|
1. |
Proceedings of the Chemical Society, Vol. 30, No. 426 |
|
Proceedings of the Chemical Society, London,
Volume 30,
Issue 426,
1914,
Page 63-76
Preview
|
PDF (828KB)
|
|
摘要:
[Issued 13/3/14 PROCEEDINGS OF THE CHENICAL SOCIETY. Vol. 30 No.426. Thursday, March 5th, 1914, at 8.30 p.m., Professor W. H. PERKIN,LL.D., F.R.S., President, in the Chair. Messrs. E. E. Turner, John E. Wood, A. Bramley, Bertram Campbell, and Ivan R. Gibb,s were formally admitted Fellows of the Chemical Society. The names of the Fellows recommended by the Council for election as official and ordinary Members of Council, 1914-1 915, were read from the Chair. The PRESIDENTannounced that the Rooms of the Society will be open for an informal meeting of the Fellows on Thursday, April 30th, from 8 to 10 p.m. Smoking will be permitted, and light refreshments will be provided. Fellows are invited to exhibit apparatus and specimens of interest, and to show experiments, and those wishing to do so are requested to communicate with the Honorary Secretaries not later than the Monday previous to the meeting.It was also stated that a meeting of the Faraday Society wiIl be held in the Rooms of the Chemical Society on Friday, March 27th, 1914, when a general discussion on “Optical Rotatory Power” will take place. Fellows of the Chemical Society are invited to attend. The meeting will be held from 5 to 6.30 p.m. 64 and from 8 to 9.30 p.m., tea being served at 4.30. Further par- ticulars can be obtained from the Secretary of the Faraday Society, 82, Victoria Street, S.W. Certificates were read for the first time in favour of Messrs.: Raymond Foss Bacon, B.Sc., Ph.D., Mellon Institute of Indus-trial Research, University, Pittsburg, Pa., U.S.A.Robert Reginald Baxter, B.A., St. John’s College, Oxford. Brojendranath Ghosh, M.Sc., 59, Hereford Road, Bayswater, W. Richard Selwyn Haskew, Cwmbran, Newport, Mon. Ralph Waldo Emerson MacIvor, 47, Victoria Street, West-minster, S.W. Henry Ratcliffe, 38, Sefton Terrace, Beeston Hill, Leeds. John Rogers, 195, West George Street, Glasgow. Percy Charles Rundell, Glenthorne, St. Albans Crescent, Wood- ford Green. Max Herbert Tagg, B.Sc., Brentor, Clayton Avenue, Wembley. Albert Watkins Maggs Wintle, Holly House, Saltcoats, Ayrshire. Of the following papers, those marked * were read : *59. ‘‘The atomic weight of vanadium.” By Henry Vincent Bird Briscoe and Harry Frank Victor Little. The ratios V0Cl3: 3Ag and VOCl,: 3AgCl have been redeter- mined.Vanadyl trichloride was decomposed by aqueous ammonia, acidified with nitric acid, and the chloride either titrated against silver according to the method of Richards and Wells (J. Amer. Chem. SOC.,1905, 27, 459), using a modified nephelometer to deter- mine the end-point, or precipitated as silver chloride and weighed. A new type of apparatus, designed for fractional distillation in a vacuum with the complete exclusion of moisture, was used for the distillation of the vanadyl trichloride and its collection in glass bulbs, and the trichloride was weighed in a manner which obviated the necessity for collecting fragments of broken bulbs. The results obtained are as follows (Ag =107.88 ;C1= 35’457) : 9 expts : VOCl, :3Ag =0.53554& 0.000008, whence V =50.950.2 expts. : VOCI, : 3AgC1=G 0.40307, whence ‘Ir=50.952. For a number of reasons these results may be slightly too low, and the rounded-off value V=50*96 is preferred. This result is in very close agreement with that deduced by McAdam (ibid.,1910, 32, 1603) from measurements of the ratio NaVO, : NaC1. DIscusSION. In reply to the President, Mr. LITTLEstated that part of the oxide of vanadium which formed the starting material had been formerly used by Sir Henry Roscoe in his researches on vanadium. A small amount of arsenic present in another portion of the oxide was incidentally eliminated when converting the oxide into vanadyl trichloride, but otherwise no initial purification of the oxide was attempted.The vanadyl trichloride, however, was fractionated until a preparation was obtained quite free from phosphorus and arsenic, and having a constant boiling point (127O). The sub- sequent