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Proceedings of the Chemical Society, Vol. 19, No. 262 |
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Proceedings of the Chemical Society, London,
Volume 19,
Issue 262,
1903,
Page 53-70
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摘要:
Issued 14/3/03 PROCEEDINGS OF THR CHEMICAL SOCIETY. VOl. 19. No. 262. Thursday, March 5th, 1903. Dr. W. H. PERKIN,F.R.S., Vice-President, in the Chair. Messrs. Brincker, Howorth, Beanes, J. E. Mackenzie, Cousins, and Desch were formally admitted Fellows of the Society. The lists of names of the Officers and Council proposed for Election by the Council were read from the Chair. Certificates were read for the first time in favour of Messrs. Henry Guest Adshead, Heysham, Wimbledon Park, Wimbledon. Harford Montgomery Atkinson, 32, Bagnall Road, Milton. George Neville Blackshaw, Agricultural College, Aspatria. Harry T. Calvert, D.Sc., West Riding of Yorkshire Rivers Board. Ben Caudmell, B.A., 28, Wigfull Road, Sheffield. Alan Fletcher, 132, Holland Road, :Kensington, W.Arthur Ernest Pitt, 66, Abbot Road, Bromley, E. Harold Russell Pitt, 8, Church Lane, Charlton, S.E. Frederick Robertson, The Hewan, Bearsden, Glaqgow. Fitzroy Owen Jonathan Roose, Oxford Road, Bournemouth. Henry Edward Stevenson, 5, Turner’s Road, Bow, London, X. James Bates Wilkinson, RLD.,Town Hall, OIdham. Of the following papers those marked * were read :-W. ‘*The mechanism of the reduction of potassium bichromate by sulphurous acid.” By H. Bassett, jun. Berthier, who investigated the action of sulphur dioxide on solu-tions of potassium bichromate and potassium chromate (Ann. Chim. Phys., 1843, [iii], 7, 77), stated that in both cases a mixture of sul-phate and dithionate was formed, but without giving details.The reaction has now been studied more fully, and the results show that 94-95 per cent, of sulphate and 5-6 per cent. of dithionate are formed, when potassium bichromate, potassium chromate, or chromic acid is reduced by sulphurous acid ; the amount of dithionate produced being independent of the temperature. Solutions containing known amounts of sulphurous acid and potass-ium bichromate were mixed, and the excess of sulphurous acid estimated with iodine and sodium thiosulphate, or the excess of chromate determined by means of ferrous ammonium sulpbate. The freshly reduced solutions do not give the reactions of either chromium or SO,, and seem to contain a compound Ei$>Cr2(S04)2 (or the corresponding acid), which slowly decomposes into Cr2(SO& and K2S0,.When sulphuric acid or potassium sulphate is added to these solutions, it enters into combination in such a may that the react8ions of SO, are not given by the resulting mixture, and as many as 6 mols. of sulphuric acid may be taken up by 1 mol. of chromium sulphate. Electrolytic experiments show that the green solutions contain a green anion which slowly decomposes into violet chromium and SO, ions. “32. “The constitution of pilocarpine, Part IV.” By H. A. D. Jowett. The author showed that the constitutional formula for pilocarpine, suggeshd by Pinner and Schwarz, is only one of several equally probable on the results hitherto recorded. The constitution of isopilocarpine has, however, been determined by a study of the reactions of dimethylglyoxaline and dimethylpyrazole and by the formation of 1-methylglyoxaline, 1 : 4(or 1: 5)-dimethyl-glyoxaline, 1: 4(or 1: 5)-methylamylglyoxaline, and probably 1 :4 (or 1 :5)-methylamyleneglyoxnline, together with ammonia and methyl- amine, when the alkaloid is distilled with soda-lime.oimetliylglyoxc~line,from isopilocarpine, boiled at 210-21 5' and formed crystalline salts ;platinichloride, m. p. 238-239' ;aurichlode, m. p. 214-215'; picimte, m. p. 167'. It is isomeric and not identical with the dimethylglyoxalines described in the following note. On oxidation, it yields ammonia, methylamine, and acetic acid. lMethylamylglyoxaline, fromisopilocar pine, boiled at 158-160' under 10 mm.pressure; platiniddoride, m. p. 198'; picrate, m. p. 134'; ccurichloride, amorphous. On oxidation, this base yielded ammonia, methylamine, and n-hexoic acid. Methylamyleneylyoxaline, which probably exists in the fraction boiling at 145-160' under 10 mm. pressure, was not isolated ;its presence was inferred from the formation of butyric acid during oxidation. isoPilocarpinolactone, on oxidation with permanganate, yielded ammonia, methylamine, and pilopic acid, whilst pilocarpine gave rise to ammonia, methylamine, and homopilopic acid. isoPilocarpine, which