P. F. Spencer, F. W. Storey, R. W. Tonkin, and J. A. Watson were formally admitted Fellows of the Society, Certificates were read for the first time in favour of Messrs. : Shelton Cottlieb Agar, Panorama House, Guernsey. Thomas William D. Gregory, 82, Moorland Road, Burslem. John Gerard Hughes, 2, Canute Road, Southampton. Ernest Arthur Jenkinson, Dauntsey Agricultural School, West Lavington. William Rest Mummery, The Firs, Shenfield, Essex. Arthur Charles Palmer, B.Sc., 17, Wansbeck Gardens, West Hartlepoo!.Samuel Shrowder Pickles, B.Sc., The Imperial Institute, S.W. Willie Macro Seaber, B.Sc., Firdale, Sheen Lane? East Sheen. James Neil Watts, P.O. Eikenhof, Johannesburg, S. Africa. 142 Certificates have been authorised by the Council for presentation for ballot under Bye-law I (3) in favour of : Surendra Prasad Sanyal, M.A., Majhowli Raj, Gorakhpur, U.P., India. Allan Sime, Kingston, Jamaica. Edward Jocelyn Wortley, Rectory, Half -way Tree, Jamaica. Of the following papers, those marked * were read : “98. The relation between absorption spectra and chemical constitution. Part VI. The phenylhydrazones of simple aldehydes and ketones.” By Edward Charles Cyril Baly and William Bradshaw Tuck.A spectroscopic investigation of the phenylhydrazones of formalde-hyde, acetaldehyde, propylaldehyde, acetone, and diethglketone shows that all these compounds exist in two forms, the true hydrazone and the azo-form, in which the hydrogen atom has wandered from the nitrogen atom to the carbon atom of the aldehyde or ketone residue, thus Ph-NH-XCH*CH, and Ph*N:N*CH,-CH,. The azo-form is the more stable, and all the above compounds readily pass over into this form under the influence of light, except formaldehyde phenylhydrazone, which polymerises. All the azo-compounds are strongly coloured, owing to the isorropesis between the unsaturated nitrogen atoms and the benzene nucleus. If the compounds are prepared from p-bromo-phenylhydrazine, the change to the azo-form takes place quite slowly ; when aldehydes and ketones are allowed to react with p-bromophenyl- hydrazine, the true hydrazone is always produced first, which is not always the case when phenylhydrazine is used, for in certain instances the azo-compound is obtained at once.As is to be expected, true hydrazones which are perfectly stable are produced by the interaction of aldehydes and ketones with phexiylmethylhydrazine. An investigation into the absorption spectra of the hydrazones of the three isomeric nitrobeuzaldehydes shows that the colour of these substances is not due LO their existence in the azo-form. It is found, however, that they exist in the quinonoid form and are somewhat similar to the nitrophenols.The formula of the parts-compound is, in all probability, Hg>N:/=\:C:N*NH*Ph. Similarly, in the case \=/of p-nitrophenylhydrazine and its acetone derivahive, these compounds are quinonoid, thus : and are comparable with p-nit,roaniline. 143 DISCUSSION. Mr. W. ROBERTSON ..p ectra asked Mr. Baly if he had examined the a of the two pure acetaldehydephenylhydrazonesindividually, inasmuch as the product of melting point 80°, found by Mr. Baly to give rise to the absorption band in the ultra-violet, is far from being a pure sub- stance. It would be of considerable interest to ascertain if this band is also shown by either isomeride in the pure state in neutral solvents. Dr. LANDERasked the authors whether the change of hydrazone to azo-compound was complete, or whether the two substances formed a mixture in equilibrium in solution.Dr. HEWITTasked Mr. Baly if he had examined any hydrazones obtained from quinolylhydrazines. Ortho-and am-quinolylhydrazines were examined some years back by Dufton (Trans., 1891, 59, 756; 1892, 61, 782), when it mas found that certain of the derived hydr- azones, more especially those prepared with ana-quinolylhydrazine, exhibited brilliant colours. The author did not, however, suggest for them any other than a hydrazone structure (compare Armstrong, Frcms., 1892, 61, 789). Mr. BALYsaid that the two isomerides mentioned by Mr. Robertson would, if present, give identical absorption bands. He hoped to extend the work in very many directions, but