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In Organic Chemistry. Published on 01 January 1922 View Article Online / Journal Homepage / Table of Contents for this issue INORGANIC CHEMISTRY. ii. 759 In organic Chemistry. Published on 01 January 1922. Downloaded 26/10/2014 14:59:11. Vapour Pressure of Hydrogen. Determinations in the Region of Liquid Hydrogen. H. KAMERLINOHONNES and J. PALACIOSMARTIXEZ (Anal. Fis. Quirn., 1922, 20, 233-242).- The vapour pressures of liquid hydrogen at temperatures near its normal boiling point were measured using a helium thermometer. By interpolation, the boiling point of hydrogen at a pressure of 759.549 mm. of mercury is given as 20.35" K (Kelvin international scale). G. W. R. Spontaneous Incandescence of Substances in Atomic Hydrogen Gas. R. W. WOOD(Proc. Roy. Xoc., 1922, [A],102, 1-9).-A number of experiments with very long hydrogen dis- charge tubes are described from which it is shown that some metals, oxides, and other substances are raised to incandescence when introduced into a stream of atomic hydrogen, the surface of the substance acting as a catalyst in bringing about the recombination of the atoms. Atomic hydrogen, practically free from molecular hydrogen, may be drawn by a pump from the central portion of a long discharge tube excited by a current of high potential. E'ire 28-2 View Article Online ii. 760 ABSTRACTS OF CHEMICAL PAPERS. polished glass surfaces, such as the walls of a glass tube, have a comparatively feeble catalysing power whilst fractured surfaces cause the recombination of the atoms, and are strongly heated. The action of water vapour or oxygen in enhancing the Balmer spectrum, and suppressing the secondary spectrum of hydrogen, is probably due to its action on the walls of the tube, which, when dry, catalyse the atomic hydrogen as fast as ii; is formed by the current. The peculiar spectroscopic phenomena observed with long hydrogen tubes, described in an earlier paper (A., 1920, ii, 569) are explained. Methods are suggested for determining the physical and optical properties of atomic hydrogen gas. J. F. S. Evidence of the Existence of Isotopes of Chlorine. M-~TA- KICHI ISHINO(Mem. CoZZ. Xci. Kyoto, 1021, 4, 311-315).-Em- ploying the method of positive-ray analysis, using the crossed- deflexion method devised by Thomson, the author has obtained evidence of the existence of chlorine isotopes of respective atomic weights 34 and 36, and of positively charged chlori6e atoms. J. S. G. T. The Decomposition of Chlorine into Atoms. Msx TRAUTZ and WALTERSTACKEL (2. anorg. Chem., 1922,122,81-131).-The apparatus employed and methods of working are described in detail. The amount of chlorine decomposed was 1.50% at 1200", 2*10yo at 1240", and 3.05% at 1280". The limit of the absorption band for chlorine was found to he 390420pp. This corresponds with 67,500-73,000 cal. as the heat of decomposition according to Trautz's " approximate " equation qo=Ahv (A., 1918, ii, 151). The heat of decomposition of chlorine calculated from the tem- perature coefficient was found to be 71,000&3,000 cal. The same result was obtained by the use of the quantum theoretical con- Published on 01 January 1922. Downloaded 26/10/2014 14:59:11. stants and also by the use of Victor Meyer's vapour density measure- ment's. With the exception of hydrogen, the heat of deconiposition of the diatomic elements found experimentally agrees with the value obtained from the equation d0=(5.78 x 1051 &@) cal., where M is the molecular weight. W. T. Vapour Pressure of Solid Chlorine and Bromine. F. A. HENGLEIN,G. VON ROSENBERG,and A. MUCHLINSKI(Z. PhysiJc, 1922, 11, 1-ll).-The vapour pressure of solid and liquid chlorine and solid bromine has been determined over a wide range of tem- perature. The following values are recorded for chlorine, 119.3" 0.0013 ; 126.0", 0.0063 ; 133*0", 0.028 ; 146-6", 0.30 ; 161.1", 2.75 ; 177.6", 17.40 ; 194.5", 6440, and for bromine 177.6", 0.0020 ; 210-0", 0.26; 228-8", 1.12; 227-0", 1.71; and 241.1", 6.44; the temperatures are expressed in absolute degrees and the pressures in millimetres of mercury. Vapour pressure formulz have been deduced for both cases and have the form : log p=-1160/T+7773 for liquid chlorine ; log p= - 1530/T+9950 for solid chlorine ; these formula are representative over the temperature ranges -95" to -78" and -154" to -112", respectively, logp= -112150/T1'36s+75030 for solid bromine over the range -32" to View Article Online INORGANIC CHEMISTRY. ii. 761 -96". From the above data a number of constants have been calculated which include the following : Chlorine, m. p. 170.0" Abs. : vapour pressure at the melting point 8.9 mm., molecular heat of vaporisation at the melting point 5300 cal., heat of sublimation of solid chlorine at the melting point 6960 cal., molecular heat of fusion 1660 cal. ; bromine : vapour pressure at the melting point 44-12 mm., molecular heat' of sublimation at the melting point 9740 citl., specific heat of sublimation 60.91 cal., specific heat of vaporisation at the melting point 45.4 cal., molecular heat of fusion 12.5 cal. From the dissociation equilibrium of the chlorine molecule and the chemical constant as determined by Stern and Tetrode the vapour pressure of diatomic chlorine has been calculated and the chemical constant for diatomic chlorine in its normal condition has also been obtained. J. F. S. Physical Constants of Ozone. E. H. RIESENFELDand G. M. SCHWAB(a. Phy&, 1922,11, 12-21 ; cf. this vol., ii, 637).