Quantitative study of concentration overload, peak asymmetry, and efficiency loss in micellar electrokinetic...

An equation is derived for the velocity of a thin zone of specific analyte concentration in micellar electrokinetic chromatography. The velocity varies with analyte concentration, because micellar solubilization changes electrical conductivity, micellar electrophoretic mobility, and the partitioning of anabyte between mobile and micellar phases. Two studies based on a weakly and a strongly retained neutral analyte are made to test a limiting form of the equation in which the first two changes are ignored. In the first study, peak asymmetries are characterized and plate numbers are measured in two types of experiments: one of fixed surfactant concentration and variable analyte concentration and one of fixed analyte concentration and variable surfactant concentration. In the second study, the isotherm describing both experiment types is measured and interpreted by the Langmuir model to evaluate the velocity equation. The equation of continuity is solved numerically for the peak profiles governed by the velocity equation. In all but one case, a good agreement is found between theoretical and experimental peak asymmetries and plate numbers in both experiment types. An equation is derived for the relative change of analyte velocity caused by the Langmuir isotherm. The change depends on the relative migration time, micellar saturation, and retardation factor. The predicted velocity changes correlate well with peak asymmetries and efficiency losses.