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Proceedings of the Chemical Society, Vol. 27, No. 380 |
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Proceedings of the Chemical Society, London,
Volume 27,
Issue 380,
1911,
Page 1-16
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摘要:
Issued 30/1/11 PROCEEDINGS OF THE CHEMICAL socmv. Vol. 27. No.380. Thursday, January 19th, 1911, at 8.30 p.m., Professor HAROLDB, DIXON,M.A., Ph.D., F.R.S., President, in the Chair. Mmrs. Henry Dent Gardner, jun., and Thomas R. Merton were Eormally admitted Fellows of the Society. Certificates were read for the first time in favour of Messrs.: John Ewart Trounce Barbary, Vellansaundry, near Camborne. Harold Christopher, B.Sc., Mona, Lucien Road, Tooting Common, S.W. Harold Edgar Dryden, 490, Stanton Road, Burton-on-Trent. James Furnival Eardley, Elmsdale, Broomhall Park, Sheffield. William Joseph Chetwynd Horne, c/o Messrs. Cleeve Bros., Lansdowne, Limerick. Reginald Hurst, 50, Culverley Road, Catford, S.E. James William MacBain, M.A., Ph.D., 71, Cotham Brow, Bristol, Edward Partington, Oakdene, Sedgley Park, Manchester.Cyril James Peddle, M.Sc., 146, Barnsley Road, Cudworth, near Barnsley. David Thomson, M.A., B.Sc., Ph.D., Viewpark, Litham Road, Strathaven, N.B. William Denham Verschoyle, 15, Winch Building, Vancouver, B.C. Bertie James Waygood, 39, Marshall Road, Levenshalme, Man- Chester. Edward Escott Wood, Hurricane House, Brymbo, N. Wales. Charles Fursdon Yates, Ronaldene, Witham Road, Isleworth. Certificates have been authorised by the Council for presentation to ballot under Bye-law I (3) in favour of Messrs. : Solomon Parley Acree, Johns Hopkins University, Baltimore, Md., U.S.A. Robert Leonard Emerson, A.B., M.D., Bmton, Mass., U.S.A. Of the following papers, those marked * were read: "1, "The interaction of alloxan and glycine."By William Holdsworth Hurtley and William Ord Wootton.The authors have examined the action of alloxan on glycine in aqueous solution. By mixing concentrated solutions of these, Piloty and Finkh (Annalen, 1904, 333,22) isolated a substance which they described as glycine purpurate. The author8 regard this product as a mixture of at least three substances. They have examined the action as it occurs in dilute solution on heating, and, unlike Strecker (Annalen, 1862, 123,363) and Piloty and Finkh (Zoc. cit.), find that formaldehyde is evolved. The reaction occurs in several stages, murexide being produced first, then a substance closely related to uramil, and finally a substance isolated by Piloty and Finkh and regarded by them as uramidoacetic acid.This, the main product of the reaction, is a pale yellow, crystalline solid, characterised by powerful reducing properties, by yielding form-aldehyde on hydrolysis or by treatment with 50 per cent. nitric acid, by the production of an amide with ammonia, and by the formation of alloxan with dilute nitric acid. The authors are of the opinion that a substance possessing these properties cannot have the formula: which is assigned to it by Piloty and Finkh; they give it therefore the following co,nstitution, which is more closely in accord with its reactions : fi(OH)*CH(N:CH,) CH(OH)--fj*( )HN.C(OH)Ujy>C(OH)* C@H)<, :C(O*).N ' and propose to name it 2 : 4: 6 : 21 : 41: 5' : 6/-heptahydroxy-5-methyleneamino-4 : 5 : 41 : 5'-tetrahydro-4 : 4l-dipyrimidyl.DISCUSSION. Dr. HURTLEP,in reply to Dr. Pyman, stated that the yield of formaldehyde in this reaction was 7.5 per cent. of the theoretical. ‘6“2. Intramolecular rearrangements of diphenylmethane o-sulph-oxide.” By Thomas Percy Hilditch and Samuel Smiles. Diphenylmethane o-sulphoxide (I)is obtained by the oxidation of thioxanthen with hydrogen dioxide, and it is converted into the red carbothionium chloride (11) by the action of hydrogen chloride (1.) (11.) in dry alcohol. This salt is more readily obtained from thie xanthenol wibh hydrogen chloride in ethereal solution, and, if excm of hydrochloric acid is removed, it is transformed into thioxamthenyl cHClchloride, C6H4<--S>C,H, Thioxanthenol is regenerated from the latter substance or from the carbothionium salt by the action of water or alkaline reagents.The transference of oxygen from sulphur to carbon, which may be effected by thus converting the