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IASMB~22/3/1897. PROCEEDINGS OF THE CHEMICAL SOCIETY, EDITED BY TH& SECBZTAi?IE8, No. 177. Sesgion 1896-7. March 18th, 1897. Mr. A. G. Vernon Harcourt, President, in the Chair. Mesers. H. P. Stevens, J. W. Walker, W. Arbuckle, N. T. M. Wilsmore, M. Wilderman, W. J. Pope, A. W. Crossley, H. R. Le Sueur, J. H. Miller, R. D. Littlefield, F.H. Neville, W. M. Heller, G. McGowan, C. M. Crossman, J. Holrnes, and F. Southerden were formally admitted Fellows of the Society. Certificates were read for the first time in favour of Messrs. Alfred Hunter Boylau, Ellerslie, Richmond Road, Ealing, W. ;Henry Norris Davidge, 37, Duke Street, Grosvenor Square, W. ; Charles Henry Field, The Elms, Green Street Green, Orpington ; Thomas Girtin, B.A., 125a, Highbury New Park, N, ;James Jones, 117, Old Christchurch Road, Bournemouth ; Charles MacCulloch, 395, Collins Street, Melbourne ; George Fowlie Merson, 65, Northumberland Btreet, Newcastle; Thomas Tickle, 4, Packenham Street, W.C.In accordance with the bye-laws, the following communication was read from the Chair :-WE, the undersigned, beg to propose Prof. William Ramsay, Ph.D., F.R.S., as President of the Chemical Society in succession to Mr. A, Vernon Harcourt, M.A., M.D., D.C.L., F.R.S. :-Baly, E. C. C. ;Baker, C. F. ;Burgess, Herbert E, ;Blount, Bertram; Blundstone, Edward R. ; Berncastle, Richard ; Cassal, Charles E. ; Chattaway, F. D. ;Chapman, Alfred C. ;Collie, J. Norman ;Chorley, John C.; Coste, J. H.; Crossley, Arthur; Dufton, 5.T.; Ekins, Arthur E.; Edwards, W. Buckland; Evans, R. C. T.; Elborne, William ;Earl, Alfred ;Elford, P. ;Forster, M. 0.;Graham, Edward ; &imwood, R. j Harley, Vaughan j Harvey, Sydney ;Baker, Julian L. j 70 Floris, R. B. ;Jackman, E. J.;Jones, Cecil ;Johnson, David ;Kipping, Stanley F. ;Kellas, Alex. M. ; Kingzett, C. T. ;Ling, A. ;Lapworth, A.; Livingston, W. T.; Littlefield, R. D.; Routledge, R.; Lamb, Edmund ; Moody, Gerald T. ;Bodmer, R.; Moor, C. G. ;Millar, J. H.; McCrae, J. ; Macdonald, GI. ; Mills, Charles ; McGowan, Geo. ; Pope, W. J.; Parry, Ernest J. ; Picton, Harold ; Plimpton, R. T. ;Richmond, H. Droop; Simpson, Arthur M.; Stevens, H. P.; Travers, M. W.; Le Sueur, H. R. ;Wade, John; Wagner, W. G. ;Wilsmore, N.T. M. ; Walker, J. Wallace ;Sworn, Sydney A. ;Cornish, Vaughan ;Sykes, Walter J.; Waterhouse, Robert ; Chattaway, William ; Priest, Martin; Marsh, J. E. ; Muspratt, Edmund K. ; Mitchell, C. A. ; Muspratt, Sydney K. ; Adams, Arthur ; Marshall, Arthur ;Wilson, John; Bone, W. A. ; Fisher, E. H. ; Chapman, Arthur J. ;Wheel-wright, E. W.; Lewis, W. H.; Sudborough, J. J.; Veley, V. H.; Walker, James ;Colman, Harold, G. ;Christopher, George ;Macnair, D. 8. ;Bell, Chichester A, ;Wertheimer, J.;Hodgkin, John ;Archbutt, Leonard; Muir, M. M. Pattison; Shaw, G. E.; Taylor, R. L.; Colmell, J. Kear; Cribb, Cecil H.; Butterfield, W. J. Atkinson; Hanes, Edgar S. : Sutherland, D. 9.; Teed, Frank L. ;Fulcher, L. W. ; Heller, W. M. ;Sandford, P. Gerald; Snaps, H.Lloyd; Knight, J. B. ; Cooper, A. J.;Adams, P. T. ;Adams, M. A.; Eiloart, A. ;Corfield, W. H. ; Muter, J. ; Muter, A. H. M. ; Dodd, W. H. ;Koningh, L. de ; Mawer, W. F. ;Lascelles, P. R. ; Bruce, James; Turpin, G. S. PROFESSORCOLLIEstated that the nomination of Professor Ramsay bad been made without his knowledge or his permission, Of the following papers, those marked % were read. "44. carbon."ofthe atomic weight On '6 M.A.,D.Sc. By Alexander Scott, The object of this paper is to call attention to the unsatisfactory nature of the experimental evidence on which the determinations of the atomic weight of carbon rest. The two methods on which reliance is chiefly placed are shown to be only in agreement because a source of error which affects both acts in opposite directions.This is due to an erroneous determination of Dumas and Stas, in 1840, of the expansion produced in potash solutions by the absorption of carbon dioxide. All later workers at this problem seem to have accepted their con- clusions without further verification. The seriousness of this source of error is apparent when we consider that over 40 milligrams is the cor- rection for the weight in VUCLCUOof the carbon dioxide in one experiment 71 alone. The correction per gram of carbon dioxide is shown to be 0.56 to 0.57 C.Q, instead of 0.15 c.c., as taken by Dumas and Stas. The probable effect