Advances in Catalysis, Vol. 7 by W.G. Frankenburg, V.I. Komarewsky, E.K. Rideal (Eds.)

By W.G. Frankenburg, V.I. Komarewsky, E.K. Rideal (Eds.)

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Am. Chem. Soc. 76, 319 (1954). 55. Wilson, A. , Proc. Roy. A133, 458 (1931); A134, 277 (1931). 56. , and Selwood, P. , J . Am. Chem. 74, 1750 (1952). 57. , and Selwood, P. , J . A m . Chem. 74, 2461 (1952). 58. Garner, W. No. 8, 211 (1950). 59. Garner, W. , and Kingman, F. E. , Trans. 27, 322 (1931). 60. Garner, W. , Stone, F. , and Tiley, P. No. 8, 254 (1950). 61. Garner, W. , Stone, F. , and Tiley, P. , Proc. Roy. A211, 472 (1952). 62. Garner, W. , Gray, T. , and Stone, F. No. 8, 246 (1950). 63.

Dowden (27) considers the active centers for carbonium ion formation to be associated with surface cation vacancies. A proton, derived from water contained in the catalyst, is attracted t o the anions surrounding the vacancy. A hydrocarbon molecule is assumed to be held by polarization forces above this lattice defect and the proton will be distributed between the hydrocarbon and the anions, forming a carbonium ion of a definite lifetime. Evidence t hat the presence of water is important in these reactions has been obtained by Hansford (82).

Further work by these authors (50) on styrene hydrogenation with nickel-iron alloy + ELECTRONIC FACTOR I N HETEROGENEOUS CATALYSIS 27 catalysts showed that the specific activity decreased with decreasing values of N ( E ) . This is a result to be expected on the Dowden theory, for a reaction proceeding a t a velocity depending on the rate of formation of, or the concentration of, chemisorbed positive ions (or radicals) on the surface (Fig. 15). The rise in activity from 80 nickel-20 iron to 100% nickel is attributed to the large increase in N ( E ) , and the fall from nickel to nickel-copper is attributed to both the decrease in the number of d-holes and t o the large fall in N ( E ) .

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