Mobile and stationary phases for SFC: effects of using modifiers

The effects of modifiers on the mobile-phase and the stationary-phase properties in packed-column supercritical-fluid chromatography were studied. Modifiers, may affect retention and improve peak shapes and efficiencies, because of (i) increased mobile-phase polarity, (ii) increased mobile-phase density, (iii) stationary-phase deactivation, and (iv) increased solvation or swelling of the stationary phase. In this paper these four parameters are evaluated and evidence to establish their relative importance is considered. The introduction of a modifier can lead to a substantial increase in the density of the mobile phase. The reliability of several methods for calculating the critical properties and densities of binary fluids is investigated. The Chueh and Prausnitz method gives the most accurate results for the calculation of the critical properties. The Lee and Kesler equation of state yields accurate density estimates. Adsorption isotherms have been measured on several stationary phases for packed-column SFC. These data suggest that stationary-phase deactivation is the most important effect of adding modifiers. Adsorption data on different stationary phases can also be used to judge their applicability. Relevant indicators are the maximum amount of modifier that can be adsorbed on the surface (saturation level) and the initial steepness of the isotherm (surface activity). The latter parameter can be related more closely to the peak shape observed in the absence of modifiers. All silica-based materials studied so far give rise to broad and highly asymmetrical peaks for certain classes of polar solutes. Different silica-based materials appear to differ in degree of activity, but the kind of interactions are the same. On a polystyrene-divinylbenzene stationary phase the mobile-phase modication effect could be studied without the interference of active sites.