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Proceedings of the Chemical Society, Vol. 18, No. 252 |
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Proceedings of the Chemical Society, London,
Volume 18,
Issue 252,
1902,
Page 115-122
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摘要:
Issued 23/5/02 PROCEEDINGS OF THR CHEMICAL SOCIET-Y. VoI. 18. No.252. Thursday, May 15th, 1902. Dr. W. H. PERRIN,E.R.S., Vice-President, in the Chair. Certificate8 were read for the first time in favour of Messrs : James Handby Ball, St. Stephen's Villa, Limerick. Bryce Chudleigh Burt, University Settlement, Bermondsey, S.E. Arthur G'rozier Claudet, 27, Daleham Gardens, Hampstead, N.W. Edgar William Foll, 40, Sutton Street, Lambeth, S.E. John Longsdon Garle, 136, Holland Road, Keneington, W. George H. Leader, Sexey's School, Blackford, Somerset. James Butler Moody, 111,Manchester Road, Burnley, Lanes. Percy Philip Phillips, Haslemere, Morris Avenue, Manor Park, E. William E. F. Powney, 67, Barretts Grove, Stoke Newingtan, N. William C.S. Stanger, 72, Belle Vue Road, Ipswich. 01 the following papers, those marked * were read : "74. ('The variation with temperature of the rurface-tensions and denaitier of liquid oxygen, nitrogen, argon, and carbon mon-oxide." By E. C. C. Baly and F. (3. Donnan. The measurements were made by the method of elevation in capil- lary tubes. The surface-tensions, molecular surface-energies, and densi- ties of liquid oxygen,nitrogen, argon, and carbon monoxide have been determined between the temperatures of 70" and 90° (absolute). In 116 the case of argon, owing to the proximity of its freezing and boiling points, measurements could only be made between 84' and 89'. The relation between molecular surEace-energy and temperature is found to be linear, thus agreeing with the results obtained by E6tvtijs and by Ramsay and Shields for non-associated liquids.dThe values found for -y(Mu)Q, the temperature-coefficient of thedt molecular surface-energy, are as follows : Oxygen..................... 1.917 Nitrogen .................. 2.002 Argon ..................... 2.020 Carbon monoxide ......... 1.996 The average value obtained by Rnmsay and Shields for non-associating liquids was 2.212. Continuations of the straight lines connecting molecular surface- energy and temperature so as to cut the temperature-axis give values for the temperature which in the case of oxygen and nitrogen agree very closely with the critical temperatures as determined by Olszetvski. In the case of argon and carbon monoxide, the temperatures so found do not agree with the critical temperatures as previously determined, "76.*I Comparison of bromonitrocamphane with bromonitrocamphor." By M.0. Forster. The close relationship between 1:1-bromonitrocamphaae, CBrNO, C,Hl4<bBrN0, and au-bromonitrocamphor, CsHl,<&, , ledc=2 9 to the expectation that the series of changes by which the former sub- stance is converted into a hydroxylic isomeride of camphor might be applied to bromonitrocamphor, and thus give rise to a hydroxylic iso-meride of csmphorquinone. Bromonitrocamphor was theref ore heated with alcoholic silver nitrate until silver bromide was no longer pre- cipitated. This treatment, which transforms bromonitrocnmphane into nitrocamphene, C,,H,,*NO,, proceeds very slowly in the case of the camphor derivative, the solution becoming yellow.Instead of the expected nitro-compound, C,oH,,O*NO,, the only crystalline product obtained was camphorquinone. The yield of quinone by the new method amounted to 25 per cent. ; the process, therefore, compares favourably with that of Claisen, but is more tedious. The comparison of bromonitrocamphane with bromonitr ocamphor has been extended to the behaviour of these subst,ances towards phenyl- hydrazine. The uncontrolled action of the base is exceedingly vigorous and yields no definite product ; under regulated conditions, however, 117 bromonitrocamphane is reduced to nitrocamphane, which may be thus obtained in a purer form than has been possible hitherto.Nitro-camphane prepared by this method melts at 157'instead of 147-148', and has [aID= + 27.0" in benzene, and + 7.4" in absolute alcohol, instead of 20.4' and 4.6" respectively. In the case of bromonitrocamphor, phenylhydrazine gives rise to nitrocamphor in a form which requires to be crystnllised only once from petroleum to produce the substance in the colourless state, melt- ing at 103' and giving [a]D= -183*S0in benzene ; as the yield amounts to 84 per cent. of the theoretical, this method appears to be a distinct improvement on the existing process. Bromine has no action