Extension of Tóth Psi function from gas-solid to liquid-solid equilibria and application to reversed-phase liquid chromatography systems.

Abstract

The extension of the Psi function developed by Tóth from equilibria taking place at gas-solid interfaces to those taking place at liquid-solid interfaces was investigated. The results were applied to conventional liquid-solid systems used in reversed-phase liquid chromatography (RPLC). The adsorbents in these systems are made of porous silica having a hydrophobic solid surface obtained by chemically bonding C(18) alkyl chains to a porous silica gel then endcapping the surface with trimethylsilyl groups. The liquid is an aqueous solution of an organic solvent, most often methanol or acetonitrile. The probe compound used here is phenol. Adsorption data of phenol were measured using the dynamic frontal analysis (FA) method. The excess adsorption of the organic solvent was measured using the minor disturbance (MD) method. Activity coefficients in the bulk were estimated through the UNIFAC group contributions. The results show that the Psi function predicts 90% of the total free energy of immersion, DeltaF, of the solid when the concentration of phenol is moderate (typically less than 10 g/L). At higher concentrations, the nonideal behavior of the bulk liquid phase becomes significant and it may contribute up to about 30% of DeltaF. The high concentration of adsorbed molecules of phenol at the interface decreases the interfacial tension, sigma, by about 18 mN/m, independently of the structure of the adsorbed phase and of the nature of the organic solvent.