Study of flow profile distortions and efficiency in counter pressure moderated partial filling micellar electrokinetic chromatography in relation to the relative buffer zone lengths

The influence of the relative buffer zone lengths on the efficiency was investigated in partial filling micellar electrokinetic chromatography using sodium dodecyl sulfate as separation additive. Varying relative zone lengths were obtained by applying identical initial separation zone lengths but different total lengths of the capillaries. Plate numbers of a homologous series of ω-phenylalcohols were measured to indicate the effect of both a changing relative zone length during the run and a counter pressure applied on the cathodic buffer reservoir. The magnitude and the course of these plate numbers are discussed on the basis of models for flow profile superposition and flow profile deformation which are caused by an intersegmental pressure arising at the boundary between the two buffer zones with different electroosmotic flow velocities. Calculation of the intersegmental pressure and of the resulting laminar flow components in the buffer zones on the basis of some equations for electroosmotic and hydrodynamic flow supported the interpretation that a long background buffer zone should be avoided in case of mismatched electroosmotic flows.