could not be reduced electrolytically, did not form diacidic salts, and on titration behaved as gi normal lactone. isoPilocarpine methiodide, with picric acid, yielded the compound previously described as methylisopilocarpine picrate, but which should be termed isopilocarpine methyl picrate. The absorption spectra of pilocarpine and isopilocarpine, kindly de- termined by Prof.J. J. Dobbie, mere absolutely identical. The following formulse were proposed for pilocarpine and isopilo- carpine : I. 11. yHEt*FH*CH,*g*NMe>CH or CHEt CH*CH,*C-N>CH ,ICO CH, CH-N 60 CH, ~!H-NM~ \/ \/0 0 and it was suggested that pilocarpine and isopilocarpine are stereo-isomerides, the asymmetric carbon atom involved being that contiguous to the carboxyl residue. The following configurations were proposed on the basis of formula I : Dibromopilocarpine or di bromoisopilocarpine, $!HEt*QH*CH,* CO CH,.& CBr-N \/0 CHEt*FH*CH:CBr-NMe*CBr:N*CO,HDibromoisopilocarpinic acid, Ico CR, \/0 56 isoPilocarpinolactone, isoPilocarpinic acid, CHEt ~H*CH:CH*NMe~CH:N*CO~HICO CH, \/ * 0 Bromocarpinic acid, CO,H*CHEt*CH,*CH:CH*NMe*CBr:N-CO,H.It was shown that the explanation given by Pinner and Schwarz of the formation of pilocarpoic acid, C111H1605N2,is quite untenable, but no suggestions as to the constitution of this substance or pilomalic acid were offered. "33. ('Preparation and properties of 1 :4(or 1 :5)-dimethylglyoxaline and 1 :3-dimethylpyrazole." By H. A. D. Jowett and C. E. Potter. These bases were prepared in order to compare their reactions with those of isopi1oc:srpine. 1:4(or 1 :5)-DirnethyZglyoxaZi.rze,obtained from 4(or 5)-methyl-glyoxaline (hitherto described as a liquid, but now obtained in crystals, m.p. 55O), is an oil boiling at 203' and forming an auo.icldoride, m. p. 215' ;platinichlo.l-ide, m. p. 239'; picrccte, m. p. 167' ;methiodide, m.p. 156'; and hydrochlovide, m. p. 145'. Bromine gave a crystalline dibvomo-derivative, m. p. 127', but at 100' under pressure the reaction mas complicated and a crystalline acid was produced. On oxidation, the base yielded ammonia, methylamine, and acetic acid, whilst by the action of potassium hydroxide the methiodide gave methylamine and acetic acid. 1 :3-Dirnethylp~rccxole)prepared from 3-methylpyrazole, is a liquid boiling at 148', which gives an nurichloride, m. p. 175'; plcctini-.chloride, m. p. 234' ; hydrochloride, m.p. 160" ;and methiodide, m. p. 256O. Bromine under ordinary conditions, or at looo under pressure, gave a dibrorno-derivative, m. p. 74' ;l-~net~~~yl~yrccxoZe-3-c~rbox~licacid, m. p. 222', was obtained by oxidation of the base. The methiodide was scarcely attacked by potassium hydroxide. Prof. C. R. Marshall states that these bases have no physiological action analogous to that of pilocarpine. 1:2.Dimethylglyoxaline forms a picrnte, m. p. 179' ; an auricldoride, m. p. 215' ;a plcitinichloricle, m. p. 230" ; and a methiodide which does not melt below 300". *34. L6 Camphor-P-thiol.” By T. 116. Lowry and G. C. Donington. Camphor-P-thiol, HS*C8H13<vH2,prepared by reducing the sulpho- CO chloride of Reychler’s campliorsulphonic acid, is a colourless solid, of characteristic and not unpleasant odour, readily volatile with steam, which crystallises from alcohol in small, glistening prisms and melts at 66’ ; [.ID= +6’ (in acetone).It is insoluble in alkalis but forms a lead salt and a mercurichloride, ClHg-S*C,,H,,O, The disulphide melts at 224’ ; [uID = -90’ (in acetone). The acetate, ScS*C,,H,,O, forms needle-shaped crystals melting at 3s’; [a]:; = -41’ (in acetone). The benzoate, BzS*C,,H,,O, melts at 59’ ; [CX]~’’= -16’ (in acetone). “35. (‘Isomeric change of dibenzanilide into benzoyl-o-amino- and benzoyl-p-amino-benzophenones.” By F.D,Chattaway. The author has previously shown (PToc.,1902, 18, 173) that acyl groups must be included among those which, under suitable circum- stances, can pass from the nitrogen of an aromatic amine into the nucleus.From the product of the isomeric change of diacetanilide at a high temperature, only that isomeride in which the acyl group has taken up the para-position can be isolated in quantity, although the ortho- compound is undoubtedly formed. The transformation of dibenzanilide, however, is precisely analogous to others of the same type, and both the ortho- and the para-derivatives can be easily isolated. The isomeric change, N(COC,H,), NHCOC6H, NHCOC,H, /\ /\I or ()COC,H,,11 -+ I \/ \/ \/COC6H, which takes place readily under the influence of hydrogen chloride, is best effected by heating aniline (1 mol.) with benzoyl