of the gases ‘(occluded ” in the copper oxide is next considered, and, as far as possible, allowed for.It is shown by many determina- tions that the experiments of Richards give the quantity as much too great, the mean result of his best experiments being 0.088 per cent. by weight of nitrogen in copper oxide made from the nitrate, whilst the experiments here described give as a mean only about 0.007 per cent. Other sources of error and the best methods of making more accurate determinations are next considered. The recalculated values are 12.008 from the combustion of the various forms of carbon, and 12.050 from the conversion of the monoxide into the dioxide. DISCUSSION. In reply to questions from Mr. GROVES, Mr. HEYCOC~~,Mr. BLOUNT, and the PRESIDENT, stated that 150 grams of the oxalate fur- Dr. SCOTT nished about 4grams of carbon.In the case of the potash solution, it was the expansion of the liquid which had to be corrected for. The rate of absorption of carbon dioxide by potash solution at any given time was affected. by the amount of carbon dioxide which had been already absorbed. Carbon monoxide was completely absorbed by potash after some time. “45;. ‘(On a new series of mixed sulphates of the vitriol group.” By Alexander Scott, lK.A,, D.Sc. This paper describes a new series of mixed sulphates of the form (M,N)”SO,,H,O. The most interesting is the ferrous cupric sulphate, the colour of which is reddish-brown; it dissolves in water, giving a blue-green solution, The composition of this salt on analysis corresponds to the formula (CuFe)SO,H,O, or (Fe5Cu,)(SO4),,7H,O.These salts are made by adding about an equal bulk of strong sulphuric acid to solutions of the mixed sulphates. DISCUSSION. Mr. SPILLER,referring to investigations he had conducted on some double sulphates of this group, crystallised from water, the results of which were communicated to the British Association ten years ago, said that he was led to the conclusion that the amount of water of crystal-lisation in such mixed sulphates was the mean of that present in their constituent salts. 72 *46. (( A synthesis of camphorollic acid." By William Henry Perkin, jun.,F.R.S., and Jocelyn Field Thorpe, Ph.D. In a previous communication (Proc., 1896, 12, 155) experiments were described dealing with the action of metallic zinc on mixtures of bromo-ethylic salts and ketones or ketonic acids ; notably on mixtures of ethylic aceto-acetate and ethylic a-brom-iso-butyrate, and of ethylic dimethylacetoacetate and ethyIic bromoacetate, and it was shown that the same hydroxy-ethylic salt, namely, ethylic-P-hydroxy-a-a-P-trimethyl glutarate was in each case produced thus : Me,:yBr +$33 QH2 and Mez:Q.y CH,Br EtOOC CH,COOEt EtOOC CH, dOOEt give Me,: F*C(OH)*FH, EtOOC bE3 COOEt This ethylic-P-hydr.oxy-a-a-a-P-tz.imethylglzcturute(b. p.165O, 30 mm.), as previously stated, splits up, on hydrolysis with alcoholic potash, into acetic and isobutyric acids. When, however, it is boiled with dilute hydrochloric acid, it does not behave in this way, but yields consider- able quantities of the corresponding P-liydroxy-a-a-P-tr~~ethyZg~~tu~c mid, COOH*C(CH,),* C(OH)*(CH,)*CH2*COOR, which is a crystalline body, separating from a mixture of light petroleum and ethylic acetate in glistening prisms melting at 1289 In the previous communication, an acid melting at 14S0, obtained by the action of alcoholic potassium cyanide on ethylic-P-brom-a-u-P-tri-methyl glutarate, was described as a trimethylglutaric acid : we now wish to correct this statement.Alcoholic potassium cyanide is appa- rently without action upon the bromethylic salt at the temperature of the boiling water bath, and, on hydrolysing the product with alcoholic potassium hydroxide, the unsaturated acid, a-a-P-trimethyZglzctuc~ic acid, COOH* CH:C(CH,)* C(CH,),COOH, melting at 148O, is produced, and not the trimethylglutaric acid as was at first supposed, This acid is remarkably stable, and is not affected by boiling with sodium amal- gam.When, however, its boiling solution in alcohol is treated with sodium, the unsaturated acid is gradualIy rednced to a-a-/3-trimethyl-glzctaric acid, COOH. CH,* CH(CH,)*C(CH,),* COOH, which crystal-lises from dilute hydrochloric acid in prismatic needles melting at 109'; the anhydride of this acid melts at 389 and yields, on treatment with aniline, an unilic ucid forming lustrous plates from dilute