Microkinetic Modeling of Surface Catalysis

Microkinetic modeling (MKM) breaks down a reaction mechanism into all known elementary steps making no a priori assumptions about dominant reaction paths, rate determining steps, and most abundant reactive intermediates. Instead this information emerges from the solution of the model. Aside from mechanistic understanding, MKM can be utilized to optimize reaction conditions and/or reactor configuration and provide guidelines for catalyst design. This chapter focuses on describing the basics of mean-field MKM. It also details how firstprinciples calculations or fast-screening methods can be used in conjunction with transition state theory and statistical mechanics to derive kinetic and thermodynamic parameters that abide to thermodynamic consistency constraints. Finally, the chapter covers analysis techniques that provide key insights into the reaction mechanism. We focus primarily on the ammonia decomposition chemistry as an illustrative example.