chloride (2 mols.) for 18 to 20 hours at about 220’.The product is hydrolysed by alcoholic hydrochloric acid, and the alcohol driven off in a current of steam. On adding water, the bases, which remain in solution as hydrochlorides, can be separated from tarry matters, and any unchanged aniline removed by making the solution alkaline with sodium hydroxide and distilling in steam. On cooling, the other bases solidify, and on dissolving the dry product in a little 58 alcohol and adding a slight excess of strong sulphuric acid, the sparingly soluble sulphate of p-aminobenzophenone crystallises out. On making the mother liquor alkaline and distilling in superheated steam, o-aminobenzophenone slowly distils over and crystallises from the distillate in a pure state.About 45 grams of p-aminobenzophenone and 15 grams of o-amino-benzophenone can be obtained from 100 grams of aniline. “36. Lr Formation of purpurogallin by the electrolytic oxidation of pyrogallol.” By A. (3. Perkin and F. H.Perkin. The methods hitherto employed for the production of purpurogallin give only a poor yield, but recent experiments made by the authors on the electrolytic oxidation of pyrogallol have shown that, in general, the quantity of purified product amounts to 37-45 per cent. of the calculated amount. The purified substance, which had all the properties of purpurogallin, and its acetyl derivative, gave, on analysis, figures which established its identity with this colouring matter. The composition of the electrolytic bath has been frequently varied, and recently a solution containing 28 grams of pyrogallol, 10 C.C.N-sulphuric acid solution, and 50 grams of sodium sulphate in 500 C.C. of water has been found to be most effective. The best results have been obtained by using a, rapidly rotating anode of platinum-iridium and a cathode of lead or graphite. The current density was 4-6 amperes with an E.M.F. of 8-10 volts. The behaviour of other phenolic substances under similar conditions is now under investigation, Gallic acid yields a small quantity of a product which probably con- tains the purpurogallincarboxylic acid recently described (T~ans., 1903,83, 199). 37. “The analysis of Reh, the alkaline salts in Indian uscw land.” By E. G. Hill.The upland barren lands of India, extending over an area of about two millionacres, which are mainly found between the Jumna and the Ganges, and also between the latter and the Gogra, contain so large a quantity of soluble salts in the soil that agriculture is practically impossible. The reclamation of this land has occupied the attention of the Government of India for many years, but less effort has been made to utilise the soluble salts. Such lands have the following general features: the soil is impermeable for a varying depth below the first few inches ; below the impermeable layer is a coarser layer, more or less porous, in which nodular limestone is generally found, and this is sometimes so thick and continuous as practically to form a rock.The upper soil is thus shallow and fitted for the concentration of soluble salts. Such land varies in appearance according to its humidity and the amount of salts which it contains. Efflorescence is frequent, and a grey colour is general. An account of the various attempts which have been made to utilise mar land has been published in the Indian Agricul- tural Ledger (1901, No. 13) by W. H. Moreland, but analyses of the soluble salts contained in these soils have not been recorded, and no attempts have been made to extract these substances and employ them on a large scale. Out of the samples analysed, none contained less than 88 or 89 per cent. of sodium carbonate, but the percentage of salt in the soil varies very materially according to the district and the sub-soil.In the districts where there is a considerable quantity of alkali in the soil, the upper layers are collected and sold under the name of sGjji mzittee. This is used by native washermen in place of soap, and in Allahabad one tradesman makes a crude soap by boiling the solution of this earth with lime and castor oil. Glass has also been made from this sodium carbonate, the chief product being the glass bangles which are so common in the country; sodium hydroxide has also repaid its manufacture, especially in the vicinity of paper mills. Both sodium carbonate and sodium hydroxide are, however, largely imported into India ;the former, especially, being employed in the aeration of mineral waters. It was thought that reh might be interesting from a chemical point of view, and