Effect of temperature on competitive adsorption of the solute and the organic solvent in reversed-phase liquid chromatography

In analysis of the temperature effect on chromatographic separations the influence of the adsorption of organic solvent on the retention properties of solute is generally not taken into account. In fact, adsorption behavior of solutes is strongly affected by competitive adsorption of organic solvents, which is temperature dependent. In this work changes of adsorption equilibrium of an organic solvent as well as a solute with temperature have been analyzed. Data of the excess adsorption of methanol from aqueous solutions on octadecyl-bonded silica have been acquired at different temperature. Experiments have been performed over a relatively narrow temperature range corresponding to typical chromatographic conditions, i.e., 10–50 °C. The competitive adsorption equilibria of model solutes (i.e., two homologous compounds: cyclopentanone and cyclohexanone) have been measured at different temperature and composition of the mobile phase. Temperature alterations to the retention properties were found to result from combined effects of changes in adsorption behavior of the organic solvent and of the solute. The influence of temperature on the separation selectivity has been considered.