alcohol melting at 1554 Although the melting points of the acid and of the anil are very similar to those of the trimethylglutaric acid which &lbiano 73 obtained from camphoric acid, it does not appear that the acids are iden- tical, and it is probable that Balbiano's acid is the isomeric a-p-p-tri- methylglutaric acid, COOH-CH(CH,)-C(CH,),* CH,*COOH, as this chemist suggests.On treating ethylic P-hydroxy-a-a-/3-trirnethylglutaratewith phosphorus pentachloride, the chlorethylic salt, namely, P-chlor-uu-/3-trimethyl glutarccte, COOC,H,C( CH,),. C(Cl) (CH,) CH,*COOC,H,, is obtained as a colourless, mobile liquid which boils at 139' (20 mm.). When this substance or the corresponding bromo-derivative is heated with alcoholic potassium cyanide in a closed tube at 160' ethylic:p-cyccno-a-a-trimethyl glutccmte, COOEt * C(Me,) C*(CN) (Me) CH, COOEt, is obtained after twelve hours as an oily liquid boiling at 180-185' (25 mm.).It is difficult to isolate in the pure condition owing to the presence of varying quantities of the ethylic salt of trimethylglutaconic acid, a substance which boils at about the same temperature as the nitrile (175'. 30 mm.). This nitrile was hydrolysed by boiling with dilute hydrochloric acid, and after filtering from the trimethylglutaconic acid, which separated on cooling, the filtrate yielded on neutralisation with ammonia and addition of barium chloride no precipitate, but on boiling, a quantity of a sparingly soluble barium salt separated. This salt was collected, well washed, and decomposed by boiling with the calculated quantity of sulphuric acid; the filtrate from the barium sulphate was then evaporated to a small bulk, when on cooling a crystalline acid sepa- rated, which melted at 157' with decomposition, and on analysis gave the following numbers :-0.1258 gram gave 0.2276 gram GO, and 0.0746 gram H20. Calc.for (C9H1406): H = 6.40 ;C = 49-50, Found : H = 6.58 ;C = 49.34. u-u-P-hi-methylt~icarballylicacid, COOH*CH,C(COOH)(Me)C(Me,)COOH. That this acid is identical with camphoronic acid is, in our opinion, proved by the following considerations :-(1) The synthetical acid gives the same results on analysis, and melts at the same temperature as camphoronic acid. (2) When equal quantities of the synthetical acid and camphoronic acid are intimately mixed, the mixture melts at exactly the same tem- perature, i.e., 157', with decomposition.(3) It gives, when dissolved in a slight excess of ammonia, no precipi- tate with barium chloride until the liquid is warmed, and then the in- soluble barium salt separates exactly as in the case of camphoronic acid. (4) When heated with acetyl chloride, both the acids are converted into an anhydro-acid, which melts in both cases at 135-136'. The anhydrocamphoronic acid from the synthetical acid gave on analysis the following results. Found, C = 54.03 ; H = 6.11. CgHI2O6Calc, C = 54.00 ; H = 6-00 per cent, In a previous communication (Proc., 1896, 12, 192),* one of us had occasion to express the opinion that Tiemann’s formula for camphoronic acid, COOH. CH(CH,)* C(CH,),*CH* (COOH),, which contains the group -CH(COOH), must be incorrect, on account of the fact that campho- ronic acid, when heated with water at 230°, is not decomposed with elimination of GO,.The experiments which we have briefly described in this communication appear to us to prove that camphoronic acid has the constitution first proposed by Bredt (Be?*.,1893,26, 3048), namely, that of an sup-trimethyltricarballylic acid, COOH. C(CH,),* CCH,(COOH)* CH,* COOH. 47. “Note on a method for determining melting points.” ByErnest H. Cook, D.Sc. So many methods have been introduced for the determination of melting points, that an apology is perhaps necessary for describing another, but the following method has been found to work so well in this laboratory, and to be so easy of manipulation, that the author ventures to place it on record.Notwithstanding, however, the theoretical simplicity of taking a melt-ing point, it is surprising that in commercial work considerable differ- ences frequently occur between analysts when reporting upon such a substance, for example, as paraffin scale. Probably most, if not all, of these differences are caused by the different methods employed. Thus it is well known that ‘‘the English test,” which consists in allowing the wax to solidify in a test-tube in which the thermometer is placed