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An analysis is given of diffusion-influenced surface reactions using models similar to those used in solution kinetics. It is shown that a pure two-dimensional model of surface reactions yields no steady state rate constant. By incorporation of adsorption and desorption processes the deficiencies in the two-dimensional results are eliminated. Expressions are derived for diffusion-controlled and diffusion-influenced rate constants for surface reactions. Expressions are also derived for the activation energies of these surface reactions. It is shown that the activation energy for diffusion-controlled reactions wiII approximately be given by the activation energy for surface diffusion. Bounding expressions are developed for the activation energy for diffusion-influenced reactions. Comparisons are made betweeen Langmuir-Hinshe1wood and Eley-Rideal mechanisms, and it is found that Langmuir-Hinshelwood mechanisms should be more important than Eley-Rideal processes for many surface reactions.

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© 1983 American Institute of Physics.