on bromonitrocamphor under conditions which lead, in the case of bromonitrocamphane, to elimination of the nitro-group and production of a tribromo-derivative. Bromonitro-camphor is also indifferent towards nitric acid, which transforms bromonitrocamphane into a new lactone ; alkalis eliminate hydrogen bromide from this compound, yielding salts of an unsaturated acid containing nitrogen.These derivatives are being investigated. *76. '(aa-Benzoylnitrocamphor and aa-benzoyliodocamphor." By M. 0. Forster and E. A, Jenkinson. heating 5 grams of enolic benzoylcamphor dissolved in 25 C.C. of glacial acetic acid with 1.5 C.C. of fuming nitric acid, is also produced when nitrogen peroxide is passed into a solution of benzoylcamphor in dried chloroform. It requires 40 parts of boiling alcohol to dissolve it and is sparingly soluble in common solvents, crystallising in rect- angular plates which melt and evolve gas at 225'.A 2 per cent. solu-tion in chloroform has [aID= + 245.2'. It is insoluble in aqueous alkalis, is indifferent towards ferric chloride, and does not give Lieber- mann's reaction. Attempts to convert the substance into aa-benzoylaminocamphor and au-benzoylhydroxylaminocamphor have been unsuccessful, but ib is readily hydrolysed by alcoholic potash, yielding a-nitrocamphor and benzoic acid. duced when benzoylnitrocamphor is dissolved in fuming nitric acid, is more readily soluble than the foinegoing substance, and crystallises from alcohol in pale yellow leaflets which melt aud evolve gas at 176-177' ; a 2 per cent, solution in chloroform has [a],= + 190.6'. Hydrolysis with alcoholic potash resolves the substance into nitro- camphor and m-nitrobenzoic acid.au-Be~azxoyZiodoccLm~rTLor,C,H,,<~l'Co' 'eH5, is not obtainable by CO the methods which give rise to the benzoylbromocamphors and benzoyl- chlorocamphors; it is prepared by adding a solution of iodine in potassium iodide to enolic benzoylcamphor disaolved in aqueous potash. The compound crystallises from alcohol in pale yellow plates which become reddish-brown when exposed to light ;it melts at 136O. A 2 per cent. solution in chloroform has [a],= +47.7". Benzoyliodocamphor is not converted into an isomeride by the action of hydrobromic acid, and hydriodic acid merely reduces it. Solutions in organic liquids rapidly undergo decomposition with liberation of iodine; ferric chloride soon produces a pale green colour, becoming bluish, and finally purple.Attempts to convert the substance into benzoylcyanocamphor and benzoylhydroxycamphor have been un-successful. "77. ''2 :4-Dibromo-5-nitro- and 2 :4-dibromo-3:5-dinitro-toluenes and their behaviour on reduction." By W. A. Davis, On nitration with fuming nitric acid, 2 :4-dibromotoluene gives 2 :4-dibrorno-5-nitrotoluene, which is converted by reduction with tin and hydrochloric acid into 4 : 6-dibromo-m-toluidine, the acetyl deriv-ative of which crystallises from alcohol in small, white prisms (m. p. 167O.) If the nitration of 2 :4-dibromotoluene be not carefully regulated, 2 :4-di6ronzo-3:5-dinitrotoluene is obtained. It crystallises from ethyl acetate in yellow prisms (m.p. 127.5') and differs from all the other bromo- and dibromo-nitrotoluenes, as it loses the whole of its bromine on reduction with tin and hydrochloric acid, giving s-tolylenediamine ; the diacetyl derivative, C,H,Me(NHAc),, crystallises from alcohol in small, hemimorphic prisms (m. p. 236-237") and is strongly electric. The removal of the bromine atoms from 2 :4-dibromo-3 :5-dinitro-toluene during reduction is apparently due to the influence of the two contiguous nitro-groups. "78.6'Note on the purification of hydrochloric acid from arsenic." By L,T. Thorne, Ph.D., and E. H.Jeffers. In the estimation of arsenic by the Marsh-Berzelius test, the use of hydrochloric acid is admittedly preferable to that of sulphuric acid.It is, however, practically impossible to purchase hydrochloric acid really 119 free from arsenic, and it is therefore necessary to remove the last traces of arsenic from it in the laboratory. The method recommended in the report of the Joint Committee of the Society of Chemical Industry and of Public Analysts (Analyst, 1902, 27, 48), namely, that of treatment of the diluted acid with hydrobromic acid or bromine and sulphurous acid and subsequent distillation is successful in most cases but occasionally fails, the arsenic then appearing to be present in a very stable or resistant form. Under these latter conditions, satisfactory results are said to be obtained if the hydrobromic and sulphurous acids are added to the strong hydro-chloric acid and the excess of