had not yet examined the sub- stances mentioned by Dr.Hewitt. *99. The rusting of iron.” By John Trengove Nance. It is known that ammonium chloride solution accelerates the rusting of iron. The author finds that interaction takes place with evolution of hydrogen and liberation of ammonia ;iron passes into solution in the ferrous state, and is not precipitated in the absence of air, owing to the excess of ammonium chloride present. The solubility of iron in solutions of different concentration does not diminish proportionally with the amount of ammonium chloride present ;hence it is probably due to the action of hydrogen ions formed by hydrolysis of the salt, as similar proportional numbers are found for the solubility of iron and for the catalytic effect of the solutions on the hydrolysis of methyl acetate. The rate of rusting of iron in these solutions varies with the concentration in a similar manner, leading to the conclusion that rusting is due to the (mainly catalytic) action of hydrogen ions.In support of this, it is found that the chlorides of weak bases accelerate rusting far more than do those of the strong bases, and that the influence of acids is roughly propor-tional to their avidities. 144 DISCUSSION. Dr. MOODYthought it unfortunate that chemists were not definitely agreed as to the exact meaning to be attached to the term rusting. It appeared desirable that the term should be limited to those changes which metals undergo on exposure to air under normal atmospheric con-ditions.With regard to the results obtained by the author of the paper under discussion, it must be borne in mind that on heating a solution of ammonium chloride at 80’ ammonia would be evolved, and free hydrochloric acid would be formed in solution. In fact, the ex- periments resolved themselves into a determination of the attack on iron by solutions of hydrochloric acid of different strengths, and the theo- retical conclusions drawn by the author appeared unwarranted. Dr. F. M. PERKINagreed with Dr. Moody that the term rusting should be used to denote the atmospheric oxidation of iron, and should not be employed in reference to oxidation by other agencies. He pointed out that many other metals were dissolved by ammonium salts, and asked whether Mr.Nance had tried the action of ammonium persulphate, which dissolved iron much more rapidly than other ammo- nium salts. The solution of the metals was evidently due to hydrolysis, and, as ferric salts are much more readily hydrolysed than ferrous salts, the explanation of the rapid solution in ammonium persulphate was to be traced to the conversion of the ferrous salt into the ferriccondition. Oxidation of iron might be brought about by any feebly ionised acid. With highly ionised acids, as long as excess of acid is present, no pre-cipitation of hydroxide will take place, but with excess of iron, hydro- lysis mill ultimately ensue. In reply, Mr. NANCEsaid that he considered his results sufficient to prove that atmospheric corrosion and rusting of iron takes place through the catalytic intervention of hydrogen ions.“100. Aromatic compounds obtained from the hydroaromatic series. Part 11. The action of phosphorus pentachloride on tri-methyldihydroresorcin.” By Arthur William Crossley and James Stuart Hills. When phosphorus pentachloride acts on trimethyldihydroresorcin, two substances are produced, a liquid boiling at 118-119° at 33 mm., which is 3 : 5-dichloro-l:1 :2-trinaethyZ-A2%ihydrobenxene, and a solid melting at 76.5’, namely, 3 :5-dichloro-1 :2 : 6-ti.imethyEbenzene. This arornotic dichloride is converted on oxidation into 3 : 5-dichloro-hmimellitic acid, crystallising from water in transparent, hexagonal plates, containing 2H,O and melting at 226-22707 at which teni- 145 pemture it is rapidly converted into its anhydride.The trimethyl eater crystallises in rhombohedra melting at 62-63', and the monomethyl eater melts at 141-142O. "101. ''Studies of dynamic isomerism. Part V. Isomeric sulphonic derivatives of camphor." By Thomas Martin Lowry and Egbert H. Magson. Measurements were given of the solubility of a series of twenty sulphonic derivatives of camphor, both :done and in presence