sulphoxide into thioxanthenol, may be carried out by the aid of heat alone, for both substances furnish thioxanthenyl oxide when they are heated to about 120O. This rearrangement. was discussed from a general point of view, and in its bearing on the behaviour of the analogous diphenylamine 0-sulp hoxide. *3. The reactions between chemical compounds and living muscle-proteins.” By Victor Herbert Veley. The main conclusions drawn by the author are as follows: (1) When it living muscle is immersed in solutions of certain compounds, a chemical change takes place between the solute and the amino-acids formed from the muscleproteins by hydrolysis; its rate can be measured by the height of response to induction shocks used as an indicating record.(2) In most cases examined, the rate of change is a logarithmic function of time represented by the equation of a reaction of the first order, namely, IK =1 /t(logro/rt),in which ro is the number of units of potential chemical change, when t =0, and rt the number d units remaining after expiry of time t. In a few cases the rate of change is a linear function of time, which, although less conclusive, does not exclude the possibility of a chemical change.If the hypothesis be correct that the chemical changes are due to a reaction between the drug, whether acid or base, and the amincFacid, either formed by hydrolysis of the muscle-proteins or present by virtue of the moribund condition of the muscle, then amino-acids should produce no change, or, in other words, the record would not differ from that of a fatigue effect. Results were given in the case of aminoacetic acid in proof of this line of argument. 4. ‘‘The decomposition of tetramethylammonium nitrite by heat.’‘ By Prafulla Chandra BQyand Hemendra Kumar Sen. Tetramethylammonium nitrite decomposes at 228--230°, but more regularly and rapidly at 250-260O. The main gaseous products of decomposition are trimethylamine, methyl nitrite, carbon dioxide, nitric oxide, nitrogen, and water.A small fraction of the salt at the same time undergoes charring with the formation of an oily liquid which soon becomes resinified. 5. “Influence of minute quantities of ferric salts and of manganese nitrate on the rate of solution of mercury in nitric acid.” By Prafulla Chandra Ray. Minute quantities of ferric nitrate (0.026 gram) or ferric sulphate (0°0025 gram) in dilute nitric acid (50 c.c.) containing 12 to 13 per cent. of the acid have a marked retarding effect on the dissolution of mercury in it. Manganese and sodium nitrates, on the other hand, accelerate the dissolution of mercury in nitric acid. 6. (‘On dl-and d-A~-m-menthenol(8) and d-and d-Az:8:(B)-m-menL thadiene.” By Walter Norman Haworth, William Henry Perkin, jun.,and Otto Wallach.An account was given of the synthesis of the substances men- tioned in the title and of many of their derivatives, by two different methods. The physical properties of all these substances have been determined and were fully discussed. 7. ‘‘The identity of xanthaline and papaveraldine.” By Bessie Dobson and William Henry Perkin, jun. The authors have made a careful study of the alkaloid xanthaline wl&h Messrs. T. and H. Smith (Phurm. J., 1893, p. 793) isolated in very small quantities from opium, and they find that this alkaloid is iden tical with pap ave raldine. 5 8. 64Amalgamscontaining silver and tin.” By Reginald Arthur Joyner.The non-existence of any compound of silver with tin other than Ag,Sn is confirmed. The “ageing” of filings of silver-tin alloy has been experimentally verified and investigated. The composition of saturated liquid amalgams of tin, of silver, and of tin with silver has been determined at a number of temperatures, and the equilibrium diagram representing the ternary systems existing below 63O has been ascertained. No ternary compound exists at these temperaturerr, and the stable solid phases are the compound AgsHg4 and a solid solution containing a small amount of mercury dissolved in tin. No solid solution exists between these two solid phases. The alloys of silver with tin are thus completely decomposed by the action of excess of mercury.At higher temperatures a ternary compound is formed. 