Theoretical and experimental study of binary perturbation peaks with focus on peculiar retention behaviour and vanishing peaks in chiral liquid chromatography

The perturbation peak theory was recently developed for acquiring binary isotherm data using the perturbation method (PM) and it was applied for some chiral systems. However, the binary plateaus of these systems were only weakly to moderately nonlinear. In this article the perturbation theory for LC, is developed for both retention times and peak areas and is verified by systematic experiments over the whole range of non-linearity. Attention is focused on non-linear effects that complicate the proper use of the PM method under moderately to strongly non-linear conditions. A serious complication was that the second perturbation peak vanished already at moderate plateau concentrations. A solution to this problem based on a firm theoretical basis and verified experimentally is presented. We also investigated a peculiar retention dependence on the binary plateau concentration, as the retentions of the two perturbation peaks of the binary plateau was compared with the single plateau peak of the more retained enantiomer. (C) 2003 Elsevier Science B.V. All rights reserved.