CE is a promising technique for the investigation of molecular interactions because it affords evaluation of multiple interaction modes, does not require immobilization of molecules, and has no dead time. In order to perform these investigations, numerous methods have been developed for determining binding constants and other thermodynamic parameters. These methods have been reviewed extensively in recent years. However, methods for determining the rates of reaction are less prolific. Nonetheless, numerous theoretical and experimental advances have been made in recent years to address this discrepancy. Some of these methods employ computer simulations to determine first-order or second-order rate constants numerically, whereas other methods calculate rate constants directly as solutions to analytical equations. It is the object of this review to provide descriptions of these methods in terms of their underlying assumptions, experimental methodology, calculation of rate constants, and inherent limitations.