it was examined in order to ascertain whether any sodium sesquicarbonate was present, since this substance occurs in other parts of the world as the native carbonates, trona and urcto.Each sample of earth was digested with hot water several times and the solution filtered. In each case, the light brown solution thus obtained yielded on evaporation large and well-defined crystals of the decahydrated normal carbonate, but fractional crystallisation gave a few monoclinic crystals imbedded in the solid mass produced by slowly evaporating the third fraction. These became opaque on being scratched and were possibly efflorescent. The solution, which contained a considerable amount of humus, was evaporated to dryness on the water-bath, the residue being freely powdered and dried in a steam oven until the weight was constant.This was a long and tedious process ;the weight diminished steadily for 48 hours, although less han half a gram of the substance was taken. There is therefore probably some hydrogen carbonate in the 60 soluble salts. When the weight was constant, a combustion was made with the following result : 0.3892 gram gave 0.0278 CO, and 0.0078 H,O with a residue of 0.3584 Nn2C03. The loss in the dried sample was thus 0.0308 gram, or approximately 8 per cent., a result which mas confirmed by igniting other portions of the dried salt in a weighed crucible. Assuming that humus is half the weight of the CO, derived from it, and that the difference between the gain in the absorption tubes and loss in the combustion boat is due to oxidation of humus, we get 0.0048 gram of humus or 0*0096 gram of CO, due to humus.This leaves 0*01SBgram of CO, due to the decomposition of sesquicarbonate at red heat. The corresponding quantity of sesquicarbonate is 0.1133, which would yield 0.0075 gram of water, The water found was 0.0078 gram. Hence the dried salt contained 29.9 per cent. of sesqui-carbonate. The above experiments were made with the Pertabgarh sample. The soluble salts in five samples from different districts were analysed with tho Following results : Allahabd AllahabadDistrict. Pertabgnrh. Renares. Pans-Ganges. ram-Jumna.Percentage of 6.3 3.1 16'6 6.5 6.5~soluble salts. Na,O ............... 57-70 5iT2 56-70 57 $0 57'61co2 ............... 39-72 39'40 36'97 39-17 39-33 A1,0, .............. 0.31 0'12 0-12 trace trace so, ............... --5'26 2'32 1-71 c1 ................. 2'06 2'6i 0.73 0.77 1-06 P205............... 0 56 0'45 0.38 0.35 0.63 1 1100.35 100.36 100'16 100.21 100-37 There were slight traces of silica and lime in each sample. These analyses indicate that the five samples have the following percentage compositions : Allaliabnd AllahabadDistrict. Pertabgarb. Benares. irzapur' trans-Ganges. trans-Jumna. PercenttLge of soluble salts. 6.3 3 .I 16% 6 '3 6.5 38. "Experiments on the synthesis of camphoric acid. Part 111.Synthesis of isoiauronolic acid." By W.H. Perkin, jw., and J. F. Thorpe. When ethyl cyanodimethylsuccinate, CO,Et*CMe,*CH(CN)*CO,Et, prepared by treating the sodium compound of ethyl cyanoacetate with ethyl bromoisobutyrate, is digested with sodium ethoxide and ethyl P-iodopropionate in alcoholic solution, ethyl cyanodimethy16utcc.netri-ccwboxylate, CO,t*C(CN)<~~~'"2'~~~~,is obtained as an oil which distils at 210-215' under 13 mm. pressure. On hydrolysis with dilute sulphuric acid, this ester is converted into colourless, crystalline substance which melts at 155-157O. When the trisodium salt of this acid is digested with acetic anhydr- ide, carbon dioxide and water are eliminated between the two carboxyl groups (a) and (b), and ketodimethylpeittametl~ylenecurboxylic acid, CH,-YH, C0,H*CH<C1\Ie2. ,is formed.This acid crystallises well, melts at llOo, yields an ethyl ester distilling at 172' (100 mm.), and a semi-csrbazone melting at 217'. The ethyl ester, when treated with magnesium methyl iodide in ethereal solution, is converted into a lactone which distils at 155-157" (50 urn.)and has a most penetrat- ing odour of peppermint. This new lactone, for which the name iso- cnmpholactone is proposed, is isomeric with campholactonc, and the close relationship which exists between these two substances is obvious when their formulae are written side by side : Ccwyholnetoize. iuoCnii~~hoZnctolLc. The above formation of isocampholactone constitutes the first synthesis of that trimethylpentamethylene ring which is the basis of camphoric acid and of so many other substances belonging to the camphor group, and it is hoped that it may ultimately be possible to obtain camphoric acid