Effects of nonequilibrium on velocity and plate height in reactive capillary electrophoresis.

Models for velocity and plate height for reactive CE are developed under the formalism of generalized nonequilibrium theory, as described by Giddings. The resultant equations are consistent with chromatographic theory and validated with an independent stochastic simulation. Moreover, unlike prior methods for CE, this model allows calculation of thermodynamic equilibrium constants and kinetic rate constants from a single, undistorted peak. The theoretical development shows that velocity is directly dependent on the equilibrium constant and is independent of the rate constant. On the other hand, plate height varies little with equilibrium constant and is inversely proportional to rate constant. The ability to evaluate equilibrium constants from velocity and rate constants from plate height is most greatly influenced by electric field strength and mobility difference. The accuracy in calculated equilibrium constants is limited by mobility difference; however, the accuracy in rate constants is limited by plate height and equilibrium constant.