of a trace of alkali. The majority of the comy>ands derived from a-bromo-camphor and a-chlorocarnphor showed an increase of solubility similar to that observed in these compounds themselves and in their p-and r-halogen derivatives (Lowry, Proc., 1906, 22,70).In the case of camphor sulphonamide, a decrease of solubility resulted from the addition of alkali, and it was found that the amide, which crystallises unchanged from acetic anhydride, had been con-verted quantitatively by Nj500 sodium ethoxide in alcoholic solution CH <gH2at 20' into the anhydramide, 1' l4 . The p-amide derived from II SO,---N a-bromocamphor could not be converted into an anhydramide, but was found to yield an acetyl derivative, the solubility of which was unchanged by t,he addition of alkali; the compound is therefore CBrformulated as NH,-SO,*C,H,3<e.oat-The P-sulphonanilides derived from a-bromocamphor and a-chloro- camphor dissolve readily in caustic soda and are reprecipitated by acids.Possibly on account of their acid properties, the anilides, CHCl which may be formulated as, for example, (78H'3<<C*CEI , do not S02--N *C,H,Br increase in solubility when a trace of alkali is added. The isomerism previously observed in the camphor sulphopiperidides (Armstrong and Lowry, Z'rc~ns.,1902, 81,1449) has now been detected in the a-bromopiperidides ;both compounds, formulated as -~ CHBr CH <VHBr 7SH14<60 and 1' l4 y=NCSHl0, SO, NC,H,, so,-0 increase in solubility when alkali is added, and probably exist in stereoisomeric forms. “102. “The densities of liquid nitrogen and liquid oxygen and of their mixtures.” By John Kenneth Harold Inglis and Joseph Edward Coates. The authors have determined the densities of liquid nitrogen and of liquid oxygen, and of a number of mixtures of the two liquids at the temperatures 74-70’ and ‘79.07O Abs.on the hydrogen scale. These are the temperatures at which the vapour pressure of pure oxygen is 100 mm. and 200 mm. respectively, and they are therefore easily reproduced. The results showed that a slight contraction took place on mixing the two liquids, this contraction being greater at the higher temperature. The densities of the pure liquids differed by about 1 per cent. from the values obtained by Baly and Dorinan (T~ans.,1902,81,907). These values of the densities of the mixtures may be used to determine the relation between the partial pressures of nitrogen and oxygen above a mixture of the two liquids and their concentrations in that mixture.It is found that the solubility of nitrogen in oxygen obeys Henry’s lam; but that the solubility of oxygen in nitrogen does not obey the simple form of that law, for oxygen dissolved in nitrogen is associated to the extent of about 9 per cent. 103. ‘( Glutaconic and aconitic acids.” By Harold Rogerson and Jocelyn Field Thorpe. Ruhemann is mistaken when he states (Proc., 1906, 22, 137) that we were not fully acquainted with his several publications dealing with these acids. When we recorded the reactions of y-and py-ulphyl substituted derivatives of 2 : 6-dioxypyridine (Trans., 1905, 87, 1682), we com- pared them with the corresponding reactions of the dphyl ,&substi-tuted derivatives prepared by Ruhemann (Tmms.,1893, 63,876).The y-and by-derivatives prepared by him (Trans.,1899, 75, 245), and which he complains have not been mentioned by us, are ary2 derivatives containing phenyl and benzyl groups in these positions, and therefore were not, in our opinion, suitable for the purpose of comparison. As a matter of fact, the behaviour of our alphyl com- pounds differs in many important respects from that of the aryl compounds prepared by him. Ruhemann has also evidently misunderstood our meaning, since he writes (Zoc. cit.) : ‘‘They state that ethyl dihydroxycinchomeronate had firat been prepared by Errera and Perciabosco, but they overlook the fact that Ruhemann and Stapleton had obtained it the year before.” The passage referred to (Trans.,1906, 89,640) is : ‘(It is evidently 147 identical with the compound prepared by Errera and Perciabosco by the action of hydrochloric acid on ethyl 2 :6-dihydroxypyridine-3 :4 :5-tricarboxylate.” We did not desire to assign priority to