itself from this lactone.When the lactone is treated with phosphorus pentabromide and the product poured into alcohol, ethyl bromo trimethylpentamethylenecarb-oxylate is formed : CH,.yBr*MeI ?Me, 9 CH,*CH*CO,Et and is an oil which distils at 165-170' under 70 mm. pressure. In an experiment in which this bromo-oster was heated with potass ium cyanide in alcoholic solution, and then with alcoholic potash, a quantity of an oily acid was obtained which was obviously inactive a-campholy tic acid, produced from the bromo-ester by elimination of hydrogen bromide and subsequent hydrolysis.This was proved by the fact that, on distillation with dilute sulphuric acid, the oil was con- verted into a crystalline acid melting at 132O, which, on examination, was easily identified as iso2cturonoZic mid, the well-known isomeric change indicated by the formulze : CH=yMeI 9%CH,*CH*CO,H --+ CH,*vMe, I CMeUK,*C*CO,H a-Camph,olytic a; id. isolmkmolic &id. having taken place. That the isolauronolic acid, thus synthesised, is identical with iso-lauronolic acid obtained from camphoric acid was shown by mixing equal quantities of the two preparations, when the mixture melted at 132: the melting point of the constituents. Furthermore, the syn- fhetical acid, on oxidation with permanganate, yielded isolauronic acid.63 39. “The rate of decomposition of diazo-compounds, Part 111. The temperature-coefficient.” By J. C. Cain and F. Nicoll. The authors have determined the temperature-coefficien ts by t,he use of Arrhenius’s formula, = Ct,e4i -To>:TiTo,Ctl the values of C being calculated from the formuld, 1 A---log A-x -= c,t as indicated in their earlier communications (l’rctcns., 1902, 81, 1412 j 1903, 83, 206). The values of A for diazobenzone-p-sulphonic acid and the chlorides of diazobenzene, diazo-o-toluene, diazo-m-toluene, diazo-p-toluene, and diazo-m-nitrobenzene do not vary much from each other, and agree with those found by Euler (Annalen, 1902,325,301) for diazobenzene chloride (11905) and diazo-p-bromobenzene chloride (13634).By the use of the temperature-coefficients thus obtained, the value of C at other temperatures has been calculated in several cdses, and shown to be in agreement with the numbers found by other observers. 40. “An analysis of the natural gas at Heathfield, Sussex.” ByH, B. Dixon and W. A. Bone. When the possibility of the industrial application OF the Heathfield natural gas was brought before the Royal Commission on Coal Sup-plies, one of the authors (H. B. D., a member of the Commission) was asked to visit Heathfield and examine the nature of the gas on behalf of the Commission. Accordingly, several samples of gas were collected and sealed up in glass tubes on October loth, 1902, and brought to Omens College for analysis.According to Mr. Richard Pearson, Managing Director of the “ Natural Gas Company,” the gas was first discoved in 1836 in a well which was being sunk at Hawkhurst in West Sussex. In the Sub-wealden boring (1873-1875), the gas was met with at Netherfield ton the South Eastern Railway. Gas was first encountered at Heathfield in 1895 in sinking a well for water in the hotel jard, about 50 yards from the station. In 1896, the same firm of well-sinkers met the gas at a depth of 300 feet in a shaft sunk for water at the station; no water was found, but the gas continued to escape, and was then used for lighting the station. At the date of the above visit, six wells mere either sunk or in wme of being sunk, aird gas had been encountered in all of them after the bores had penetrated through the 300 or 400 feet of surface bed of sandstone and marl which forms, according to Mr. Pearson, the impervious lid to the natural holder of gas.The gas was issuing from the bore-holes at a pressure OF between 140 and 200 lbs. per square inch, and was being used to drive gas engines and to light (with incandescent mantles) the station and a number of houses in the village. When lighted at an inch pipe at the month of a bore-hole, the gas burnt with a large flame giving a fairly good light, the flame being more luminous than that of fire-damp from coal mines. In an argand burner, the gas burnt with a moderately lumin- ous flame, but gave little light in an ordinary bats-wing, so that it was difficult to understand how the gas could contain 5g per cent.of ethylene, as was stated, unless, indeed, the free oxygen, also said to be present, was sufficient to destroy its lighting power. The analyses, however, showed that neither ethylene nor free oxygen was present in the gascollected. To avoid the