Effect of various modifiers on selectivity in packed column subcritical and supercritical fluid chromatography

A number of common mobile phase modifiers were characterized by chromatographing monofunctional probe solutes on a cyano-bonded stationary phase under subcritical and supercritical conditions. Solvatochromic analysis techniques were used to characterize the relative selectivity, efficiency, and eluotropic strengths of the various modified mobile phases, Analysis of the combined results suggests that modifier choice may be made in a rational manner to either enhance or mask a particular type of molecular interaction, This control is necessary for challenging applications such as chiral separations. The relative effects of each modifier property change depending on whether the chromatographic system is subcritical or supercritical, thus making Knowledge of the phase equilibria associated with the mobile phase essential.