9. “Studies of the constitution of soaps in solution. The electrical conductivity of sodium stearate solutions.” By Richard Charles Bowden. At 90° the equivalent conductivity of sodium stearate in aqueoua solution is about half that of sodium acetate, being 88.3 mhos in a, weight-normal solution, about 77 for solutions between N/2-and N/20-, but rising to 125.9 in N/lOO-solution. It is considered that these measurements demonstrate the presence of a high concentration of free electrolyte in solutions of sodium stearate. The change in conductivity with the dilution differs from that in solutions of sodium palmitate, but it is not less remarkable. Attentiqn waa drawn to the connexion between these phenomena and the analogous behaviour of certain non-aqueous solutions as well as to the salting out from soap solutions of acid sodium salt by means of concentrated solutions of sodium hydroxide.10. “Additive compounds of phenols and phenolic ethers with aromatic polynitro-derivatives.” By John Joseph Sndborongh and Stanley Hoskinga Beard. The authors described a number of additive compounds prepared from s-trinitrobenzene and phenols, phenolic ethers, and cyclic oxygen derivatives. Many of the compounds are coloured, but aa a rule are much paler than the additive compounds of amines and s-trinitrobenzene. 6 11. ‘‘ The effect of contiguous unsaturated groups on optical activity. Part VI. The influence of the carbonyl group on optical rotatory power.Part VII. The relative influences of aromatic and hydroaromatic nuclei on optical rotatory power. Part VIII. The influence on optical activity of two contiguous unsaturated groups in comparison with that of one unsaturated group at varying distances from the optically active complex.” By Thomas Percy Hilditch. (1) The author has sought to obtain evidence of the effect of the system *CO*CO,H on optical rotatory power, in order to effect a comparison with that of the group -CH:CH*CO,H, which is now fairly well known. From investigation of the menthyl esters and brucine salts of ketonic acids of the pyruvic, mesoxalic, and phenylglyoxylic series, it appears that the carbonyl group increases the initial effect of the carboxyl group on the molecular rotatory power of the optically active alcohol or acid, and its influence is thus very similar to that of an ethenoid bond.(2) The relative influences of aromatic and hydroaromatic nuclei on optical activity have been invest,igated by means of the salts iormed from corresponding aromatic and hydroaromatic bases with optically active acids (camphoric, camphor-.rr-sulphonic, and tartaric acids). The results show consistently that so long as an aromatic group is contiguous to the basic nitrogen atom, a well-defined optical anomaly persists, but this disappears wherever the radicle attached to the nitrogen is fully reduced. It was also pointed out that “ring. formation,” which is usually stated to produce a large alteration in rotatory power, does so only when the asymmetric carbon atoms form part of the ring system.(3) Rupg (;1nnalen, 1903,327,157) has stated that the nature of the effect of unsaturated groups on optical activity is determined by their nearness to the asymmetric atoms. Experiments have been carried out to decide whether, in ccrtain cases, it is the proximity of an unsaturated system to the ,;sj-;nmetric complex, or the con- jugated unsaturated groups present, which causes the anomaly in rotatory power, and it appears that whilst both causes undoubtedly operate, the latter is the more powerful factor. 12. “The relative effects of ethylenic and acetylenic linkings on optical rotatory power.” By Thomas Percy Hilditch.d-Methylhexylcarbinyl B-phenylpropionate, cinnamate, and phenylpropionate, and the neutral and acid menthy1 esters of 7 succhic, furnark, and acetylenedicarboxylic acids have been examined with respect to the relative effects of the ethylenic and acetylenic linkings on optical rotatory power ;the former series is interesting in view of the simplicity of the asymmetric svstem in the alcohol used and the similarity of this compound to amyl alcohol. From a general survey of the fourteen series of active salts or esters of these acids now available for comparison, it is seen that in twelve cases the fully saturated member is least anomalous in optical activity, whilst in the other two the ethylenic and acetylenic compounds respectively possess the smallest rotatory power.On the other hand, it is concluded that there is no general rule to cover the relative effects of the double and triple carbon linkings, and that the influence of the acetylenic (+carboxyl) residue is in general much less well defined than that of the ethenoid (+carboxyl) group. 