fractionation of this product was effected in a vacuum, and no further boiling-point observations were made. *60. “The isomerism of the oximes. Part 111. The hydroxy- benzaldoximes.” By Oscar Lisle Brady and Frederick Percy DUlUl. The authors have investigated the hydroxybenzaldoximes, but have failed to obtain stereoisomerides or any confirmation of the existence of the supposed isomeric m-hydroxybenzaldoxime described by Jowett (T., 1902, 81,707). Dollfus (Ber., 1892, 25, 1924) assumed that in the monoacetyl derivatives of these oximes the oximino-group was acetylated, but the authors have been able to show that in the case of phydroxybenzaldoxime it is the phenolic hydroxyl that is acetylated, and not the oximino-group, the com- pound thus being p-acetoxybenzaldoxime.This and the parent hydroxy-oxime have been proved to possess the anti-configuration, and the stereoisomeric p-acetoxybenzsynaldoximehas been prepared. In the case of the acetyl derivative of salicylaldoxime, however, it has been shown that the oximino-group is acetylated. DISCUSSION. Dr. PYMANpointed out that Dr. Jowett laid no claim to the discovery of a stereoisomeric m-hydroxybenzaldoxime. The oxime had been prepared from m-hydroxybenzaldehyde amongst half-a- dozen other derivatives for the purpose of identification, and the discrepancy of melting point was noted, but not fully investigated.In reply to the President, Mr. BRADYstated that it would probably be difficult to obtain stereoisomeric oximes from 4: 5-methylene-o-tolualdehydeon account of the methyl group being in the ortho-position with respect to the oximino-group ;with reference to the methoxybenzaldoximes, the two isomeric 66 pmetlioxybenzaldoximes had been obtained, but the ortho-com-pound existed only in one form; the meta-compound had not been investigated. In reply to Dr. Pyman, he said that there was no wish on the part of the authors to suggest that Dr. Jowett claimed to have obtained an isomeric nz-hydroxybenzaldoxime ;they were, however, of the opinion that it was impossible to obtain a compound melting at 138O by recrystallising m-hydroxybenzaldoxime from benzene.“61.‘‘The constituents of the leaves and stems of Daviesia latifolia.” By Frederick Belding Power and Arthur Henry Salway. Daviesia latifolia, R. Br. (Nat. Ord. Leguminosae), is a shrub indigenous to Victoria, Australia, where, on account of the bitter taste of the leaves, it is known as the “Native Hop Bush.” An examination of freshly collected material, consisting of the leaves and stems of the above-mentioned plant, has shown that its bitterness is due to a crystalline benzoyl derivative of a new disaccharide, the latter (glucoxyZose) yielding on hydrolysis 1 mole-cule of dextrose and 1 molecule of xylose.The bitter compound possesses the empirical formula C25H28012,H20,melts at 147--148O, and has been designated dibenzoylglucoxylose. Besides a small amount of an aromatic essential oil, the follow- ing additional constituents of the plant have been isolated or identified : benzoic, salicylic, pcoumaric, and fumaric acids, and a mixture of fatty acids, consisting of palmitic, stearic, and linolic acids; a quercetin glucoside, C2,H,0,,, which is probably identical with rutin ; myricyl alcohol ; hentriacontane; a phytosterol, C2,H4,0; and a sugar which yielded 6-phenylglucosazone (m. p. 210O). The resinous material, from which some of the above-men- tioned substances were obtained, amounted to about 8.6 per cent.of the weight of drug employed. DISCUSSION. Dr. POWER,in reply to a question by the President, stated that the recent chemical examination of hops had revealed the presence of no substance similar in character to the bitter principle of Dauiesia leaves. It was also noted that no botanical relationship exists between the leguminous shrub, Dauiesia latifolia, R. Br., and t,he common hop plant, Huniulus Zupulus, L. In reply to a question by Mr. Baker, it was explained that the new disaccharide, glucoxylose, had only been directly isolated in 67 the form of its crystalline benzoyl derivative, dibenzoylglucoxylose. The amount of the latter compound present in the leaves appeared to be somewhat less than 1 per cent.