gives results from 2&to 3 degrees Fahr. lower than the “American test,” in which the wax is melted in an open dish. Both these methods again differ slightly from the capillary-tube plan, and in this process a different result is obtained when an open tube is used than when it is closed.There are in fact many precautions which are necessary to be observed if concordant results are to be obtained, and it is much to be desired that some distinct and definite regulations should be made with reference to the matter. The apparatus employed is a beaker filled to the brim with water ; inside this, and separated from it on all sides, is a smaller one. The smaller beaker is partly filled with mercury in which is placed a ther-mometer. A stirrer is used to keep the water in the large beaker of uniform temperature. A cardboard or other disc covers the smaller beaker when the operation is in progress. The whole is heated from below by means of a sand bath.When the melting point to be deter- * The formula given here from kredt’s constitution of camphoronic acid is a misprint, it should be COOH-C(CH&-C(CH8)(COOH)-CH,oCOOH. 75 mined is under 30” it is better to replace the sand bath by an evapor- ating dish containing water. The process is conducted as follows. The material whose melting point is to be taken is placed on three or four small pieces of thin ferro- type plate or other thin metallic sheet, or on the cover glasses which are used for microscope slides. If ferro-type or other metallic slips are used, care must be taken to remove the varnish or other coating in order that good metallic contact can be had with the mercury. The slips, with the substance on them, are now placed on the surface of the mercury and the heat applied until the substance melts.The solidify- ing point is obtained by raising the temperature above the melting point and allowing the beaker to cool, noting the thermometer when the fist solidification takes place. For temperatures between 100’ and 200°, the larger beaker is filled with paraffin wax. The following precautions have been found to be necessary :-( 1) The temperature must be made to rise very slowly. (2) The liquid in the outer beaker must be frequently stirred. (3) Not less than 2.5 cm. in depth of mercury must cover the inner beaker. (4) Sufficient volume of water must be allowed between the two beakers. The minimum distances to give good results are 1 in.between them laterally and 1&inch at the bottom. (5) The inner beaker must be immersed a sufficient depth in the water. This point is of great importance, the least distance between the top of the mercury and the top of the water being 3 inches. A greater distance is, however, to be preferred, (6) The whole apparatus should be protected from draughts. (7) The disc should be kept on the smaller beaker during the determination. The following examples will show the degree of accuracy to be ob- tained in ordinary working, some of the results being obtained by students who have never taken a melting point determination before. Paraffin wax (l), 49.8, 49.7, 49.5, 49.8. Paraffin wax (Z), 46.2, 46.0, 46*0,46.0. Paraffin wax (3), 46*5,46*3,46*5.Ortho-mono-nitro-phenol 44.5, 44-7.- Urea, 131.0, 131.5, 131.2. 48.“Velocity of urea formation in aqueous alcohol.” By James Walker, D.Sc., and Sydney A. Kay, B.Sc. The authors have investigated the rate of formation of urea from ammonium cyanate in pure water, and in mixtures of water and alcohol containing 10, 30, 50, 70, and 90 per cent. by volume of the latter. The alcohol acts in two ways: first, it diminishes the degree of dissociation of the cyanate and thus retards the action by diminishing the number of active molecules ; secondly, it increases the rate at which the ions produced by the dissociation interact. The 76 second mode of aotion outweighs the first, so that there is on the whole a marked acceleration as the water of the solvent io replaced by alcohol.If the reverse transformation of urea into cyanate, and the degree of dissociation of the latter at the various stages of the process9 are taken .into consideration, the requiremellts of the law of mass-action are strictly fulfilled. Methylic alcohol, acetone, glycol, glycerol, and cane-sugar exert a similar accelerating effect when part of the water used as solvent is replaced by them, From the displacement of the point of equilibrium between cyanate and urea by change of temperature, it is calculated that the trans- formation of ammonium ions and cyanic ions into urea is accompanied by a heat evolution of about 5,000 cal. per gram-molecule. 