hydrochloric acid gas boiled off before distil- lation commences.If large quantities of hydrochloric acid are wanted, this method is inconvenient and wasteful, owing to the large quantities of hydrochloric acid gas evolved. The whole of the arsenic may readily be removed by means of a modification of the well-known Reinsch test for arsenic in the following manner. The hydrochloric acid to be purified is diluted with water till its specific gravity is about 1.10, then raised to the boiling point, and a piece of fine copper gauze introduced. The gauze should be of about 100 meshes to the inch, and of as pure copper as possible. When a couple of litres of liquid are being dealt with, thegauze should be about four inches square and coiled very loosely (about 16 to 2 turns) round a long glass rod flattened at the end, as in this way it can be readily introduced and removed, besides being brought into better contact with the liquid.The whole is then kept just boiling for an hour. Bythis time, the gauze will have become more or less blackened, and should be replaced by a second piece and the digestion continued for another hour, If this piece is also blackened, a third is used, and so on, until the gauze remains perfectly bright after about an hour’s digestion. With moderately good acid, two, or at most three, pieces of gauze are sufficient. The gauze is then removed, and the acid at once trans-ferred to a retort and distilled from a fresh piece of gauze, It is advis-able, as a precaution, to reject the first 20 per cent.of the distillate, though even this is very rarely contaminated if the digestion is care-fully carried out, and from 100 to 200 C.C. should be left behind in the retort, The method is simple and requires but little attention, and it is not necessary to use the purest acid; even good muriatic acid, commercially free from arsenic,” may be satisfactorily employed, The acid obtained is the constant boiling point acid, which is about the most suitable strength for use in the Marsh-Berzelius test, The gauze must, of course, be gently ignited before being used, and should not be introduced until the acid is just beginning to boil. It is also preferable not to allow the digested liquid to cool in contact with 120 the air before transferring it to the retort, as the copper gauze would be much attacked and its efficiency for the present purpose consider- ably lessened by the consequent oxidation.79. “The radioactivity of thorium compounds. Part 11. The cause and nature of radioactivity.” By E. Rutherford and F. Soddy. The authors find that thorium from which ThX has been separated regains its activity with time, whilst the activity of ThX decreases with time. At the end of three weeks, the activity of the former again reached a maximum value, and the activity of the latter almost completely disappeared. ThX possesses a distinct chemical behaviour which differentiates it from thorium.Ammonia is the only reagent of those tried capable of separating it from the latter. Ammonium carbonate, oxalic acid, and sodium phosphate give precipitates with normal activity, and the residues from the filtrates are inactive. Using the radioactivity of the residues from the filtrates after pre- cipitation of the thorium by ammonia, as a means of determining the amounts of ThX present, it was found that the amounts produced in varying intervals of time bet ween successive precipitations agree with the requirement that ThX is being continuously produced by thorium compounds at a constant rate. The rate of production of ThX and the rate of decay of its activity are apparently unaffected by known agencies, Both changes proceed independently of the chemical and physical conditions of the molecule.The source of the energy required to maintain the radioactivity of thorium over indefinite periods is therefore to be found in a chemical change producing new types of matter. Many of the results obtained by the authors in their investigation of the thorium emanation are now capable of explanation. Emanating power appears as a property of ThX and not of thorium, and is pro-portional to the activity of the ThX present, The decay and recovery of emanating power of ThX and thorium are completely analogous to the decay and recovery of radioactivity, These results find their simplest explanation in the view that a secondary change is proceeding in ThX. One of the products is gaseous, and in the radioactive state constitutes the emanation.This change appears more allied to ordinary chemical reaction than the primary, for it is affected by the conditions. The residual activity of thorium