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Abstracts of the Proceedings of the Chemical Society, Vol. 4, No. 54 |
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Proceedings of the Chemical Society, London,
Volume 4,
Issue 54,
1888,
Page 63-68
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摘要:
ABSTRACTS OF THE PROCEEDINGS OP THE CHEMICAL SOCIETY. No. 54. Session 1888-89. May 17th, 1888. Ah*. W. Crookes, F.R.S., President, in the Chair. Certificates were read for the first time in favour of Messis. John Alexander, M.A., 14, Caledonia Place, Perth ; Charles Brad- shaw, 174, Nottingham Street, Sheffield ; Lewis Edmunds, 8, Graftoii Street, Piccadilly, W. ; William Humphrey Gibson, 107, King’s Road, Brighton ; Joseph Henry Maiden, Sydney, New South Wales ; Henyy Alexander Miers, M.A., Eden Cottage, Beckenham, Kent ; Franli Mousley, Phillimore Terrace, Walham Green, S.W. ; James Henrj- Rymer Paterson, 10, Millerfield Place, Edinburgh ; George Woodyatt l’rocter, 18, Alice Street, Sunderland ; Herbert I%.. Seeley, 11, Corir Market, Halifax. The following were elected Pellows of the Society :-George ‘l’hornas Evvaiis, Jolm Campbell Fell, Albert Harrison, John €3 nrch-mere Hariiwn, MA., Egbert Grant Hooper, John Hughes, Henrj-James Kirlimin, William Parsons, Henry Charies Reynolds, Frank Goodell Wait.The following papers were read :-40. ‘‘ Researches on the Constiitution of Azo-and Diazo-derivatives. IV. Diazo-amido-conipounds.” By Professor Meldola, F.R.S., and IF. W. Streatfcdd. Expressing the constitution of the mixed diazo-arnido-conipoullds by the general formula X*N,H*Y,the authors point out that in former papers they had given evidence that the alkyl-derivative X*N,R’.Y was capable of existing in three isomeric modifications :-(1) from the action of X.N,.OH on Y*NHR’; (2) from the action of Y-N2*OHon XmXHR’; (3) froni the direct all<ylntion of the compound produced hj-the action of X*N,.OH on Y.NHz: or of Y-N,*OHon X-NH,.The only known case at present established is that of the ethyl- tleiivatires of para-meta-dinitrodiazoamidobenzene,and the object of the present investigation has been to obtain other series of isomeric triplets. The triplet of methyl-derivatives is first described. By tbc direct methylation of the mixed para-meta-compound a derivative ot' m. p. 148" is obtained. By the action of diazo-p-nitrobenzene chloridr. on methyl-1,2-nitraniline a derivative is obtained mclting at 168". '1'11th third isomeride, formed by the action of diazotisecl in-nitraniline 011 methyl-p-nitraniline, melts at li6-li7".The triplet is thus show11 to confirm the isomerism indicated by the ethyl-derivatives. Methyl-derivatives of p-dinitrodiazoarnidobenzene (in. p. 219') and the coi-re- sponding ,m-compound (m. p. 127-128") have also been prepare(]. A considerable number of other new diazoamitlo-compounds havcb heen obtained in the course of a search for triplets of alkyl-derivatives, of which two members at least are requiretl as solids. It] has beeir found that mixed diazoamido-compounds cannot be obtained from thc nitranilines and p-chloraniline, as the resulting product is always a. mixture of the two symmetrical compounds. A very small quantity only of the mixed compound (p)No?.c,H*.N,H.c6H,cl(p) is formed under certain conditions by the action of diazotised p-nitraniline ~II y-chloraniline.In conclusion, the authors give a series of numerical rtwilts obtained by the analytical method described bF them in a former l):tf)er,arid which show that the amount of azonaphthol-compo~~ii(1, X*N,*C',,,H,)*OH/3+ Y*N,.C,,H,-OH$, produced by the deconz~osition of tlic diazoamido-compounds by liyclrochloric acid represents the qwintitative resolution :-2X*N,H*Y + 9HC1 = X.N,*CI + S-NH, + Y.N,*Cl + Y-NH,. -'1. '* 'l'he Colonr of some Caihli Compouiicls." By Tlionxxs Cariielle~-,1 ).S(s., and Joliii Alexandei.. M.A., University Collegt., I )nndcc~. -1careful iii\Tes tigation of a iiiiii. ber of iiietdlic derivatives of ortlio-niicl para-niti*ophenol Elas given tlie following results :-(1) In it11 cases without exccption the colour passes towards the red end of tlic spectruiii as the temperature rises.Organic compouuds thus beliave like inorganic substances. (2) The coiour of tlie ortho-derivative is nearer tlie red end than that of the corresponding para-compouiicl . Pai*a-conipounds almost always melt higher thin either of the corre- sponding ortho-or meta-compounds, and the piaobability is that of two isomeric bodies which are of different colour the one with the lowela melting point will have a colour nearer the red end of the chroniatic .scale than the one with the higher melting point. This is only what ~e should (I y~ioi-iexpect, for the compound with the lower melting point is at a correspondingly higher temperature than the other, and according to (1) the higher the temperature the more does the colour pass towards the red end.