“62. 6L The composition of some mediaeval wax seals.” By James Johnston Dobbie and John Jacob Fox. An account was given of the examination of the composition of a number of medizval seals, ranging in date from the thirteenth to the beginning of the sixteenth century. The seals were found to consist of beeswax alone, or of beeswax mixed with resin in various proportions. The resin could not be identified except in two cases, in which it gave the reactions for colophony. The red seals were coIoured with vermilion, the green with verdigris, the brown and black with verdigris and organic matter. The beeswax which formed the sole constituent of an impression of the Great Seal of 1350 was practically unaltered in chemical and physical properties, except as regards its power of absorbing iodine, which was slightly less than that which beeswax usually exhibits.63. ‘‘ Experiments on the rate of nitrification.” By Richard Moore Beesley. Solutions of nitrogenous substances were inoculated with a mixed culture of nitrifying and hydrolytic organisms, which were obtained from a secondary contact bed, and the nitrification was allowed to proceed under strictly comparative conditions, with the object of determining the comparative rate of nitrification. The following substances were employed : carbamide, thio-carbamide, uric acid, asparagine, glycine, acetamide, methylamine sulphate, aniline sulphate, ammonium oxalate, and ammonium sulphate. The solutions, with which were incorporated suitable mineral media, were made of such a strength as to contain 100 milli-grams of nitrogen per 500 C.C.The’course of the nitrification was followed through by means of periodic determinations of the ammoniacal, nitrous, and nitric nitrogen figures. Under these conditions it was found that the various substances nitrified at approximately the same rate, with the exception of thiocarbamide and aniline sulphate, which com-pletely failed to nitrify. Evidence has also been obtained to the effect that in the bacterial oxidation of nitrogen, compounds inter- mediate between ammonia and nitrous acid are formed. 68 64. Studies of the constitution of soap solutions. The alkalinity and degree of hydrolysis of soap solutions.” By James William McBain and Herbert Ernest Martin.From electromotive force determinations, the dissociation product of water at 90° is calculated to be 69.7 x 10-14; this result is chiefly of interest in discussing the high real temperature-coefficient of the hydrogen electrode, which is ignored by recent convention. The hydrolysis and true alkalinity of soap solutions has been quantitatively determined for the first time. In concentrated solu- tions hydrolysis amounts to only a fraction of a per cent., and even in 0-O1N-sodium or potassium palmitate it only amounts to 6.6 per cent., and thus the high conductivity of soap solutions is definitely shown not to be, due to free alkali. The novel suggestion was advanced that it may be due to highly charged aggregates or micelles exhibiting even an equivalent conductivity comparable with that of ordinary ions (see McBain, Trans.FaTaday SOC.,1913, 9, 99; Kolloid. Zeitsch., 1913, 12, 256). This suggestion, if con-firmed, may apply to such diverse cases as protein salts, dyes, and certain non-aqueous solutions. In the presence of even one equivalent of free palmitic acid soap solutions are still appreciably alkaline. On the other hand, the alkalinity of solutions containing an excess of alkali is practically that of the added alkali. There is thus no measurable sorption or formation of basic soap in the presence od O.1.N-alkali. Sodium chloride at first decreases, but in larger amounts again increases, the alkalinity of soaps, in accordance with the suggested rule that any influence tending towards coagulation increases the alkalinity of these solutions.65. The influence of configuration on the condensation reactions of polyhydroxy-compounds. Part I. The constitution of mannitoltriacetone.” By James Colquhoun Irvine and Bina Mary Paterson. Mannitoltriacetone has been selected