would be explained if the chemical change which produces ThX produces also a second kind of active matter, closely allied to thorium in its properties. The radiations of this residual part are composed entirely of rays non-deviable in the magnetic field, whereas the other two components of thorium radio- 121 activity comprise both deviable and non-deviable radiation. In this respect, uranium and thorium are analogous (compare following paper).The present result, that radioactivity is the consequence of changes Andependent of the conditions-in which new types of matter are formed, leads to the conclusion that radioactivity is the manifestation of sub-atomic chemical change.80. ‘(The radioactivity of uranium.’’ By F. Soddy. During an investigation of the radioactivity of uranium (conjointly with Prof. Rutherford), great differences arose between the results obtained and those of previous workers. These are traced to the methods employed for measuring radioactivity. UrX, prepared by Crookes’ original method (Proc. Roy.floe., 1900, 66,409), although intensely active to the photographic plate, is almost inactive to the electrometer under ordinary circumstances. The uranium from which it is separated is inactive to the sensitive film, but its activity to the electrometer is very nearly normal.This is due to the dual character of uranium radiation (Rutherford, Phil.Mag., 1899, [v], 47, 109). The a-or easily absorbed radiabion is without appreciable action on the photographic film, and contributes by far the major portion of the ionisation effect observed by the electro- meter. The p-or penetrating radiation, on the other hand, causes the whole of the photographic effect, but being little absorbed by gases, and constituting but a small proportion of the total radiation, its ionisation effect cannot be well observed by the electrometer without special arrangements. UrX possesses all the P-with none of the a-radiation, the latter being completely retained by the uranium. The @-is wholly deviable in the magnetic field, the a-radiation not at all.This explains the con- clusion o€ Becquerel (Compt. rend., 1902, 134, 208), who worked solely with the photographic method, that the whole of the uranium radiation is deviable in the magnetic field. The discovery of Becquerel that inactive uranium recovers its activity with time (Compt. rend., 1901, 133, 977) therefore points to a continuous production of UrX by the uranium. This continuous production can be observed by means of the @-radiation in uranium originally freed from UrX after three days. The published methods of Crookes (Zoc. cit.) and Becquerel (Compt. rend., 1900,131,137) fail to remove the a-radiation of uranium, or even to diminish its quantity. As in the case of thorium, this constitutes a residual activity comprising only non-deviable radiation, and it has not I22 yet been found possible to remove it by chemical means.Experiment shows that if it is a secondary radiation caused by UrX, it must take over a year to decay to half its value after the exciting cause is re-moved. It seems therefore more probable that it is caused by a second type of non-uranium matter, produced from the uranium by the same change as he UrX. ADDITIONS TO THE LIBRARY. I. By Donation. Paetzold, Ernest. Beitrage zur pharmacognostischen und chemischen Kenntnis des Harms und Holzes von Guajacum officinal0 L., sowie des “Palo balsamo.” Pp. 11’7. Strassburg i. E. 1901. From Ed. Schaer. IngIe, Herbert. Manual of agricultiiral chemistry.Pp. 412. London 1902. From the Author. Btittger, Wilhelm. Grundriss der qualitativen Analyse vom stand- punkte der Lehre von den Ionen. Pp. 249. Leipzig 1902. From the Author. 11. 89 Purchctse. Windisch, Wilhelm. Das chemische Laboratorium des Brauers. Anleitung zur chemisch-technischen Betriebskontrolle f iir Studierende und Praktiker. Pp. 373. Berlin 1902. Long, John H. A text-book of urine analysis for students and practitioners of medicine. Pp. 249. Chicago 1900. RESEARCH FUND. A meeting of the Research Fund Committee will be held in June. Applications for grants, to be made on forms which can be obtained from the Assistant Secretary, must be received on or before June 9th. At the next meeting, on Wednesday, May 28th, at 5.30. p.m., the following papers will be communicated :-“Taxin.” By T. E. Thorpe, C.B., F.R.X.,and G. Stubbs. ‘I Some excessively saline Indian well waters.” By J. W. Leather. ‘‘ Soil samples.” By J. W. Leather. RICHARD CLAY AND SOITS, LINITED, LONDON AND BUNGAY.
ISSN:0369-8718
DOI:10.1039/PL9021800115
出版商:RSC
年代:1902
数据来源: RSC
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