13. ‘(The direct action of radium on ammonia.” By Edgar Philip Ptrman. The rate of decomposition of ammonia by the direct action of radium bromide has been measured approximately. The pressure of the ammonia, together with its decomposition products, decreased for five weeks, and then steadily increased. The reaction appears to be of the first order. 14. 66 Cupritartrates and analogous compounds.’’ By Spencer Umfreville Pickering.By adding potassium hydroxide to copper tartrate just short of alkalinity, and precipitating by alcohols, a cupritartrate of the formula (~2H,02*CuO),(C02)4E2Cu,H,0is obtained, and by the further action of the alkali and water, two others derived from this by the partial substitution of copper for the potassium were also prepared. Analogous compounds of saccharic and mucic acid were obtained, (C4H8O4*CuO),( C02),K2Cu,H20, as also was an a-cupri-Alltartrate, (C2H,0,*CuO)4(C02),K,Cu2,,(CuC03)2,N~C03. six compounds, when dried at a temperature just below that at which they decompoae, gave minimum molecular weights agreeing with these formulz, and inconsistent with the view that the copper displaces the hydrogen in the alcoholic hydroxyl.Probably this hydrogen is displaced by the group (CuIIOH)I, the copper in the carboxylic portion of the molecule being present as (CuIVO)I1, as in the cupricitrates. Quinic acid forms analogous compounds, but these were not obtained in a pure condition. 15. Molecular association in water.” By Cyril James Peddle and William Ernest Stephen Turner. Following on the work of Meldrum and Turner, which revealed the existence of molecular association in water of a number of amides and anilides (Tram., 1908, 93,876; 1910, 97, 1805), it was shown that molecular association in water is of frequent occurrence. A number of carboxylic acids, phenols, and mines have now been examined. Except in the case of the aliphatic amines, most of the substances are distinctly associated. Benzoic acid is more associated in water than in benzene.The apkearance of water among the solvents which permit association, so contrary to the general experience and belief in its dissociating power, waa explained on the supposition that molecular association in water is really due to a dissociation of complex water molecules, a view suggested in connexion with the amides, and now further developed and applied to other associated solvents. 16. Note on the preparation of thiobenzanilide.” By Edward de Barry Barnett. Thiobenzanilide can readily be obtained in 90 per cent. yield by the following modification of Bernthsen’s method (Bey., 1878, 11, 503). Twenty grams of benzanilide are intimately mixed with 10 grams of finely ground phosphorus pentasulphide and 10 grams of finely ground phosphorus trisulphide.The whole is then cautiously heated over a naked flame with continual shaking until fusion takes place. After cooling, the mass is extracted several times with boiling acetone or alcohol, the united extracts rendered strongly alkaline with sodium hydroxide, and then poured into a large bulk of water. The dark solution obtained on filtration is then saturated with carbon dioxide, when the thioanilide is obtained as a yellow, crystalline precipitate, which need not be further purified. Attempts to apply the above method to the preparation of thie formanilide and thioacetanilide were not successful, owing to the large quantity of tarry matter formed.6i17. Organic derivatives of silicon. Part XIV. The preparation of tertiary silicols.” By Frederic Stanley Kipping and John Edward Hackford. Tertiary silicols, R,Si-OH, can be prepared by treating silicones, R,SiO, with a Grignard reagent ;termolecular silicones, (R,SiO),, dihydric silicols, R,Si(OH),, and substituted metasilicic acids, R-SiOaOH, may also be employed for this purpose. The following compounds were prepared : BenzyZda’ethyZsGicoZ, SiEh(CH,Ph) *OH; benz ylet hylpropglsilicol, SiEtPr( CH,Ph) *OH; plienyl~thylethylsilicol, SiMeEtPheOH ; phenyldiethyl8&col, SiEhPh*OH;dzbeltzylmethylsil~col, SiMe(CH,Ph),*OH ;triphertyl-siticol, SiPh,-OH ;tm’benzylsilicol, Si(CH%Ph),*OH. When phenyl- ailicon trichloride is treated with steam, it gives the anhydride of phenylmetasilicic acid, whereas with water it gives the acid.The anhydride is insoluble in all neutral liquids which were tried, and is probably highly polymerised. 