as a test substance in an endeavour to correlate the configuration of polyhydroxy-comp‘ounds with their capacity to enter into condensation with aldehydes or ketones. It was found that, when dissolved in aqueous alcohol con- taining minute quantities of hydrogen chloride, the ketonic residues could be removed from mannitoltriacetone in the definite stages indicated below : Mannitoltriacetone +mannitoldiacetone -++ mannitolmonoacetone +mannitol.69 Mannitoldiacetone crystallises in needles melting at 37-39O, and has [a],+ 15’75O in alcohol; on methylation it was converted into dimethylmannitoldiacetone(b. p. 140-141°/ 13 mm., [a], +21*9O), which, on hydrolysis, gave dimethylmannitol (needles, m. p. 93O, La], -S.SSO)a This compound, on oxidation with nitric acid, was converted into dimethylmannonic acid, which was isolated in the form of the corresponding lactone (m, p. 112-114°). In a parallel series of reactions, mai2/zitolmoiLoacetolce (needles, m. p. 85O, La], in alcohol +23*2O) was converted into tetramethyl-mannitolmonoacetone (b. p. 138-140°/ 11 mm., [a],+ 32.Z0), from which tetramethylmannitol was obtained.The compound boiled at 167--169O/13 mm., showed [a]D-12.54° in alcohol, and gave, on oxidation with nitric acid, a tetramethylmaiinonic acid (b. p. 180-182°/12 mm.) incapable of forming a lactone. It was also found necessary to examine the form of tetramethyl-mannitol obtained by the reduction of tetramethylmannose. The compound thus produced boiled at 177O/11 mm., and showed [a],+39*8O in alcoholic solution, and is thus isomeric with the product obtained by the hydrolysis of tetramethylmannitolmono-acetone. Moreover, on oxidising tetramethylmannose by means of bromine, a second form of tetrarnetkylniatL)io?~icacid was isolated, which was readily transformed into tetramethylmn,znonolactoize (b. p. 174O/11 mm., La],+ 78-8O+ 38.5O in aqueous alcohol).From these results, the following conclusions are drawn : (1) in mannitoltriacetone the ketonic residues are symmetrically linked to a-carbon atoms; (2) the stabilities of the three residues are unequal; (3) the least stable residue is linked to a primary alcoholic group ;(4) the most stable residue is linked to the remain- ing primary alcohol group. 66. “The formation of ethers from mannitol. An example of steric hindrance.” By James Colquhonn Irvine and Bina Nary Paterson. In attempting to prepare mixed ethers by the alkylation of dimethyl- or tetramethyl-mannitol, it was found that the reaction was completely arrested at a stage when a penta-substituted derivative was formed. Thus, 3 : 4 : 5 : 6-tetramethylmannitol, when subjected to the action of silver oxide and ethyl iodide, was converted into the corresponding tetramethylethylmannitol (b.p. 140°/8 mm.), and, in a parallel reaction in which methyl iodide was used, the product consisted of pentamethylma?anitol (b. p. 137--138O/8 mm.). As the latter compound was converted, on oxidation with nitric acid, into a pentamethylmannotzic acid 70 (b. p. 110°/0.18mm.), the resistance to methylation was evidently presented by one of the terminal hydroxyl groups. Notwithstanding the configuration symmetry of mannitol, the remaining primary alcohol group behaved in a different manner, and was readily methylated. The combined results of the research support the view, expressed in the preceding communication, that the terminal alcohol groups in mannitol preferentially assume fixed positions, with the result that three adjacent hydroxyl groups are arranged on the same side of the carbon chain.Only two of these three groups undergo methylation, and the stereochemical formula of pentamethyl-mannitol is as follows: OMe 7 7 ?Me ?Mef)H bH,-C--C-C--C---CH, bMe OMe H H As the silver oxide method of methylation has frequently been employed to discriminate between different types of sugar deriv- atives, it was necessary to apply the process to 2: 3:5: 6-tetra-methylmannitol in order to ascertain if the secondary alcohol group resisted substitution. The reaction yielded the pentamethyl-mannitol described above, so that the previous conclusions regard- ing constitution in the sugar group, which are based on the methyl- ation process, are not affected adversely by the results of the present investigation.The specific rotations of the partially methylated mannitols now described display a number of regularities from which it is possible to allocate a qualitative rotatory power to each of the four asymmetric systems in mannitol. 