New insights on the retention mechanism of non-polar solutes in reversed-phase liquid chromatographic columns

Abstract

A clarification of the retention mechanism of non-polar solutes in octadecyl reversed-phase chromatographic columns is attempted based on a systematic comparison of the retention in C 18 and C 2 columns under the assumption that the retention in C 2 columns is due to adsorption. The comparison involves curve fitting procedures and tests based on the properties of special functions suggested in the present paper. For the application of this approach the retention behaviour of six non-polar solutes, benzene, toluene, ethylbenzene, propylbenzene, isopropylbenzene and tert-butylbenzene, is studied from aqueous mobile phases modified with methanol, isopropanol, acetonitrile and tetrahydrofuran using C 18 and C 2 reversed-phase columns. It was found that the retention mechanism in C 18 columns is not the same in the four modifiers. In particular, our results show that the adsorption mechanism has a significant contribution in mobile phases modified by acetonitrile and tetrahydrofuran, the partition mechanism is likely to predominate in isopropanol–water mobile phases provided that the mole fraction of isopropanol is higher than 0.2, whereas the case of MeOH is rather obscure, since the various tests did not give a clear picture about the retention mechanism in methanol–water mobile phases.