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Abstract
In this work, we investigated the intermolecular interaction between the stationary phases and solutes and retention behavior in liquid chromatography by thermodynamic analysis. The intermolecular interactions between four stationary phases chemically bonded with octadecyl (ODS), phenyl (Ph), pyrenyl (PYE), and β‐cyclodextin bromide (β‐CD), and 53 solutes including 27 compounds of p‐substituted alkylbenzenes (PSABs), 14 compounds of polyaromatic hydrocarbons (PAHs), and 26 compounds of substituted benzenes were examined by using both methanol–water and acetonitrile–water as mobile phases. It has been observed that there are obvious differences in π–π intermolecular interactions among the stationary phases of ODS, Ph, and PYE by plotting ln k′ with enthalpies (ΔH). Based on the thermodynamic analysis on the interaction between β‐CD column and solutes, it was known that the solutes having similar molecular lengths with β‐CD resulted in large enthalpy changes in the host–guest interaction. Besides, both hydrophobic and host–guest interactions make contributions to the retention of solutes on the β‐CD stationary phase; and the structures of solutes have critical influence on the retention. Further, from the thermodynamic point of view, the retention mechanisms such as partitioning or adsorption in liquid chromatography have been discussed.