18. ‘‘o-Carboxganilides of the augars.”By James Colquhoun Irvine and Alexander Hynd. The conditions under which the common reducing sugars con-dense with anthranilic acid have been ascertained, and it is found that the best results are obtained when solutions of the sugars in dilute alcohol are mixed with excess of the acid and kept in the cold for several weeks. In this way, galactose-, mannose-, rhammse-, and maltose-cwarboxyadides have been prepared. Lactose gave a negative result. In the case of fructose, the product could not be obtained pure, and the corresponding glucose compound has already been prepared (Trans., 1909, 95,1553).The condensation proceeds by reaction between the amino-group and the reducing group of the sugar, as all the products behave ae acids. The compounds appear to be y-oxides, as they show extremely rapid mutarotation comparable in magnitude and direc- tion with that given by anilides and methylated anilides. Glucose also condenses with alanine in a similar manner to give glucosealanide (m. p. 114O), which, judging from its optical behaviour, exists in a-and &forms, which are interconvertible at goo. A parallel investigation carried out with tetramethyl glucose shows .that reaction does not proceed readily between amin& compounds and the methylated sugar, and even ammonia and hydrogen cyanide are without action in the cold.Tetramethgl glucose-p-phenetidid e, -P-napht hylamlide, and -p-toluidide were, however, prepared. The latter alone is crystalline (m. p. 144O), and shows extensive mutarot ation. 19. The iodobenzenemonosnlphonicacids. Part 111. 2 :3-Di-iodo-and 2 :3 :4 :5-tetraiodo-benzenesulphonicacids.” By Mary Boyle. 2 : 3-Di-iodobenzenesulphonicacid has been prepared by treating p-nitroanilineo-sulphonic acid with iodine chloride, the nitregroup 10 being removed after the displacement of the aminegroup by iodine. A new and convenient method of obtaining the initial nitroarnine acid in large quantities has been devised.The di-iodosulphonic acid separates from mineral acid solutions in shining crystals, and yields crystalline salts and a well-characterised chloride; its methyl and ethyl esters have been prepared. The ‘tetruiodo-acid is prepared from m-iodoaniline-p-sulphonic acid ; its c?z,ZoP.ide differs from those containing two or three iodine atoms in possessing a distinct yellow colour. 20. 44 Occurrence of pentathionic acid in natural waters.” By James Scott Maclaurin. Pentathionic acid has not previously been found in natural waters. This may be due to the fact that in ordinary analyses of mineral waters no special search is made for such compounds. Some account of the circumstances that led to the discovery of the occurrences of the acid should therefore be of interest. The water in which it was found was obtained from a, lake on White Island. This island, which is the summit of a volcano, lies in the Bay of Plenty about thirty miles from the mainland.The lake covers an area of approximately 15 acres, and has a mean temperature of about llOo (Fahr.). The water is of a very unusual character, containing a great variety of salts and much free hydre chloric acid. In examining it for iodine by the potassium nitrite test, the author noticed the formation of a brown colour, which suggested the presence of a ferrous salt, but, on titrating with potassium permanganate, more permanganate solution was used than the iron (previously determined gravimetrically) could require, even if all were in the ferrous state, and judging by the colour of the water, much of the iron was in the ferric state. There was no organic matter to cause this excessive reduction, and on adding LT/10-iodine solution no appreciable action took place, showing that the reduction could not be caused by sulphur dioxide or hydrogen sulphide.After removing sulphates by means of excess of barium chloride, and heating the filtrate with bromine