The Abraham's solvation parameter model, based on linear solvation energy relationships (LSER), allows the accurate characterization of the selectivity of chromatographic systems according to solute-solvent interactions (polarizability, dipolarity, hydrogen bonding, and cavity formation). However, this method, based on multilinear regression analysis, requires the measurement of the retention factors of a considerably high number of compounds, turning it into a time-consuming low throughput method. Simpler methods such as Tanaka's scheme are preferred. In the present work, the Abraham's model is revisited to develop a fast and reliable method, similar to the one proposed by Tanaka, for the characterization of columns employed in reversed-phase liquid chromatography and particularly in hydrophilic interaction liquid chromatography. For this purpose, pairs of compounds are carefully selected in order to have in common all molecular descriptors except for a specific one (for instance, similar molecular volume, dipolarity, polarizability, and hydrogen bonding basicity features, but different hydrogen bonding acidity). Thus, the selectivity factor of a single pair of test compounds can provide information regarding the extent of the dissimilar solute-solvent interactions and their influence on chromatographic retention. The proposed characterization method includes the determination of the column hold-up volume and Abraham's cavity term by means of the injection of four alkyl ketone homologues. Therefore, five chromatographic runs in a reversed-phase column (four pairs of test solutes and a mixture of four homologues) are enough to characterize the selectivity of a chromatographic system. Tanaka's method is also analyzed from the LSER point of view.
Keywords: Chromatographic retention; Chromatographic selectivity; Column characterization; HILIC; Linear solvation energy relationships; Reversed-phase.
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