Self-Consistent Calculation of the Rates of Dissociative Adsorption and Desorption with the Adsorption Isotherm on the Rough Surface of an Adsorbent

Abstract

The fulfillment of the self-consistency condition in the description of adsorption and desorption the rates of dissociating vapor molecules on the rough surface of an adsorbent (equilibrium and tempered from an equilibrium state) is considered. The adsorption process causes the reconstruction of the equilibrium near-surface region of the adsorbent, but does not change the state of the tempered surface. The adsorption–desorption rates are calculated taking into account the interaction of the nearest neighbors in the quasi-chemical approximation. Four models are considered for the description of a nonuniform surface: the initial averaged multilayer model with different types of adsorption sites (and Henry constants), a model containing all the sites available for adsorption, and three types of its averaging. The first type of averaging is associated with the transition to a single-layer nonuniform surface containing different types of adsorption sites with different Henry constants, the second is associated with the transition to a set of effective uniform monolayers in the multilayer transition region, and the third is associated with the transition to a single-layer effective uniform surface. The condition of self-consistency is fulfilled in the last two types of averaging and is violated in the first type of averaging, as well as in the averaged model taking into account the differences between the types of sites. It is found that the state of a nonuniform surface (equilibrium or tempered) does not affect the self-consistency of the description of the rates of adsorption and desorption in the latter two types of models. The influence of taking into account the effects of correlation of the interaction of species on the condition of self-consistency is shown. The neglect of the effects of correlation of interacting species leads to the violation of the self-consistency condition in all models.