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A computer-simulated model of affinity capillary electrophoresis is developed. Unlike existing models, it is able to describe the situation where the concentrations of sample molecules and ligand molecules are commensurable, or even the situation where the zones occupied by these molecules are not mixed initially. The model permits to study the dependence of the spatial and temporal distributions of sample molecules on various parameters such as reaction rate constants, concentrations of sample and reagent, electromigration velocities of sample and reagent and sample injection volume. A collection of peak shapes for different values of parameters is presented. The dependence of peak variance on the ratio of the time of analysis to the characteristic time of reaction is studied.

Electroinjection analysis has been demonstrated to provide reaction kinetics information. Reactants are injected continuously from opposite ends of the capillary for the duration of the experiment, and reaction product formation occurs at the boundary where the zones merge. The width of the product signal measured by the detector depends on the ratio of the fluxes of reactants. The boundary moves toward the detector where the products are measured. A sharp peak at the edge of the main flat product signal peak was observed and most probably corresponds to the metastable intermediate product of reaction, a unique capability of this technique. A theoretical explanation and an experimental verification of the possibile use of electroinjection analysis for the study of reaction kinetics is given.

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