This work applies the methods of statistical mechanics to two processes relevant to thermoluminescence; (1) the charging of traps, and (2) the discharging of traps. Assuming thermal and diffusive equilibrium, we calculate the trap ionization probabilities over a wide temperature range and for a variety of traps in YAG:Ce. The goal is to investigate whether a statistical approach yields results consistent with experimental thermoluminescence observations. We are able to reproduce with good accuracy the glow curves of several traps observed in YAG:Ce. Our calculated glow curves are shown to be consistent with systems exhibiting second order kinetics. For systems of traps that are at or near thermal and diffusive equilibrium with the conduction electrons, the results indicate that the position of a glow curve peaks is determined by two factors: the trap depths and the density of conduction electrons.