By J.R. ANDERSON (Eds.)

ISBN-10: 0120580020

ISBN-13: 9780120580026

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**Additional resources for Chemisorption and Reactions Metallic Films**

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9: frequency factors adjusted for complete compensation at 363 °K. 1 the overall rate (curve A) lies very close to the plot for patch 1. At temperatures between 300 and T' an almost linear plot with Eact ~ 21 is obtained. Above T' pronounced curvature occurs as the smaller patch with the higher activation energy plays an increasingly dominant role in the reaction. 1 (curve B) then above T' the apparent activation energy is ^ 30 but at lower temperatures curvature away from this value gives successively lower apparent activation energies.

This includes the case of i = 0, that is the undeuterated parent. The computation of xi(t) is relatively straight forward since stepwise exchange must lead to a binomial product distribution: Bolder et al. give an explicit expression (their equation 39) to compute #i(t) from a(t) (or <£(t)). In stepwise exchange, kinetic isotope effects do not alter the nature of the product distribution, only the overall reaction rate. Furthermore, if the deuterium atoms are provided from the source not all with equal reactivity, the product distribution will remain binomial, although the a(t) (or <£(t)) functions then become complicated, since one is dealing with parallel reaction paths.

Since, as the surface fills blocked sites are shared by more than one adsorbed entity, v will decrease as coverage increases. It is readily shown (Baker, 1966) that the configurational differential entropy of adsorption is given by * s - - K h ( ^ ) (III)-(19) and there follows the isotherm equation p c* = ^(r^w) b,T,e -' (ΠΙ)-(20) 28 J. R. ANDERSON AND B. G. BAKER where b(T) and e _ e / R T are the same as the corresponding terms in the simple Langmuir isotherm. Here vM is the number of blocked sites per adsorbed entity for a surface regularly packed to capacity, and Θ is defined as the ratio of the number of adsorbed entities per unit area to the maximum allowed.

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