49. “Action of alkyl haloids on aldoximes and ketoxime’rr.’’ ByWyndham R.Dunstan, F.B.S.,and Ernest Goulding. The authors find that, when formaldoxime, acetaldoxime, and acetoxime are heated in alcoholic solution with an alkyl iodide or bromide, they are converted into compounds of alkyloximes in which the alkyl group is united to nitrogen R’CHN(R)O and R’,CNCH(R’)O. These deriva- tives are isomerides of the little known ethers of the oximes RCH :NOR’ and R’,CNOR, and are to be regarded as derivatives of the tautomeric or isoximido-forms of the ordinary aldoxime or ketoxime R’CHNH R’XNH\6/ and V in which the alkyl replaces the hydrogen of the 0 amido-group. Their constitution has been proved by their hydrolysis into @substituted hydroxylamines, NH(R)OH, and the corresponding aldehyde or ketone. B’ormddoxime, when mixed with methyliodide, either in alcoholic or ethereal solution, is converted into a crystalline salt of the formula (CH,NOH),CH,I. It has been previously shown (Dunstan and Bossi, Proc., 1894, 10,65)that formaldoxime forms salts with monobasic acids which contain three molecules of the oxime, (CH,NOH),HCI, &c.On hydrolysis, followed by reduction, one molecule of methylamine hydro- chloride and two of ammonium chloride are produced, and on heating near its melting point (102’) only two molecules of formaldoxime distil from it. The formula of the compound may therefore be written (UH,NOH),,CH,N(CH,)O.HI. The base corresponding with this salt could not be separated. Methyl bromide heated with formaldoxime furnishes the corresponding hydrobromide.Acetddoxime combines with methyl iodide, forming the hydriodide of 8 base which has so far only been obtained in the liquid state even 77 after a process of fractional precipitation of an alcoholic solution by ether. On hydrolysis, this salt furnishes acetaldehyde and /3-methyl- hydroxylamine. There can, therefore, be no doubt that its formula is CH,CHN(CH,)O.HI. Methyl bromide combines in the same manner, forming the corresponding hydrobromide. Ethyl iodide forms the hydriodide of the ethyl derivative, CH,CHN(C,H,)O.HT. Neither of the salts has been crystallised and the corresponding bases are highly unstable. Acetoxime.--By heating acetoxime with methyl iodide, a red liquid is obtained which, on concentration, deposits red crystals with a fine green lustre.The mother liquor furnished the little-known metl@mine hy-dviodide (CH,NH,.HI) in glistening, crystalline plates (from alcohol- and ether). This is a very stable non-deliquescent salt, melting at 220’ with partial decomposition. The red crystals were proved by analysis to be a methylacetoxiine periodide of the formula [(CH,)2CN(CH,)0.HI],T. On hydrolysis, it breaks up into acetone and /3-methylhydroxylamine. Many attempts were made to isolate the hydriodide from the per- iodide, and also to prepare other salts from this compound, including the base, but without success, owing to the great instability of these substances. The hydrobromide appears to be formed-when methyl bromide is heated with an alcoholic solntion of acetoxime, but this salt could not be cry stallised. PASTEUR MEMORIAL LECTURE.The Pasteur Memorial Lecture will be delivered by Professor Percy Frankland, Ph.D., F.R.S., at an extra meeting of the Society on Thursday, March 25th, at 8 p.m. ANNIVERSARY MEETING. The Anniversary Meeting will be held on Wednesday, March 31st, at 3 o’clock in the afternoon. ANNIVERSARY DINNER. It has been arranged that the Fellows of the Society and their friends shall dine together at the Criterion Restaurant on Wednesday, March 31st, at ‘7 p.m. The President, Mr. A. G. Vernon Harcourt, in 78 the Chair. Z’he Secwtcwies will be gelctd to receive rt,ot$cation from those Peellows who intend to be pesent befoye $?&lay, Mcwch 26t?~,so that the $rial awangenzents mcby be cornpZeted. At the Meeting on April lst, the following Paper will be received. The authors have announced their intention of being present. ‘‘On the oxidation of a-y-dimethyl-a’-chloropyridine.” By E. Aston and J. Norman Collie, Ph.D., F.R.S. RICBARD OLAY AND SONS, LIMITED, LONDON AND BUWGAY. Page Missing From 79-98
ISSN:0369-8718
DOI:10.1039/PL8971300069
出版商:RSC
年代:1897
数据来源: RSC