water, a further precipitate of barium sulphate was formed, showing that some sulphur compound was present. It seemed probable that this was one or more of the polythionic acids, most probably pentathionic acid. In order to prove the truth or otherwise of this surmise, the water was boiled with mercuric cyanide (Debus, Trans., 1888, 53, 278).The reaction between mercuric cyanide and pent& thionic acid is as follows: Hg(CN), +H2S,06=HgS + S2+ 2S03+ ZHCN. 11 If the mercury in the precipitate (HgS+ S,) be determined, the equivalent amount of hydrogen in the pentathionic acid can be calculated, and, by precipitating the SO, in the filtrate as barium sulphate, the oxygen and part of the sulphur can be estimated. The remainder of the sulphur can be determined in the first pre- cipitate (HgS+ S,). The results so obtained approximated roughly to the formula H2S,0,. The value for oxygen was, however, too& high, and it was thought probable that this was due to the oxidising action of the ferric chloride and hydrogen chloride present in considerable quantities in the water.Attempts to remove these oubstances by the ordinary methods were unsuccessful, but the difficulties were met by shaking the water with slightly less magnesium oxide than was necessary to neutralise the free acid, and then precipitating the iron with potassium ferrocyanide. Although the hydrochloric acid could be nearly neutralised by this means, the chlorides so formed reacted with the mercuric cyanide, so that instead of a precipitate of the composition HgS + S,, one containing a large proportion of mercuric chloride was obtained. This rendered the determination of the hydrogen in the pentathionic acid more difficult and less trustworthy than in the absence of mercuric chloride. It was therefore decided tu be satisfied with the approximate values for hydrogen already found, but to redetermine the sulphur and oxygen.For this purpose 2000 C.C. of the water were precipitated in the cold with slightly less barium chloride solution than was necessary to throw down all the SO,. After twenty-four hours, the barium sulphate was collccted, and the filtrate was divided into three portions, A, B, and C'. In 9,the small amount of SO, still remaining was estimated by adding excess of barium chloride and keeping for twenty-four hours. This determination was made in the cold, because boiling causes slight decomposition of penta-thionic acid. In B, the total sulphur was determined by oxidising with bromine water and precipitating with barium chloride. C was boiled with mercuric cyanide, the precipitate collected, and the SO, in the filtrate determined by boiling with solution of barium chloride.By subtracting the amount of barium sulphate obtained in d from the amounts found in B and C respectively, the sulphur and oxygen of the pentathionic acid were readily calculated. The results so obtained gave S505.v2. The complete analysis of the water, in percentage composition, ia as follows: 12 Si02.......... . . .... . . 0.0080 Mn ......... ........ 0-0014 TiO, ..,....... . .... 0*0080 A1 ..... . . . . .... . . . . 0.3330 soy . . . . . ....* .* . . . .. ‘1.6634 Ca ...... . ... . ... . . . . 0.1497co*... . .......... . ... 0’0130 Mg .................. 0-0790 P,O, ........* . . ... nil K .,.,................ . 0.0884 %OB ...* . . ... . ..* 1 . 0-0310 Na . . ............... . 0’2154 As&, ..,. . .. .. . . . . . . 0-00056 Mo . . .*. .... . ........ trace c1 .....,. . .......... 4.8210 cu .. ...... . .. . . .. . .0 Br ...... . . . ... . . . . . . 0.0034 NH4 ...... . . ,. . . .. O.ib9l I .... . ..... .. . . . ... . . . trace H (in HCl) ........ 0.1328 0(basic)............ 0.5306 H,S&O, ....... . . . . 0.0240 Fe . . ..... . ......... . 0-1456 9 -24236 These results may be restated as follows: NH,Cl . . .. . .. . .... 0.0273 MnSOc ............ 0-0038 KC1 ........,..... . 0.1654 CUSO, .. . ... . . ..* .. . . trace 1..NaCl . . ..... . ... .. . , 0.0379 MOO, .......*. ... KBr.. ....... . ...... . . 0-0051 SiO,. .,... . . ........ . . 0.6b80 KI .................. trace TiO, ..... . ....,.... 0-0030 N%SO, . . . .. . ,. . ... 3.6191 B,OS . . . . . ..... . .... 0-0310 MgSO, ............ 0.8948 As20, .. . ,. . . . ..,.. . . 0*00056 CaSO, ............... 0‘5090 co, ..... . . . ,... . . .. 0.0130 A],( ......,.. 