Several modes of the often used ACE processes are simulated based on the principle of dynamic complexation. of interacting species in a capillary column. The model is built on the mass transfer equation, to provide insight into the detailed analyte migration and interaction processes in CE. Normal ACE, Hummel-Dreyer method, vacancy affinity CE, vacancy peak method, and CE frontal analysis are simulated based on typical ACE conditions, and the results are compared with the detector responses of real CE processes using BSA and warfarin as a model system. Remarkable resemblance between the simulated results and the experimental observations was demonstrated for well-buffered ACE systems.