Lattice-gas model in kinetic theory of gas-solid interface processes

Abstract

The improvement of the experimental methods for investigating surface processes changes the existing ideas about the role of the different factors of the gas-solid system and the mechanisms of the processes. The recent studies have confirmed the conception of surface processes as the ones taking place in the condensed phases. At the same time, the surface processes generally are described by fairly rough models based on the law of mass action, which is true of the ideal systems. The contradiction is eliminated to a certain degree when a lattice-gas model which takes into account the proper volume of the adspecies and adspecies interaction is used. On this basis it is easy to consider the effect of the local environment on the activation barrier of an elementary process. This enables one to apply it extensively to be the atomic-molecular processes associated with a change in the spatial arrangement of the adspecies and their chemical conversion. The review describes the development of the kinetic theory of the surface processes at the gas-solid interface using on the lattice-gas model and its modern modifications. Applications of the theory to the adsorption-desorption processes and the catalytic reactions are considered. The reaction rates in the condensed phases and the role of the correlation effects of the interacting adspecies and the distribution of the system's components are described. The lattice-gas model helps us explain the empirical principles of the adsorption processes; a variable order of desorption rate; the splitting of the thermodesorption spectra on the homogeneous surfaces; an increase in the sticking coefficient with coverage at its small values; phase transitions in the adlayers and their effect on the adsorption-desorption rate and the diffusion coefficients; a great mutual effect of the adspecies of the different kinds on the rate of the elementary processes; the dependence of the course of a process on the conditions in which the initial surface coverages are formed; multiplicity of the steady states of the reaction systems and the isothermal oscillation conditions of the reaction mode; etc. At present the theory of surface processes enables one to take into account a wide range of the real properties of the gas-solid system: the lateral interaction between the adspecies and their phase transitions, surface inhomogeneity, a limited mobility of the adspecies and the solid body surface atoms, the rearrangement of the subsurface solid region and so on. The joint influence of the factors mentioned above are also taken into account. Theoretical results are compared with the numerical calculations by the Monte Carlo methods.