Kinetics of liquid phase photocatalyzed reactions: An illuminating approach.

Analysis of photocatalyst kinetics to date have relied largely on Langmuir-Hinshelwood rate forms, which assume equilibrated adsorption of reactants and, correspondingly, a slow, rate-controlling surface step. Alternatively, and more generally, a pseudo-steady state analysis based upon the stationary state hypothesis for reaction intermediates may be applied. We show here that only this second approach is consistent with the reported intensity dependence of apparent adsorption (and desorption) binding constants, as well as the catalytic rate constant. In consequence, we show that for at least some photocatalyzed reactions, adsorption/desorption reaction equilibria are not established during reaction, because the substantial reactivity of an adsorbed active species (e.g., hole (h+), radical (*OH), etc.) causes a continued displacement from equilibrium of the adsorbed reactant concentration.