possible loss of free oxygen by partial combustion in thetube while the drawn-out ends were being sealed, a sample was collected by closing the ends of the tube with paraffined indiarubber; it gave the same result. The gas was transferred by means of a Tijpler pump from the collect- ing vessels into small tubes stiaading over mercury. The analyses mere made over mercury in a modified McLeod appnratus, all the re-agents being freshly prepared. A.Pvelimincwy examination for carbon dioxide, oxygen, unsatzcr-cited Iqldrocarbons, ccnd carboiz monoxide. (1) The absence of carbon dioxide and oxygen was proved by expos- ing the gas successively to the action of (a) strong potassium hydroxide solution and (b) strongly alkaline pyrogallol solution. In neither case was there any appreciable absorption. (2) The absence of unsaturated hydrocarbons was shown in two separate experiments in which samples of gas were successiveIy treated with (a) fuming sulphuric acid and (b) strong potassium hydroxide solution. No change in volume occurred in either experiment. (3) The gas always showecl an appreciable contraction (as nearly as possible 1 per cent.) when successively treated with ammo-niacal cuprous chloride and dilute sulphuric acid.No precipitate of cuprous acetylide was formed. Since the foregoing experiments exclude the possibility of this contraction being due to oxygen or un-saturated hydrocarbons, it can only be attributed to the presence oE carbon monoxide. B. Bxplosion analyses fo)* satui-ated hydrocwbons, with, possibly, hp&-ogen, after renaovd of ccwbojh monoxide. After removing the carbon monoxide from a considerable volume of 65 the gas (by means of ammoniacal cuprous chloride and dilute sulphuric acid), the contraction, C, obtained on exploding measured volumes of the residual gas with a large excess of oxygen and air, was determined, and also the absorption, A, when the products of explosion were subsequently treated with strong potassium hydroxide solution.The following results were obtained : 1. 2. 3. Voll~meof gas taken (corr.). ..... 48.25 55.70 58-75 Volume of oxygen and air added 457.45 468.30 465.45 c ....................................... 94.35 109.10 115.20 A ....................................... 48.25 55-90 58.80 CIA .................................... 1.956 1.952 1.959 C. Proof that the gas does szot contc~inJ*es ?qdrogen. Before the foregoing results could be interpreted, it was necessary to ascertain whether the gas contained free hydrogen. This was done by exposing some of the gas, after removing carbon monoxide, to the action of “oxidised” palladium sponge at 100’ for twenty minutes in an apparatus similar to that described by Bone and Jerdan (Trans., 1901, 79, 1044), and afterwards redetermining the ratio C/A, when the residual saturated hydrocarbons were exploded with excess of oxygen and air.The results obtained were as follows : 4. 5. Volume of gas taken (corr.) ......... 62.3 55.3 Ox3gen and air added .................. 472.5 493-0 C .......................................... 121.8 108.2 A ......................................... 62.2 55.4 CIA ....................................... 1.958 1.953 A comparison of these numbers with those given above shows clearly that the gas contains an appreciable quantity of free hydro4 gen. The five explosion analyses indicated, however, the presence, besides methane, of a small proportion of some higher saturated hydrocarbon which is probably ethane.Assuming this to be the case, the percentage composition of the gas, after removing carbon monoxide, calculated from the five analyses, is as follows : 1. 2. 3. 4. 5. Mean. Methane.., 94.10 93-58 94.40 94.30 93.90 94.10 Ethane ... 2.95 393 2.77 2-76 3.13 2.97 Nitrogen, by difference.. ...................... The original gas, therefore, had the following composition : Carbon monoxide ............................................ 1-00 Methane ................................................ 93.16 Ethane ........................................................ 2.94 Nitrogen, or other inert gas (by difference) ...........2.90 I00.00 41. ‘{Chemical composition of cooked vegetable foods.” By Miss K,I. Williams. The following constituents : water ; total nitrogen (by Kjeldahl’s method, modified to include the nitrogen of nitrates) ; ash ; sulphur ; phosphorus ; cellulose (by Schulze’a potassium chlorate method) ; woody fibre (by digestion with dilute sulphuric acid) ; carbohydrates convertible into dextrose ;fat ;and waste, were estimated in a series of vegetable foods including broccoli, Brussels sprouts, dried peas, oatmeal (coarse Scotch), and macaroni, these determina- tions being carried out on both the raw and the cooked materials. 