Kinetic Analysis of High-Rate and of Low-Rate Regimes in CO Oxidation on Pt Group Metals: Evidence for Vibrational Excitation of the O-Rich Adlayer and for Thermal Equilibrium of the CO-Rich Phase

Abstract

Abstract Proper reduction of available literature data on the heterogeneous CO+O2 reaction on Pt group metals allows one to describe the parallel process of CO desorption, in extended intervals of temperature and gas composition, both in the High-Rate regime of an oxygen rich surface and in the Low-Rate regime of a CO rich surface. The outcome of this analysis is the determination of “apparent” as well as of “true” activation energies for both CO oxidation and desorption and their dependence on surface coverage by O or by CO-adspecies. The conclusion is reached that non-equilibrium conditions of vibrational excitation of the adlayers prevail in the HR regions, while Boltzmann equilibrium characterizes LR regimes in extended temperature and pressure intervals. These results have been discussed in the framework of a theoretical model that predicts hyperthermal vibrational states of the adlayer, which depend on the efficiency of energy dissipation into the metal.