Liquid chromatographic capacity factors (k') were measured for thirty two compounds including alkanes, aromatic hydrocarbons, esters, ketones and alcohols in an octadecyl bonded silica gel (ODS)/ (methanol-water) system. The k' of each compound was compared with the partition coefficient (P) in the liquid-liquid system consisting of dodecane and the methanol-water of a composition identical to that used in the chromatography (the molar fraction of methanol in the mixture, 0.4 -1.0).A ratio, k'/ P, increased with decrease in P. The k'/ P ratio of a relatively polar compound was noticeably affected by the composition of methanol-water.The energy difference in the solute-solvent interactions occurring in the methanol-water phase and in the dodecane phase was estimated using the scaled particle theory. It was found that the more strongly a solute interacted with a polar solvent, such as methanol and/ or water, than a nonpolar solvent such as dodecane, the more easily the solute transfer tended to occur from the polar phase to the ODS phase rather than to the dodecane phase.
KeywordsReversed-phase liquid chromatography, retention, capacity factor, partition coefficientReversed phase (RP) separation mode with an alkylbonded stationary phase is widely used in high performance liquid chromatography (HPLC). It is applied to a variety of compounds with a polar solvent or solvent mixture, e.g. methanol-water, as the mobile phase. The alkyl group bonded to a stationary matrix contributes to the retention of sample compounds in the stationary phase. Various surface-modified silica gels with different lengths of alkyl chains were 1 2 The most popular bonded-phase for RP-HPLC, today, is octadecyl-bonded silica gel (ODS). The general trend of RP separation is: the more the hydrophobicity of a compound, the more strongly it is retained on the stationary phase.Solute distribution in the RP mode has been discussed from various viewpoints, such as the partition between the alkyl moiety of a stationary phase and the mobile phase used3, the solvophobic adsorption on the alkylated surface of the stationary phase4 and a combined function of the partition and the adsorption.5 And also the contribution of the organic solvent extracted from the mobile phase with the alkyl moiety of the stationary phase was suggested.6 The solute retention mechanism in an RP system and the physical properties of alkylbonded phase were studied by many investigators. However, some problems to be clarified much more still remain.The relationship between the capacity factor in reversed phase liquid chromatography and the partition coefficient in liquid-liquid systems, such as octanol/ water7'8 and hexadecane/ (methanol-water)9, has been studied by many investigators. Many such studies tend to apply such a relationship to characterizing compounds with regards to quantitative-structure-activity relationship. 10,11In our approach to elucidation of the characteristics of an alkyl-bonded phase, a liquid alkane was taken as the reference material with which the alky...