42. “The density of nitric oxide. Preliminary notice.” By R. W. Gray. It seemed doubtful whether nitric oxide had been obtained in a state of sufficient purity to admit of the accurate determination of its density and other physical constants.The value obtained by Leduc (Comnpt. 7*end.,1893,116, 322) for the density does not agree absolutely with the value found by Victor Meyer and Daccomo (AnmaZen, 1887, 240,326), while Olszewski’s results (Compt.rend., 1885, 100, 940) for the vapour pressures of the liquefied gas certainly suggest the possibility of im- purity in the sample be used. Nitric oxide, when prepared by many of the usual methods, contains sniall quantities of nitrous oxide and nitrogen. The higher oxides of nitrogen which are generated at the same time are apparently com- pletely absorbed when passed through tubes containing potassium hydr- oxide in solution and in the solid form, and the gas then liquefies to a blue liquid which does not change in tint after repeated fractionation. The nitrogen present cannot be entiiely removed by solidifying the nitric oxide by means of liquid air and pumping off the uncondensed gas ;a small quantity remains behind in the solid nitric oxide and can only be removed by liquefying and allowing a large portion of the liquid to boil away Owing to the ease with which liquid nitric oxide becomes super- 67 heated, it was found impossible to separate by fractionation the nitrous oxide present, unless the upper part of the bulb containing the liquefied gas was kept below the melting temperature of solid nitrous oxide.M7hen this was done, the densities of different fractions of the gas were found to agree. The mean value for the weight of 1 litre of nitric oxide, prepared in two different ways, is 1.3402 grams at (lat. Paris). 0’and 760 mm. pressure Until confirmed by further experiments, this value is not considered as final, but it is interesting to note that, assuming the truth of Avogadro’s law for oxygen and nitric oxide under standard conditions of temperature and pressure, the ratio of the atomic weights so deduced for oxygen and nitrogen is 16 : 14.001. The work is being continued with the object of making further experiments on the density of this gas and of determining its com-pressibility and other physical constants. 43. (‘Hydrolysis of urea hydrochloride.” By J.Walker and J. K. Wood. A comparison method was described which permits the hydrolysis of a salt such as urea hydrochloride to be determined by the catalysis of cane sugar or methyl acetate with an error not exceeding 1 per cent. ;the results obtained with these two compounds being identical. Within the limits 25-40°, temperature has practically no influence on the hydrolysis of urea hydrochloride. The influence of dilution on the degree of hydrolysis x is expressed X2by the relation ____--constant.(I-x)v The addition of sodium chloride very slightly diminishes the value of x. The dissociation constant of urea, calculated from the hydrolytic experiments, is 1.5x 10-14 at 25O. 44. ‘(The affinities of some feebly basic substances.” By J.K. Wood. By means of the methyl acetate method, together with some solu-bility experiments, the author has obtained the following results at 40.2’ : 68 Percentage Percentage Djssoc ia-hydrolysis Dissocia-of hpdro-of hydro-tionBase. :hloride in Base. chloride in decinornial constant.iecinorrnal constailt solution. solnti on. ~ soCreatiiiiiie ......... 8’96 3.57 x 10-l’ Dimethy1pyroiie 86 0.0065 x 10-11 Acetogcanamine.. 9.8 296 ,) Santhine ...... 85-5 0*00i6 ,) y,fiemicsrbazide ... 10.1 2-61 ,, Acetanilide.,.... 88.9 0.0044 ,yGlycocyamine .., 11’0 2.32 Caffeine ......... S9.i 0*0040 Creatine ........... 12.3 1.81 ,, Urea ............ 90-4 0’0037 ,, y,Guanine ............17’9 0.81 Acetamide ...... 91.3 0’0033 ,, Acetonesemicarb-Nitroguanidiu e 94-0 0*0021 ,,_-azone ........... 26 9 0.32 ,, Propionitrile ... 97 -Acetoxime ......... 34.3 0.175 ,, Cyneol., .......... 95 Aminocaffeine ... 55-0 0.047 ,, Biuret ............ >99 --Theobromine ...... 73.0 0.016 ,, denzamide ...... >99 ADDITIONS TO THE LIBRSRY. I. Doncttioizs. Cohen, Julius Berend. Theoretical organic chemistry. London 1902. From the Author. Gregory, William. A handbook of inorganic chemistry, being a new and greatly enlarged edition of the “Outlines of inorganic chemistry.” 