Errera and Percishosco, but merely wished to establish the identity of our compound, an object which seemed to us better attained by referring to the method of preparation adopted by these chemists, rather than to the more indirect process used by Ruhemann and Stapleton.We have carefully re-read the paper by Ruhemann and Orton (Bey., 1894, 27,3449), and are still of the opinion that the remark (Trccns., 1906, 89, 634), “ Ruhemann and Orton suggest that aconitic acid correspouds to fumaric acid in constitution, whereas the malenoid form is represented by aceconitic acid,” is not an overstatement of the case, since probability surely implies suggestion. Regarding the criticism of our formula for these acids and the remark that, if they were correct, then the action of ammonia on ethyl aconitate might be expected to yield a five-membered ring com- pound besides citrazinamide, me cannot too strongly emphasise the remarks we made in our reply to Feist and Beyer (Trans., 1906,89, 650), which were to the effect that our formulzte for these compounds are merely an effort to represent diagrammatically a state of equili- brium between two tautomeric forms.104. “The chemistry of organic acid thiocyanates’ and their derivatives.” By Augustus Edward Dixon.Compounds of the class R*CO(CNS), when reacting with primary nitrogenous bases, present marked differences of behaviour, according to the nature of the hydrocarbon radicle, R. If R be aromatic, these compounds behave in ordinary circumstances principally as thio-carbimides, uniting additively with the base employed to form in each case R symmetrically disubstituted thiocarbamide : R*CO*NCS+ R‘NH,=RCO*NH*CS*NHR’. On the other hand, if R be a fatty radicle, the function of the associated group, -CO(CNS), varies greatly with the conditions-notably temperature and the nature of the base presented. In such cases, the end-products contain both disubstituted thiocarbamide and a mixture of substituted amide with thiocyanic acid, the latter substances originating through double decomposition : R*CO*SCN+R’NH, =R*CO*NHR+H-SCN. The interposition of an oxygen atom between the radicle R and the group CO(CNS), where the former belongs to the aliphatic series, increases the thiocarbimidic power of the resultant molecule : thus, phenacetyl “ thiocyanate,” Ph-CH,*CO(CNS), and phenoxyacetyl “thio-cyanate,” Ph*O*CH,*CO(CNS), readily yield the reaction for thio- 148 cyanic acid, whilst carbo-benzoxy-“ thiocyanate,” Ph*CH,*O*CO(CNS), does so to a very trifling extent. A number of substituted thioureas and thiocarbamides are described, resulting from the action of ammonia or other bases on various thiocarbimides, RO*CO*NCS,where R = phenyl, o-tolyl, p-tolyl, and benzyl respectively.When acetylphenylbenzylthiourea was heated under diminished pressure, a liquid distilled over having the general properties of acetyl ‘‘ thiocyanate ” ; this fact is regarded as confirmatory of Hawthorne’s view (Tmns., 1906, 89,566) that acetylthiocyanate is identical with acetylthiocarbimide. Phenylchlorocarbonate united directly with thiourea to form a cum-pound of formula NH:C(NH,)*S*CO*OPh,HCl; on treating with dilute alkali, diphenyl carbonate and thiourea were obtained and not the corresponding base. Unlike the fatty derivatives obtained from methyl or ethyl chlorocarbonate, the hydrochloride, when decomposed by heating, did not yield a pseudo-thiourea, NH:C(NH,)=S*Ph. 105. The molybdilactate and the tungstilactate of ammonium.” By George Gerald Henderson.The observations recorded in a previous paper (Trans.,1903,83, 259) on the influence of molybdic and tungstic anhydrides on the specific rotations of solutions of alkali I-lactates pointed to the conclusion that compounds of the type RO,(C,H,O,M), are formed both when the respective anhydrides are dissolved in hot solutions of the alkali lactates and when alkali molybdates and tungstates are heated with solutions of lactic acid. Attempts have since been made to isolate the molybdi-and tungsti-lactates so produced, only one of which, namely, potassium molybdilnctate, had already been obtained in crystalline form, and then in very small quantity and in a slightly impure