2’1090 HC1 . . .. . . .. . .. ... 4.8338 Fe,(SO,), ... ...... 0.2600 H,$06 . . .. . .. .. ... 0.0240 FeSO, ... . .. . . ., ..... 0.1976 9‘24236 21, ‘(/MKethyl-&X-dodecadiene and P-methyl-A,,-decadiene.” ByVictor John Harding, Gertrude Mand Walsh, and Charles Weizmann. An account was given of the preparation of the above-mentioned hydrocarbons from the corresponding tertiary alcohols : CH,:CH*[CH,],*CMe~*~H+CIi2:CH*[CH2],*CMe:CH2. CH,*[CH,],*C~::CH*CMe,*OH-+ CH,*[CH,],*CH:CH*CMe:CH,.22. b6Determination of the vapour pressures of hydrates by 8 dynamical method.” (Preliminary note.) By James Riddick Partington. The vapour pressures of copper sulphate hydrate (CuS0,,5H20) and racemic acid hydrate have been determined by comparing the amounts of water removed from the hydrate and from pure water by a stream of air in a special apparatus. The values in the first case are higher than the tensimetric (static) values; in the latter case, the vapour pressures exhibit a maximum with respect to extent of dehydration as independent variable. Both phenomena are found to be mathematical consequences of the initial formation of an unstable lower hydrate, or unstable anhydrous substance, which passes slowly into a stable form.13 23. ‘‘A simple demonstration of Wibbs’s phase rule.’’ By James Riddick Partington. The proof of the phase rule given by Gibbs (Scientific Papers, vol. 1, pp. 62-100) is far too difficult to present to beginners in physical chemistry, and the following much simplified exposition of Gibbs’s original demonstration haa been found quite intelligible to students, and may be useful to teachers. The assumption is made that it is possible to have a state of equilibrium between several phases at a definite temperature and pressure ; this will be characterised by certain definite relations between the compositions of the phases (for example, a solid salt, saturated solution, vapour of the solvent). Let p, 8=total pressure and temperature of the system.n=number of components. r= ,* ,)phaaes. For each pair of phases there must be some condition satisfied for each component, such that this particular component does not pass from one phase to the other. The r-phaaes may now be arranged in (T-1)pairs, namely, (1, 2), (2, 3), (3,4), .. ((T -l), T), and there will therefore be (T-1) conditions to be satisfied for each component in all the phases, that is, (T -1) equations defining the equilibrium. It is evident that such pairs aa (1, 3), (2, 4), etc., need not. be considered, since, if phase (1) is in equilibrium with phase (Z), and phase (2) with phase (3), then (1) will also be in equilibrium with (3). If this were not the case, we could, by enclosing (l),(Z), (3) in a ring-shaped tube, so that there are three surfaces of separation, set up a continuous circulation at a uniform temperature, which is contrary to the second law of thermo dynamics.For all the components there will therefore be m(r -1) equations. The number of variables is made up of: (i) the pressure p, (ii) the temperature 8, (iii) the number of concentrations =~(n-l), since for each phase we have (n-1) fractions of the total maw for the n components, the last (nth) fraction, being obtained by subtracting the sum of all the others from the total mass,is fixed, and is not an independent variable, theref ore : number of variables =2 + r(n-1). The number of variables left undetermined =number of variables -number of equations =2 + r(n-1) -n(r -1) =2+n-r.14 This, however, is defined as the number of degrees of freedom (,?; of the system, hence: P+r=n+2 . . . . . . . ((1)-If any component is absent from a particular phase (for exampj 3, the vapour phase, or a solid phase), there is one variable less, b1 t also one boundary condition less, for migration of that componex t cannot occur with respect to the phase considered. The equation (L ) is therefore still true. 24. ‘(Cholesterol and fatty acids.” By James Riddick Partington. The solids separating from a fused mixture of cholesterol with palmitic, stearic, or oleic acid are found, by an examination of the freezing-point curves, to be either pure substances, or mechanical mixtures of these substances, and not compounds, as has been previously assumed. 25.