Sticking coefficient and pressure dependence of desorption rate in the statistical rate theory approach to the kinetics of gas adsorption. Carbon monoxide adsorption/desorption rates on the polycrystalline rhodium surface.

The statistical rate theory (SRT) fundamental kinetic equation for the Langmuir model of adsorption reveals some features which are difficult to understand. These are the infinitely high adsorption rate for zero coverage limit, infinitely high desorption rate at full saturation of the surface and dependence of the desorption rate on the adsorbate pressure. These features do not allow for a correct formulation of such important physical parameters as sticking and initial sticking probabilities. In this work these peculiar features of the fundamental SRT kinetic equation are discussed and explained. It is shown that the non-physical behavior of the SRT kinetic equation follows from neglecting possible changes of adsorbate concentration near the adsorbing surface. A simple model accounting for the changes of adsorbate concentration close to the adsorbing surface is discussed. As a result, it was shown that application of even such a simple model leads to fully physical behavior of the SRT kinetic equation for the Langmuir model of adsorption. The model is used to build up equations describing the kinetics of adsorption/desorption of carbon monoxide on the energetically heterogeneous rhodium surface. The values of the parameters in these equations were determined from the analysis of equilibrium adsorption isotherms and from the description of experimental conditions. One additional parameter (having well defined limiting values) had to be adjusted in order to satisfactorily reproduce kinetic data. The experimental data used in this work were taken from the article by Yamada and Tamaru (T. Yamada and K. Tamaru, Surf. Sci., 1984, 138, L155).