67. (‘The relative strengths of ammonium and the substituted ammonium hydroxides as measured by their action on a pseudo-base. Part I.” Charles Kenneth Tinkler: The method employed depends on the spectroscopic determination of the amount of the ammonium form of a pseudo-base converted into the corresponding carbinol by the action of a soluble base. 1-Hydroxy-6 : 7-dimethoxy-2-methyltetrahydroisoquinolinehas been employed as the pseudo-base.By comparing the ultra-violet absorption spectra of the pseudo- base, in a solution of a soluble base, with those of mixtures of known composition of the hydro-compound (I) and the chloride (II), 71 it is possible to estimate the amount of the carbinol and ammonium forms of the substance present. The general result of the investigation is to show that the bases employed increase in strength in the order: ammonium hydroxide, trimethylammonium hydroxide, methylammonium hydroxide, dimethylammonium hydroxide, tetramethylamonium hydroxide, which is in accordance with the results obtained by other investigators. The present investigation has also shown that the conversion of the ammonium form of the pseudo-base into the carbinol is in accordance with the law of mass action, that is, concentration of ammonium form of pseudo-base x concentration of hydroxyl ion = K x concentration of carbinol.68. L6 The interaction between nitric acid and brucine in the presence of metallic nitrates.” By Edward Henry Rennie and Alfred Ernest Dawkins. The authors have investigated the effect of metallic nitrates on the interaction between nitric acid and brucine, and have found that the time required to produce a colour of standard depth is very much reduced by the addition of nitrates to the acid. This is in general accord with the results of previous investigations on the effect of nitrates on the interaction between nitric acid and copper (T., 1908, 93,1162; 1911, 99, 1035). 69.‘‘ Derivative8 of 3 :4-diimethoxyacetophenoneand 4 :5-dimeth-oxy-o-tolyl methyl ketone: and the synthesis of phenyl-glyoxalines containing substitnents in the benzene ring.’’ By Henry Stephen and Charles Weizmann. The authors have prepared some compounds derived from 3 : 4-dimethoxyacetophenone and 4 : 5-dimethoxy-o-tolyl methyl ketone, and also some new phenylglyoxalipes. 4: 5-Dimethoxy-o-tolyl chloromethyl ketone melts at 89O and boils at 180°/ 12 mm. ;the corresponding dihydrozy-compound melts at 129O and boils at 18’i0/12 mm. Compounds of the type of o-chloroacetophenones were found on reduction with zinc dust and acetic acid to lead to the formation of acetophenones, with elimination of chlorine.4: 5-Dihydroxy-o-tolyl methyl ketone melts at 168O. Phthalimino-3 : 4-dimethoxyacetophenone (compare D.R.-P. 209962), obtained from the corresponding chloro-ketone by con- 72 densation with potassium phthalimide and by condensation of veratrole with plithaliminoacetyl chloride, melts at 202O. Phthalamino-3:4-dimethoxyacetophenone melts at 174O; the amino-ketone hydrochloride obtained from this melts at 218O (compare Pictet, Ber., 1909, 42, 2943). 4 : 5-Bimethoxy-o-tolyl phthaliminomethyl ketone melts at 159O, and the phthtalamino-compound at 172O. 4: 5-Bimethoxy-o-tobyl aminomethyl ketotte hydrochloride melts at 204O, and is similar to the lower homologue. By condensation of the hydrochlorides of these aminoaceto-phenones with potassium thiocyanate and potassium selenocyanate (compare Gabriel, Ber., 1894, 27, 1037), the following glyoxalim derivatives were prepared : 2-Thiol-4-(3' : 4~-dimethoxyphenyl)-glyoxaline, N--C C,H,( OMe),SH'C<NH.b4 9 melting at 132O, and 2-thiol-4-(3/ : 4f-dimethoxy-o-tolyl)-glyoxaline, melting at 155O.The corresponding selenomercaptam melted at 115-117O and 163O respectively. The above thiol compounds give the sulphur-free derivatives by oxidation with 10 per cent. nitric acid or ethyl nitrite. 