state (Fmns., 1899, 75, 554).The results mere disappointing 80 Ear as the metallic salts were concerned, but, on the other hand, well-defined, stable ammonium salts of molybdilactic and tungstilactic acids were easily obtained. Thus, finally, crystalline derivatives of the tartar emetic type have been prepared from all the hydroxy-acids which were selected for examination, and in the latter case, as in the others, the author’s suggestions regarding the constitution of these compounds are supported by the results of experiment. Molybdic and tungstic anhydrides are dissolved, the latter with some difficulty, when heated on the water-bath with solutions of alkali lactates. The reaction comes to an end when the substances are present in the proportion of one mol.anhydride to two mols. lactate, and no reduction of the anhydride occurs unless a trace in excess of that 149 amount is added, provided that the solution is not heated to boiling. Addition of alcohol to the concentrated solutions causes the separation of colourless, viscous liquids which do not become crystalline even on prolonged contact with the mother liquor. When left in a vacuum desiccator over sulphuric acid, the syrupy liquids slowly dry to amorphous, glassy masses, which are extremely deliquescent, very readily soluble in water, and fairly so in dilute alcohol. Owing to the failure of all attempts to induce these substances to crystallise, they could not be obtained in a satisfactorily purified state, but an analysis of the compound of molybdic anhydride and sodium lactate, partially purified by dissolving in a little water and precipitating with alcohol, showed that its percentage of sodium was only a little higher, and of molybdenum a little lower, than that required by the formula Mo0,(C3H,08Na),.Similar results were obtained by experiments with calcium and barium lactates. The anhydrides are dissolved fairly readily by hot solutions of these salts, but the compounds formed could not be isolated except as vitreous solids, which analysis proved to be somewhat impure. The results were different when ammonium lactate was used. Molybdic anhydride was readily dissolved when heated on the water- bath with a solution of the salt, and, as in the case of the metallic lactates, no reduction took place unless a greater proportion of the anhydride than one mol.to two mols. lactate was added. After heating for some time, the solution was concentrated to a small bulk, and, after cooling, a quantity of a crystalline salt separated. The salt was purified by crystallisation from water, dried in a desiccator over sulphuric acid, and analysed : 1.0 gave 0.097 NH3. NH3= 9.7. 0.5 ,, 0.235 MoS,. M0=28.2. Mo0,(C3H40,NH,), requires NH3= 10-0; 1410 =28.2 per cent. Ammonium moh~bdikuctnte, MOO,(C3H403NH&, forms small, colour- less crystals which are fairly readily soluble in water and insoluble in alcohol. It is stable in the dry state at the ordinary temperature, but undergoes decomposition with loss of ammonia when heated in a steam oven.It is also stable in aqueous solution, but is hydrolysed on warming with dilute alkalis or mineral acids. When silver nitrate is added to a solution of the salt, a yellow precipitate is formed which quickly turns black if exposed to light. Anwbonium tungstilactate, ?V0,(C3H40,NH,),, was prepared and purified in a similar manner. It is a cdourless, crystalline salt, closely resembling and apparently isomorphous with the corresponding molyb-dilactate, than which it is somewhat more stable, as it does not begin to decompose when heated until R temperature of about 120° is 150 reached, when ammonia is evolved. It dissolves in water fairly readily and without change. Analysis of the purified salt, dried at looo, gave the following results : 0.5 gave 0.406 NH,.NH, =8.12. 