- An account of the determination of a number of physical constants of pure ozone which was prepared as previously described by the authors (Zoc. cit.). The following values are put on record : m.. p. -249-7", b. p. -112.4" ; critical temperature, -5" ; specihc gravity at -183", 1.71&0-1; change of density with temperature, l/d=n+bT+cP, where a=0-51193, b=0.0004559, c=0.000003929 ; density at the boiling point, 1.46 ; coefficient of expansion, 0.0025 ; critical density, 0-537 ; critical pressure, 64.8 atmospheres. The authors show that neither in the gaseous nor in the liquid state is there any other molecular species present than that represented by the formula 0,. J. F. S. Solubility of Sulphur Dioxide in Suspensions of Calcium and Magnesium Hydroxides. WM. THOMPSONSMITH and Published on 01 January 1922. Downloaded 26/10/2014 14:59:11. REGINALDB. PARKHURST(J. Amer. Chem. Xoc., 1922, 44, 1918- 1927).-The solubility of sulphur dioxide has been determined in water, milk of lime, and milk of magnesia, at partial pressures of sulphur dioxide up to 760 mm., and femperatures from 5" to 60". All proportions of calcium and magnesium hydroxides were used in suspensions of a total alkalinity of one equivalent per litre. It is shown that the concentration of sulphur dioxide as sulphurous acid is proportional to its partial pressure. With solutions of the same alkali concentration, the percentage salting-out effect increases with, but more than in proportion to, the temperature. With solutions of constant temperature, the percentage salting-out effect increases with the alkali concentration, but is less than propor- tional to it. Varying proportions of calcium and magnesium hydroxide have no effect on the equilibrium concentration of sulphur dioxide as sulphurous acid. J. F. S. The Physico-chemical Study of the Lead Chamber Process. lMAx FORRER(BUZZ. Xoc. chim. BeZg., 1922, 31, 254-293).-A detailed description of a form of apparatus in which sulphur di- oxide, nitrogen peroxide, water, oxygen, and nitrogen may be brought into contact with each other under definite conditions View Article Online ii. 762 ABSTRACTS OF CHEMICAL PAPERS, of pressure, temperature, and, in the case of liquids, surface of -reaction. The proportions of these substances could be varied at will. It is shown that, in such a system, the formation of sulph- uric acid only occurs in presence of a liquid phase, so that the system must be heterogeneous; the formation of the acid takes place in a shorter time and the yield is increased if a liquid, either sulphuric acid or water, is present at the outset. Further, the rate at which water vapour is supplied during the course of the reaction exerts a considerable effect both on the velocity of reaction and on the concentration of the product. Under certain conditions, the acid formed may disappear, which appears to indicate that the reactions assumed to take place in the chambers are at least partly reversible. For low concentrations of the gases, there is an optimum rate of intake €or water vapour : this gives.the best yield and, at the same time, the most concentrated acid. As the gas concentration increases, the optimum point shifts in the direction of diminution of water supply; a curve'is given showing the speed of reaction plotted against concentration of gas. The relation between these two factors is much less complex when the composition of the liquid phase is constant. The author infers from his experimcntzl results the existence of an intermediate substance of which water is a constituent ; it is, however, decomposed in presence of an excess of water. He points out that, of the series of reactions which occur, the slowest is the " limiting reaction " in that it conditions the rate of formation of the product and shows that, in practice, the reaction velocity is strongly influenced by the rate of supply of nitrogen peroxide and water, but is practically unaffected by the supply of sulphur dioxide. An attempt is made to calculate the order of the reaction, and, for this purpose, the heterogeneity of the system and the non- equivalence of the reactants are neglected.
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