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Journal of Physical Chemistry B, Vol.101, No.30, 5875-5888, 1997
Solvophobic Theory and Normalized Free-Energies of Nonpolar Substances in Reversed-Phase Chromatography
A simplified version of the solvophobic theory is employed to reexamine a large set of retention data with nonpolar and weakly polar eluites in reversed phase chromatography (RPC) to test certain predictions by the theory and to clarify further the roles of the mobile and the stationary phase in the retention process. The free energy of retention in RPC is expressed in terms of the nonpolar surface area of the eluite, the pertinent interfacial tensions, and the energetics of eluite-stationary phase interactions in the gas phase. Within this framework changes in retention free energy per unit water accessible nonpolar surface area are evaluated in the entire range of the organic modifier concentration by using thermodynamic data for the retention of nonpolar eluites on alkyl silica bonded phase in gas chromatography and for the transfer of nonpolar solutes from the hydroorganic solvent to the gas phase. The normalized retention free energy parameters thus obtained according to the theory are in excellent agreement with those evaluated from experimental retention data using methanol, acetonitrile, tetrahydrofuran, and 2-propanol as organic modifiers in RPC. Furthermore, these parameters are found to be the same from column to column for a particular stationary phase and therefore characterize the RPC retention process. Analysis of experimental retention data obtained with various bonded phases indicates that the stationary phase chain length has a much smaller effect on the changes in selectivity of nonpolar aliphatic eluites than the mobile phase concentration. The results demonstrate the usefulness of the solvophobic theory for the evaluation of physicochemical parameters associated with retention of hydrocarbonaceous eluites in RPC and confirm the dominant role of the mobile phase in governing the retention and selectivity changes in RPC of nonpolar eluites.
Keywords:PERFORMANCE LIQUID-CHROMATOGRAPHY;ENTHALPY-ENTROPY COMPENSATION;CHEMICALLY BONDED PHASES;DILUTE AQUEOUS-SOLUTIONS;CAVITY SURFACE-AREA;HOMOLOGOUS SERIES;HYDROPHOBIC-INTERACTION;PARTITION-COEFFICIENTS;PERFLUOROALKANOATE ESTERS;TEMPERATURE-DEPENDENCE