0.5 ,, 0.268 WO,. W=42.5. WO,(C,H,O,NH,), requires NH, =7.94 ; W =42.9 per cent. My thanks are due to Mr. Hugh E. Brown for assistance in this work. ADDITIONS TO THE LIBRARY, I. Donations. Berkenhout, John. First lines of the theory and practice of philo-sophical chemistry. pp. xxiii + 434. London 1755. (Recd. 2/5/06.) From Mr. A. W. Laurie. British Institute of Preventive Medicine. Transactions. First series. London 1897. (Reference.) From the Lister Institute. Ferguson, John. Bibliotheca Chemica : a catalogue of the alchemical, chemical, and pharmaceutical books in the collection of the late James Young, of Kelly and Durras, Esq., LL.D., F.R.S., F.R.S.E.2 vols. pp. xxi + 487, 598. Glasgom 1906. (Recd. 24/3/06.) From the Trustees of the late Dr. James Young. Institute of Chemistry. Proceedings, 1878, 1879, 1881-1 902. London. (Reference.) From the Institute. Lister Institute of Preventive Medicine. Collected papers. No. 1. 1904, (Refeyence.) From the Institute. Morgan, J. Livingston R. Physical chemistry for electrical engineers. pp. viii + 230. New York 1906. (Recd. 3/5/06.) From the Publishers : Messrs. John Wiley & Sons. University College, London. Physiological Laboratory. Collected papers. Vol. XIII. 1903-1905. (Recd. 15/3/06.) From Professor E. H. Starling, F.R.B. II. By Purchase. Albu, AEbe?.t, and Neuberg, Carl. Physiologie und Pathologie des Mineralstoff wechsels nebst Tabellen uber die Mineralstoffzusam-mensetzung der menschlichen Nahrungs- und Genussmittel sowie der Mineralbrunnen und -B%der.pp. 247. Berlin 1906. (Recd. 21/3/06.) Granger, AZbei-t. La ceramique industrielle. pp. x + 644. Paris 1905. (Kecd, 16/5/06 .) 151 Clroth, Pad Heinrich. An introduction to chemical crystallo-graphy. Authorised translation by Etqh Marshall. pp. xii + 123. London 1906. (Recd. 16/5/06.) Ingalls, Walter Renton. The metallurgy of zinc and cadmium. pp. xviii+ 701. ill. New York 1903. (Recd. 24/3/06.) Kijnig, J. Die Untersuchung landwirtschaf tlich und gewerblich wichtiger Stoffe. 3rd Edition, pp. xxiv + 1083. ill. Berlin 1906. (Rectl. 16/5/06.) Mann, Gustav. Chemistry of the proteids. Based on Otto Cohnheim’s ‘‘Chemie der Eiweisskorper.” pp.xviii + 606. London 1906. (Recd. 21/3/06.) Meyer, Fkto~,and Jacobson, Paul. Lehrbuch der organischen Chemie. I1 Auflage. I Band, I Teil, 1 Abteilung. pp. 448. Leipzig 1906. (Red 21/3/06.) Minet, Adolphe. The production of aluminium and its industrial use. Translated, with additions, by Leonard Waldo. pp. vi + 266. ill. New York 1905. (Recd. 24/3/06.) 111. Pamphlets. Bayliss, W. M. The kinetics of trgptic action. (Reprinted from the Archives des sciernces biologiques, 11, 1904.) Bihar Planters’ Association. Report of the Indigo Research Station, Sirsiah (under subsidy from the Government of Bengal) for the year 1905-1906. By Cyil Bergtheil. pp. 29. Calcutta 1906. Day, Arthur L., and Shepherd, E.8. Quartz glass. (From Scimce, 23, 1906.) Kahlenberg, Lozci8. On the nature of the process of osmosis and osmotic pressure with observations concerning dialysis. (From the Trans. Wisconsin Acad. of Xciences, 15, 1906.) Thornson, R. T.,and Dunlop, H. On the examination of cod-liver oil and other fish liver oils. Part 11. pp. 8. Glasgow 1906. RESEaRCH FUND. A Meeting of the Research Fund Committee will be held in June next. Applications for grants, to be made on forms which can be obtained from the Assistant Secretary, must be received on-or before Monday, June 4th; 1906. Those Fellows who received grants in June 1905, or whose grants, allotted in June of previous years, have not been closed, are reminded that reports must be in the hands of the Hon.Secrztaries not later than Friday, June 1st’ 1906. 152 0L’E)VEI MElMORIAL LECTURE. The Oleve Memorial Lecture will be delivered by Professor T. E. Thorpe, C.B., F.R.S., on Thursday, June 21st, 1906, at 8.30 p.m., before the business of the Ordinary Meeting. EXTRA MEETINGS. An extra meeting wili be held on Thursday, July 5th, at 8.30 p.m., and the new Session will begin on Thursday, October 18th. At the next Ordinary Meeting, on Thuraday, June 7th, 1906, at 8.30 p.m., the following papers will be read : “Ammonium selenate and the question of isodimorphism in the alkali series.” By A. E. H. Tutton. ‘‘An improved Beckmann apparatus for molecular weight determina -tion.” By 3. M. Sanders. ‘‘Resolution of lactic acid by morphine.” By J. C. Irvine. It. CLAY AND SONS, LTX, BREAD ST. HILL, E.c., AND BUNOAY, SUPFOLK.
ISSN:0369-8718
DOI:10.1039/PL9062200141
出版商:RSC
年代:1906
数据来源: RSC
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