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ISBN-10: 0120580020

ISBN-13: 9780120580026

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As an example, let us consider that the surface consists of patches, each of proportion χ{ which are in equilib­ rium with a gas, and that on each patch adsorption is described by a simple Langmuir isotherm *lP (ΙΠ)-(26) 1 + at p The constant ai is a function of the heat and entropy of adsorption and has values which are different on each patch, so that different fractions, #i, of each patch are covered, subject to equation (III)-(23) for the total coverage 0. While there need not be any direct functional relationship between the heat and entropy of adsorption, it is usually found that a high heat of adsorption is associated with a large loss of entropy.

ANDERSON AND B. G. BAKER principles. If adsorption occurs under simple nondissociative Langmuirian conditions, it is reasonable to write fa(0) = (1 — 0) and fd(0) = 0; in confirmation, if E a and Ed are independent of 0, equating r a and rd leads to the form of the simple Langmuir isotherm. For the corre­ sponding case of binary dissociative adsorption, an expression for fa(0) may be written if we assume t h a t adsorption requires a pair of vacant sites. If adsorption in the localized layer is random (zero inter­ action energy), the chance of obtaining each vacant site of the pair is (1 — 0), so fa(0) = (1 — 0)2, and in an analogous way fd(0) = 02.

UNIFORM SURFACES 1. Steady-state Surface Coverage Rate expressions are constructed by analogy with simple kinetic theory in terms of the individual surface entities taking part, and it is 40 J. R. ANDERSON AND B. G. BAKER the surface concentrations of the latter t h a t are related to bulk pressures or concentrations via the adsorption isotherms. Thus, for instance, if the rate of a catalytic reaction between gases (A, B , . . X) is controlled by a surface reaction r between N types of surface species (1, .

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Chemisorption and Reactions Metallic Films by J.R. ANDERSON (Eds.)

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