70. ''A delicate colorimetric method for detecting and estimating nitrates and nitrites." By Edmund Albert Letts and Florence Williamson Rea. The authors have used diphenylbenzidine (Kehrmann and Micewitz, Ber., 1912, 45, 2641; Wieland, Ber., 1913, 46, 3300; compare also Bull. SOC.chim., 1914, [iv], 15, 186) for detecting and estimating small quantities of nitrates, the test being quite sensitive up to 0*00005 milligram of nitric nitrogen, the depth of blue colour depending on: (1) the temperature, the colour being deeper at higher than at ordinary temperatures; (2) the time that elapses after mixing the nitrate solution with sulphuric acid and diphenylbenzidine ;and (3) the amount of nitrate present.The estimation of nitrates by the new method depends on the depth of the blue tint, and is carried out in small porcelain crucibles. The method may also be employed for estimating both nitrites and nitrates in a mixture of the two.‘671. The solubility of the nitrates of potassium, barium, and strontium, and the stability of the double nitrate of potassium and barium.” By Alexander Findlay, Idwal Morgan, and Ivor Prys Morris. The isothermal curves for the system potassium nitrate-barium nitrate-water have been determined at the temperatures gelo, 21.1°, and 35*0°, and for the system potassium nitrate-strontium nitrate-water at the temperatures 20.0° and 40*0°. The forma- tion of a double nitrate of potassium and barium was confirmed, and insight into its range of stability acquired. No evidence of the formation of a double nitrate of potassium and strontium was obtained. 72. “The azeotropic mixtures of ethyl acetate and water.” By Richard William Merriman.Wade a‘nd Merriman (T., 1911, 99, 997) defined an azeotropic mixture as one which distilled at a constant temperature without change of composition; such a mixture is necessarily one with a maximum or minimum boiling point. The definition is obviously only applicable to perfectly miscible liquids, but the extension of the term to partly miscible liquids or to non-miscible liquids should not cause confusion. For example, if a mixture of ethyl acetate and water containing 8.43 per cent. of water is distilled under a pressure of 760 mm., the boiling point remains constant at 70*37O, and the distillate contains 8.43 per cent. of water at every stage of the distillation. The boiling point is also a minimum to the extent that no other mixture of ethyl acetate and water has a lower boiling point; but, owing to the fact that this mixture of ethyl acetate and water of constant boiling point forms two layers right up to the boiling point, the composition of the mixture in the distilling flask may be varied within wide limits without affect- ing the boiling point or the composition of the distillate.* This fact was clearly pointed out by the author in the original com-munication (T., 1913, 103, 1797), so that Lattey’s criticism (this vol., p.33) appears to be unnecessary. The rest of Lattey’s criticism cannot be applied to partly miscible liquids, such as ethyl acetate and water, as the whole of the deduc- tions depend on the use of Duhem’s equation, which is applicable only to perfectly miscible liquids.* A mixture of any two liquids having two layers right mp to the boiling point must form a mixture of oonstant boiling point with a minimnm boiling point, and. give a distillate havitig a constant composition. 74 In the accompanying figure (Zoc. cit.) the region above the line AB is experimenGzlly unrealisable, but the dotted curve below AB is the most probable form of the P/y curve for mixtures of ethyl acetate and water, although mixtures of triethylaniine and water give a curve of different shape (Lattey, T., 1907, 91, 1965). Lattey’s assertion that the calculation given on p. 1799 of the original communication (Zoc. cit.) is simply an application of Dalton’s law of partial pressures, is not strictly true.It -is well known that Dalton’s law of partial pressures can only be applied to mixtures of saturated vapours when the liquids are absolutely non-miscible (Young, “Stoichiometry,” 253, 260). 