3rd ed. ill. London 1853. From the Lawes Trust. Lang, K. Das chemische Laboratorium an der Universitat in Heidelberg. ill. Carlsruhe 1858. From the Lawes Trust.Low, David. An inquiry into the nature of the simple bodies of chemistry. 2nd ed. London 1548. From the Lames Trust. DIarignac, Jean-Charles Galissard de. CEuvres completes, publi6es hors shie sous les auspices de Ia Socikt4 de physique et d’histoire naturelle de GenBve: par E. Ador. vol. ii. Wmoires et critiques, 1860-1887. Geneva 1903. From the Family. Parkes, Samuel. A chemical catechism for the use of young people ; with copious notes for the assistance of the teacher, to which are added a vocabulary of chemical terms, useful tables, and a chapter of amusing experiments. ill. London 1806. From the Lames Trust. Violette, J, H. AT., and Archambault, P. J. Dict,ionizairo des analyses chimiques, ou rgpertoire alphabdtique des analyses de tous leu corps naturels et artificiels depuis l’origine de la chimie jusqu’a 69 nos jours, avec l'indication du nom des auteurs et des recueils 06 elles ont 4th ioshrhes.2 vols. Paris 1851. From the Lawes Trust. Weltzien, Karl, and Lsng, H. Das chemische Laboratorium an der grossherzogl. polytechnischen SchuIe zu Carlsruhe. ill. Carlsruhe 1853. From t,he Lnwes Trust. 11. By Purchase. Schnabel, Carl. Lehrbuch der allgemeinen Huttenkunde. 2nd ed. ill. Berlin 1903. Hoppe-Seyler, Ernst Felix Immanuel. Handbuch der physiologisch- und pathologisch-chemischen hnalyse f iir Aerzte und Studirende. Edited by H. Thierfelder. 7th ed. ill. Berlin 1903. Liebrich, Oscar. Ueber die Wirkung der Borsiiure und des Borax. (Ein zweites Gutachton.) ill.Berlin 1903. Liipke, Robert. Grundzuge der Elektrochemie auf esperimenteller Basis. 4th ed. ill. Berlin 1903. 111. PibT?'&Z,hhtS. Borns, Henry. Die Elektrochemie im Jahre 1896 (1897-1901). Citron or Cedrat Oil (Citrus Medica). A review of recent' research work on the constants of this oil. 1903. Harrison, John Burchmere. Report on the agricultural work in the Botanic Gardens and the Government Laboratory for the years 2896-1901. British Guiana, Georgetown, Demerara 1902. Van Slyke, L. L., and Hart, E. B. Some of the compounds present in American Cheddar Cheese (being BulE. No. 219, New York Agric. Exper. Station). 1902. Collins, Sidney Hoare. Composition of Milk in the North of England. London 1903. Collins, Sidney Hoare.Sugar in Swedes. Part 11. London 1903. Stocks, Herbert Birtwhistle, and H. Graham White. Sizing and sizing materials. London 1903. Pstten, Harrison Eastman. Influence of the solvent in electrolytic conduction. 1902. Freer, Paul C. The preparation of benzoylacetylperoxide, and its use as an intestinal antiseptic in cholera and dysentery. Manila 1902, Taylor, Robert Llewellyn. On the reaction of iodine with mercuric oxide in presence of water. Manchester 1902. Smith, Alexander, and Holmes, Willis B. On amorphous sulphur. (Univ. of Chicago Decennial Publications.) Chicago 1902. Cutolo, Alessandro. Contributo all' analisi degli olii. (li'.*orn the BulE. Xoc. Nut. Napoli, 15, 1901.) 70 ANNIVERSARY DINNER. It has been arranged that the Fellows of the Society and theii.friends shall dine together at the Whitehall Rooms, Hobel MBtropole, at 6.30 for 7 o’clock, on Wednesday, March 25th, 1903 (the day fixed for the Annual General Meeting). The price of the tickets will be One Guinea each, including wine. The Secretaries will be glad to have, at as early a date as possible, the names of Fellows and their guests who propose to dine. All applications for tickets must be received not later than Wednesday, March 18th. Tickets will be forwarded to Fellows on receipt of a remittance for the number required, addressed to the Assistant Secretary, Chemical Society, Burliagton House, W. ANNUAL GENERAL MEETING. The Annual General Meeting of the Society for the Election of Officers and other business will be held on Wednesday, March 25th, at half past four o’clock in the afternoon.At the next meeting, on Wednesday, March 18th, 1903, at 5.30 p.m., the following papers will be communicated : ‘‘ Essential oil of hops.” By A. C. Chapman. ‘‘A compound of dextrose with hydroxide of aluminium.” Ey A. C. Chapman. LL Action of phoe,phorus haloids on dihydroresorcins. Part 11. Di-hydroresorcin.” By A. W. Crossley and P. Haas. ‘(The constitution of cofnmine.” By J. J. Dobbie, A. Lauder, and C. K. Tinkler. “The decomposition of mercurous nitrite by heat.” By P. C. R%y and J. N. Sen. H.ILUARD CLAl-ASD SONS, LIMITED, LONUOK AND BUlr’GAl-.
ISSN:0369-8718
DOI:10.1039/PL9031900053
出版商:RSC
年代:1903
数据来源: RSC
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