A novel cellulose trisphenylcarbamate/1-octyl-3-methylimidazolium tetrafluoroborate [CTPC/[OcMIM]BF4] gas chromatographic stationary phase was prepared and characterized utilizing thermodynamic parameters and LSER methodology. The results revealed that the interaction model of each probe molecule on the CTPC/[OcMIM]BF4 stationary phase was invariable within the temperature range studied because of an excellent linear relationship between lnk and 1/T for each probe molecule. The chromatographic retentions of all probe molecules on the CTPC/[OcMIM]BF4 stationary phase were enthalpy-driven processes. The main interaction forces of the stationary phase with probe molecules are hydrogen bonding interactions, dispersive interactions and dipole–dipole interactions. Moreover, the contribution of each interaction is in the order of hydrogen bonding interaction > dispersive interaction > dipole–dipole interaction. The mixture of CTPC and [OcMIM]BF4 used as capillary gas chromatography stationary phase had high column efficiency and good film-forming ability, which was suitable for the separation of both nonpolar and polar compounds. Particularly the separation efficiencies of aromatic amines on CTPC/[OcMIM]BF4 are superior to those on the commercial SE-54 column.
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