73. ‘‘ Diazotisation of aminomesitglenes.” (Preliminary note.) By Gilbert T. Morgan and Joseph Reilly. Although the study of diazotisation processes is greatly simplified in the mesitylene series by the fact that coupling to form azo-derivatives is prevented by the symmetrical distribution of the three methyl substituents, yet comparatively little attention has been devoted to aminomesitylenes from this point of view. Diaminomesitylene is readily converted into either amii20-mesitylenediazonium chloride or mesitylenebisdiazonium sulphate ; the former salt yields aminomesityleneazo-&naphthol (bright red needles, m.p. 173O), whilst the latter gives rise to mesitylenebisazo-&naphthol (maroon-red nodules, m. p., indefinite, 270-275O). The bisazo-derivatives can also be produced by successively diazotising the monoazo-compound and coupling with &naphthol. Other diazonium salts illustrating the two stages of diazotisation of diaminomesitylene are under examination, together with the corresponding triazides and the azo-dyes obtained by coupling the mono- and bis-diazonium salts with 2 : 4-tolylenediamine and other bases and phenols. 74. The variable rotatory powers of the d-a-bromocamphor-/I-sdphonatee.” By William Jackson Pope and John Read. In applying d-a-bromocamphor-P-sulphmic acid to the resolu-tion of externally compensated bases, the authors have observed discrepancies amongst the molecular rotatory powers of the salts obtained; they now trace the latter to the occurrence of dynamic isomerism in the acid, and have been able to isolate stereoisomeric ammonium d-a-bromocamphor-/3-suIphonates which exhibit the molecular rotatory powers [MIMG1+ 371O and + 176O.75 75. “The optical activity of compounds of simple molecular con-stitution. Ammonium d-and. Z-chloroiodomethanesulphonates.” By William Jackson Pope and John Read. The authors have prepared externally compensated chloroiodo- methanesulphonic acid, CHClI*SO,H, and have resolved it into its optically active components by crystallisation with d-and I-hydroxyhydrindamine, brucine, and strychnine. Ammonium cl-chloroiodomethanesulphonate has the molecular rotatory power [1s1]5461+43m70in aqueous solution; the optical activity is very per- sistent, and the salt does not undergo racemisation when its aqueous solution is heated in a sealed tube at 130-150°.76. The lower limits of inflammation of methane with mixtures of oxygen and nitrogen.” By Albert Parker. The lower limits of inflammation of methane have been deter- mined, when mixed with pure oxygen, when mixed with oxygen (80 per cent.) and nitrogen (20 per cent.), and so on down to an admixed gas containing only 13.5 per cent. of oxygen. The mix- tures were sparked in a spherical glass vessel of 2.5 litres’ capacity, the lower-limit mixture being taken as the one containing the smallest quantity of methane, in which the flame travelled through- out.With pure oxygen, the lower limit of methane is found to be 5.99 per cent., whereas with air the value is only 5.77 per cent. Ths most probable explanation of the higher value for oxygen is that the specific heat of oxygen is greater than that of nitrogen at the ignition-temperature of methane. A reduction in the oxygen content of the admixed gas from 20 to 13.5 per cent. causes an increase in the lower limit of methane to 6-29 per cent. 76 ANNUAL GENHRAL MEETING. The Annual General Meeting will be held on Thursday, March 26th, 1914, at 4.30 p.m., when the President will deliver his address, entitled ‘‘Recent Researches on Tautomerism.” At the next Ordinary Scientific Meeting, on March 19th, 1914, at 8.30 p.m., the following papers will be communicated: ‘:The ignition of some gaseous mixtures by the electric dis-charge.” By H. F. Coward, c. Cooper and J. Jacobs. “Deliquescence. Part I. The deliquescence of salts of ammonium bases.” By C. J. Peddle. (‘Hydrazoximes of methyl- and phenyl-glyoxals.” By B. B. Dey. RICHARD CLAY AND SONS, LIMITED, BREAD ST. HILL, F-C., AXD BUXOAY, SUFFOLK.
ISSN:0369-8718
DOI:10.1039/PL9143000063
出版商:RSC
年代:1914
数据来源: RSC
|
|