On the measurements of electrophoretic mobilities by means of capillary isotachophoresis at a constant voltage.

A method for measuring electrophoretic mobilities by means of isotachophoresis (ITP) at a constant voltage as described by H. Carchon and E. Eggermont (Electrophoresis, 1982, 3, 263-274) is analyzed. An error made in this work, disregarding the pH shift arising at the initial discontinuity on the leader-terminator boundary, has been corrected. This method has been carefully studied and generalized for the presence of constant electroosmotic flow in a capillary. The limits of its applicability and the diffusionless ITP theory in general are discussed. A detailed study of the evolution of initial discontinuity (stationary boundary) showed some anomalies not reported previously, particularly non-monotonic concentration profiles in the vicinity of stationary boundaries. Moreover, in some cases, diffusion effects and the contribution of H+ ions can also strongly influence the behavior of moving boundaries. Computer modelling (confirmed by experimental data) showed that these effects could lead to the decay of the ITP train, despite the fact that the steady state diffusionless ITP theory predicts its stability.