‘‘ Salts of the dinitrodihydroxybenzenes.” By William Bayliss Shaw. Although the dinitrodihydroxybenzenes have been known for some years, no systematic investigation af their salts has been carried out. The author has prepared a complete series of the alkali-metal salts of 3 : 5-dinitroquinol, 3 : 5-dinitrocatechol, and 4 : 6-dinitre resorcinol by the addition of an alcoholic solution of the metallic hydroxide to the nitro-compound dissolved in an indifferent solvent, such as ether. In the case of the quinol and catechol derivatives, two series of salts have been prepared, having the formulae: OH OM’ OH OM’ /\I N02(,NOz and /\NO,!,)NO, (\OM’ ; N02\)N0, and /\OM’ NO,\jNO, ’ OM’ OM’ Only the neutral salts of dinitroresorcinol have been obtained.A sharp dour distinction exists in the quinol and catechol series between the neutral and acid salts. The acid salts of the forms OH OH 15 are all of an orange or red tint, whilst the neutral salts are almost black. The neutral salts of dinitroresorcinol resemble the acid salts of the other two series, no darkly coloured substances having been found. It has also been possible to prepare, although not in a high degree ofpurity, salts of the formuh: OAc OAc /\ /'\OM' NO,,)EO, NO,j\//NO, OM' by employing the dinitrediacetate in place of the free nitro-compound, since one of the acetyl groups is much more easily removed than the other.By acting on a neutral salt with methyl sulphate, the correspond- ing monomethyl ether can be obtained. The. introduction of two methyl groups by this means has not been accomplished. All attempts to methylate 4: 6-dinitroresorcinol with methyl sulphate have failed. Some fifty new salts have been prepared, and it is hoped to publish full details shortly. ADDITIONS TO THE LIBRARY. I. Donations. Bothamley, Charles Herbert. The Ilford manual of photography. pp. vi+218. ill. Ilford. ad. (Recd. 7/1/11.) From Messrs. Ilford, Ltd. Dyer, Berncwd, and Shrivell, F. W. E. The manuring of market garden crops. pp. 144. ill. London 1910. (Recd. 16/1/11 .) From the Authors. Martindale, W.Harrison, and Westcott, W. Wylzn. ‘‘ Salvarsan ” or ‘‘ GO6 ” (Dioxy-diamino-arsenobenzol). Its chemistry, pharmacy, and therapeutics. pp. xv+ 77. London 1911. (Recd. 3/1/11.) From the Publishers : Messrs. H. K. Lewis. Scott, Alexander. An introduction to chemical theory. 2nd edition. viiif272. London 1911. (Red 11/1/11.) From the Anthor. 16 11. By Purchccsc. Fischer, Perdinand. Kraftgas, seine Herstellung und Beurteilung, pp. viii +236. ill. Leipzig 191 1. (Recd. 18/1/11.) Gildemeister, Eduard, and Hoffmann,Friedrich. Die atherisohen Ole. 2nd edition. Vol. I. pp. viii+697. Leipzig 1910. (Recd. 15/12/ 10.) Neubauer, Carl Thodor Ludwig, and Huppert, R&l Kugo, Analyse des Harm. 11th edition. 1st half. pp. xiv+682. ill, Wiesbaden 1910.(Recd. 18/1/11.) Salmon, WilZiam. Medicina Practica : or, the Practical Phyfiician : Shewing the true method of curing the most usual diseases incident to human bodies. . . To which is added, the chymical works oE Hermee Trismegistuq Kalid King of Persia, Geber King of Arabia, Artefiue Longajvus the Jew, Roger Bacon, Nicholas Flammel’s Hierogly phicks. George Ripley’s Marrow of Alchymie. And an account of their lives. pp. [xxviii] + 696. ill. London 1707. (Hsfevertce.) Stift, Anton, and Gredinger, Wilhehn. Der Zuckerruben bau und die Fabrikation des Rubenzuckers. pp. viii +667. ill. Wien 1910. (Recd. 18/1/10.) At the next Ordinary Scientific Meeting on Thursday,February 2nd, 1911, at 8.30 p.m., the following papers will be communicated : (‘The constancy of water of crystallisation in hydrated salts.Part I.” By H. B. Baker and G. H. J. Adlam. “Different methods of applying the Grignard reagent.” By H. Davies and F. S. Kipping. (‘The orientation of the nitro-group in nitromyristicinic acid.” By A. H. Salway. “ The condensation of aromatic aldehydes with nitromethane.” By F. G. P. Remfry. “The phosphoric acids.” By A. Holt and J. E. Myers. “ The determination of solubility coefficients by aspiration.” By-W. J. Jones. ‘(The triazclgroup. Part XVI. Interaction of nitrosates an& sodium azide.” By M. 0. Forster and F. M. van Gelderen. R. CLAY AND SON8, LTD., BREAD 8T. TIII,I., P.C., AND BUNQAY, SUPFOLH.
ISSN:0369-8718
DOI:10.1039/PL9112700001
出版商:RSC
年代:1911
数据来源: RSC
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