(3) A comparison of the nitrophenates of metals belonging to the same sub-group shows that the colour passes towards the red end as the atomic weight of the metal increases. This accords with the results observed by one of the authors (Phil. Mag., 1884 [5],18,130) in the case of inorganic salts. (4) When the same salt occurs in both the anhydrous and hydrated state, the colour passes towards the red end as the qiiaiitity of water of crystal- lisation diminishes. The exceptional behaviour in this respect of such inorganic salts as copper sulphnte is possibly due to the breaking down of the crystals on dehydration, which of itself frequently makes a coloured body become white or nearly so.(.5) As regards the salts investigated, the para-compound always takes up a larger quantity of wat,er of crystaliisatinn than the correspondby ortho-compound. DiscITSSIOK . Dr. ARMSTRONGremarked that the facts advanced were far too few to justify the very general conclusions arrived at by the authors ; all who had worked with the nitrophenols were well aware that the colour changed on heating in the manner described; and there was no novelty in the statement that the psranitrophenates crys tallised with the larger proportion of water. Referring to the suggested explanation of the colourlessness of dehydrated copper sulphate, he quoted calcium parachlorodiorthonitrophenafe as one of the exceptions to which such an explanation did not apply : this compound could be obtained either in yellow anhydrous crystals, or in deep-orange hydrated crystals.Mr. FRZSWELLmentioned magnesium and barium platinocyanide as instances of loss of colour taking place without loss of crystalline form ; the hydrated magnesium compound was of a splendid red colour, but when gently heated it became lemon-yellow, and when anhydrous it was white ; if care were taken, the dehydration could be effected without the dightest apparent injury to the crystals. Professor THOKPEsaid that he and Professor Judd had recently had occasion to examine the cyanides referred to, and he thought l3iat in reality the dehydrated crystals were mere pseudomorphs.Xr. WARINGTONmentioned having succeeded in expelling the ammonium sulphate from ammonium magnesium sulphate without changing the form of the crystals. 42. “The Identity of nat,ural and artificial Salicylic Acid.” ByW. N. Hartley, F.R.S. In order to determine whether natural and artificial salicylic acid 66 are the same substances, specimeiis prepared by Kolbe’s process ailti from oil of winter-green were carefully recrystdlised and examined by means of the spectrum. They were found to give identical series of photographs, and hence the same curve. 43. “ Researches on the relation between the Molecular Structure of Carbon compounds and tllieir Absoi-ption-spectra. (Part VIII.)” By W. N. Hartley, F.R.S.Isoineric Cyesols, Di1c.ydruxybeuxe’yles and Hydroxybenxoic Acids.-T he ultra-violet spectra of these substances were carefully examined, with the object of ascertaining how fay they are alike or different from each other. The oscillation frequencies of the extreme rays traiisniitted by 1mgrm.-molecule of the four series of substances, including xylenes previously examined, are the following :-Xylenes. Hydroxy-benzoic acids. I-- Ortho ............... 3611 3433 3466 3359 Met,a ................ Pam ................ 3580 3537 3413 3359 3399 3151 3080 2986 It appears from this table that the law which determines the order of greatest absorption is not the same in the series of isomeric hydro- carbons as in the series of cresols and dihydroxybenzenes.In the hydroxybenzoic acids it is the reverse of that in the xylenes. The curves of niolecular vibrations afford evidence of the relative extent to which energy is dissipated during the formation of the mole- cules of the substances, and they are classified according to the indi- cations of the curves. 