The Behaviour of the Centres of Activity of Saturated Surfaces during the initial stages of Unimolecular Reactions
Published online by Cambridge University Press: 24 October 2008
Extract
The theory of catalytic action recently advanced qualitatively by Pease, Taylor, Armstrong and Hilditch, Constable, which the author has endeavoured to treat quantitatively, is extended in this paper to the explanation of the effect of pressure and inert diluents on catalytic action on saturated surfaces. The results are shown to be in agreement with experiment, and further inferences may be made concerning the relative mean lives of the reactant and the diluent on the surface.
- Type
- Research Article
- Information
- Mathematical Proceedings of the Cambridge Philosophical Society , Volume 23 , Issue 2 , April 1926 , pp. 172 - 182
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- Copyright © Cambridge Philosophical Society 1926
References
* J. Amer. Chem. Soc. vol. 45, pp. 1196, 2235, 2297 (1923).CrossRefGoogle Scholar
† Proc. Roy. Soc. A, vol. 108, p. 105 (1925)Google Scholar; also J. Phys. Chem. vol. 28, p. 911.Google Scholar
‡ Trans. Farad. Soc. vol. 17, p. 670 (1922)Google Scholar; Proc. Roy. Soc. vol. 108, p. 111.CrossRefGoogle Scholar
§ Proc. Roy. Soc. vol. 107, p. 274 (1925).Google Scholar
‖ Proc. Roy. Soc. vol. 108, p. 374 (1925)Google Scholar; Nature, vol. 116, pp. 278–9; vol. 117, pp. 230–237 (1926).Google Scholar
¶ See following papers.Google Scholar
** J. Amer. Chem. Soc. vol. 45, pp. 887, 900 (1923).CrossRefGoogle Scholar
†† J. Amer. Chem. Soc. vol. 40, p. 1400 (1918)Google Scholar; also vol. 38, p. 2267 (1916); and Trans. Farad. Soc. vol. 17, p. 606 (1922).Google Scholar
‡‡ J. Amer. Chem. Soc. vol. 38, p. 2267 (1916) et seq. (loc. cit.).Google Scholar
* Zeit. für Phys. vol. 26, p. 117 (1924).CrossRefGoogle Scholar
† For experimental evidence see Norrish, J. Chem. Soc. vol. 123, p. 3007Google Scholar; Hinshelwood, and Pritchard, , J. Chem. Soc. vol. 123, p. 2725 (1923).CrossRefGoogle Scholar
‡ This is a fundamental hypothesis of the Langrauir-Frenkel theory.Google Scholar
§ There is very strong evidence in support of this constancy for alcohol and copper; it appears however that at very high.pressures the velocity should fall with pressure, because the escape of the molecule is retarded.Google Scholar
‖ Zeit. Phys. Chem. vol. 60, p. 61 (1907)Google Scholar; Bodlander, and Kopper, , Zeit. Electrochem. vol. 9, p. 556 (1903)CrossRefGoogle Scholar; Berl, , Zeït. anorg. Chem. vol. 44, p. 267 (1905).CrossRefGoogle Scholar
¶ Henry, , Phil. Mag. (iii), vol. 9, p. 324 (1836).Google Scholar
** Engelder, , J. Phys. Chem. vol. 21, p. 676 (1917).CrossRefGoogle Scholar
†† Ipatieff, , Ber. deutsch. chem. Ges. vol. 37, p. 2996 (1904).Google Scholar
* Adkins, and Nissen, , J. Amer. Chem. Soc. vol. 46, p. 809 (1923).CrossRefGoogle Scholar
† J. Amer. Chem. Soc. vol. 47, p. 123 (1925).CrossRefGoogle Scholar
‡ Chem. Met. Eng. vol. 26, p. 650 (1922).Google Scholar
* Constable, “Mechanism of Catalytic Decomposition”, loc. cit.Google Scholar
* I.e. the most active in the distribution: see Constable, Proc. Roy. Soc. A, vol. 107, p. 376 (1925).Google Scholar
* Constable, Nature, vol. 116, p. 739 (1925).CrossRefGoogle Scholar
* J. Amer. Chem. Soc. vol. 47, p. 1235 (1925).CrossRefGoogle Scholar
† E.g. C2H4 and H2 (Pease, loc. cit.).Google Scholar
* Verified by Hinshelwood and Pritchard for poisonous action of O2 on the decomposition of N2O2J.C.S. vol. 127, p. 330 (1925)Google Scholar: I have confirmed this poisonous action of O2, on the platinum catalyst and results agree with the equation deduced. Under conditions to be discussed later, this formula is rigorously true, and no longer an approximation when the pressure of poison is small.
* Hinshelwood, and Bark, , J. Chem. Soc. vol. 127, pp. 1114–6.Google Scholar The effect of hydrogen on the decomposition of NH3 by platinum decreases as temperature rises. Langmuir, , Trans. Farad. Soc. vol. 17, p. 621 (1922), shows that the poisonous action of H2 and CO on their respective reactions to form H2O or CO2 is marked at low temperatures but vanishes as the temperature is raised.CrossRefGoogle Scholar
† Pease, loc. cit.Google Scholar
* J. Amer. Chem. Soc. vol. 47, pp. 132, 133, figs. 4 and 5 (1925)Google Scholar. The modification in this law of poisoning caused by the formation of a complex between the reactant and the poison which is more highly reactive than the adsorbed reactant alone will be considered in a later publication. When this occurs the curves show a point of inflection, as is Been in the observations quoted.Google Scholar
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