Position and intensity of system (eigen) peaks in capillary zone electrophoresis

The intensity of system (or eigen) peaks encountered in capillary zone electrophoresis (CZE) can be predicted by considering mass balances for each of the analyte constituents and each of the constituents in the background electrolyte (BGE). As a result of coherence, in each zone the proportions in which the constituent concentrations vary are fixed; they are determined by the composition of the BGE and the nature of the analyte constituent (if present) and described as eigenvectors of a transport matrix. Considering the effect of an injection, the mass balances for all constituents can be satisfied only via the intensity of each zone. This leads to an n-equations, n-unknowns problem, with the intensities as the unknowns and the mass balances as equations. The latter can be easily solved to obtain the intensities of the zones, of analytes as well as of system peaks. In this work the approach has been applied to CZE systems with two co-ions in the BGE, and experimental results have been compared to the predictions obtained from the model. Agreement was seen to be reasonable, but the quantitative comparison often failed, probably due to experimental difficulties. (C) 2002 Elsevier Science B.V. All rights reserved.