44. “A Definition of the term Atomic Weight and its reference to the Periodic Law.” By W. N. Hartley, F.R>.S. The atomic weights are too f~equently viewed by those who become familiar with them in the capacity of teachers or as students, eitheras proportional weights, as combining weights, or as mere numbers with which calculations can be made for analytical or other purposes. That they are real measures of the puniatity of matter in tlie atoms of the elements is often overlooked. The reason of this is due to the ambiguous use of the word weight.A weight is a measure of the attraction between the earth and the matter weighed, or as it is more fRmiliarly stated, a measiire of the earth’s athachion for the bodj- 67 wcighed. The common method of determining relative quantities of matter is by weighing, and though the determination of the weightof a body does not actually determine its mms, yet the weight of a sub-stance is proportional to its mass. A so-called atomic weight is therefore a numerical proportion. There are 70 elements and 70 atomic weights, and these represent 70 different quantities of matter in 70 different' atoms; or in other words, they represent matter in 70 different states of condensation.I am of opinion that t'he teaching of chemistry is very much facili- tated by the use of the following definition, which I have used for some years past, and I would recommend its general adoption :-The atomic weight of an eleinen,t is the ratio of the mass of its atom to the mass of an atom of hydrogew. The term atomic weight should be abolished and atomic mass sub- stituted. Similarly, molecular weight should be defined as the mass of a molecule or molecular wzass. The statement that the molecular weight of a conipound is the sum of the weights of the atoms of the elements contained in it becomes simplified thus :-The mass of Q molecule is the sum of the mass of its constituent park Whatever remarks are applicable to the inconveniences arising from the term atomic weight, they may be emphasised in dealing with the Periodic Law.If we accept it as correctly stated, thus:-The properties of the elements are a periodic function of their atomic weights; then the ambiguous use of the word weight, and the tendency to see in the atomic weights only a series of numbers, obscures the true meaning of the law. A quotation from a recently published paper of great interest affords evidence that an important corollary of the law has been overlooked. Thus Professor Roberts-Austen refers to the fact that " Carnelley has given strong evidence in favour of supplementing the law as follows :-" The properties of compounds of the elements are a periodic function of the atomic weights of their cvnstituent' elements.' " (Proc.Roy. SOC.,43,425, 1888.) This was recognised by Mendelejeff,for he headed the columns in his table of the atomic weight's with their most characteristic oxygen HM HMand hydrogen compounds, such as M,O, MO, Ma03, M40,, M30 , &c. 25 Furthermore, he predicted the properties of the various hydrates, oxides and salts of scandium with most remarkable accuracy when he described those of eka-boron. Inasmuch as the properties of compound substances depend almost entirely upon their composition, and that both the chemical and physical properties of the elements are a periodic function of their so-called atomic weights, it follows that the periodical relationship must influence the compounds into which the ntoms enter.During the last six years I have made a practice of stating the periodic law ina much more concise and at the same time comprehensive manner, thus :-The properties of the atoms aye a periodicfunction of their masses. Thus the chemical and physical properties of both elements and compounds are directly connected with the quantity of matter enter- ing into them. In ally graphic representation of the periodic law the fact that it is upon the mass of the atoms that their properties depend should appear prominently. The diagram of Dr. G. Johnstone Stoney, F.R,.S., useci to illustrate his paper on the “Logarithmic Law of Chemis%ry,” recently read before the Royal Society, has on this account done a pre-eminent importance.The elements are distributed on a logarithmic curve of the second order, their masses being represented by volumes which are propor-tional to radii by which the curve is described and which are derived from numbers which are the cube roots of the atomic weights. Its most essential feature is a representation of the ratios of the masses of the atoms of other elements to the mass of the atom of hydrogen, and the consequent variation in chemical and physical properties accords with the positions of the elements upon the diagram. At the next meeting on June 7th there will be a ballot for the election of Fellows, a,nd the following papers will be read :--“The Chemical Action of some Micro-organisms.” By R. War-ington, F.R.S. By J. H.’‘ The Optical and Chemical Properties of Cao~tcho~c.’~ Gladstone, F.R.S., and W. Hibbert. IIAIXXISON AXD BONS, PRINTERS IN OKDINAKY TO HE& MAJESTY, ST.MARTIN’S LANE.
ISSN:0369-8718
DOI:10.1039/PL8880400063
出版商:RSC
年代:1888
数据来源: RSC
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