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Applications of the solvation parameter model in thin-layer chromatography

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Abstract

The limited capability of the solvation parameter model to describe retention for silica gel layers and columns is possibly due to problems in separating out the simultaneous contributions of solute and solvent adsorption interactions to the experimental retention property (logk or RM) as well as possible limitations of the descriptors employed by the model to represent interactions at the adsorbent surface. The heterogeneous energy distribution of adsorption sites that result in site-specific interactions and the steric requirements associated with immobile sites for solute adsorption in the preferred configuration at the adsorbent surface are not easily handled for varied compounds. The separate solute, S°, and solvent adsorption parameters, ε°, of the competition model can be modeled independently with reasonable success, so to the experimental values of the solute adsorption cross-sectional area, AS. On the other hand, the definitions of S° and AS in the competition model are difficult to reconcile with their properties indicated by the solvation parameter model. This suggests co-mingling of solute and solvent properties among the main parameters of the competition model leading to additional uncertainty in model predictions for varied compounds. The reduction in the contribution of site-specific and steric interactions to the retention mechanism for reversed-phase separations on chemically bonded layers together with the formation of a more extensive solvated interphase region provides a more favorable fit of the solvation parameter model for both layers and columns. These models emphasize the importance of water in the mobile phase and the general contributions of mobile phase interactions on the retention mechanism. In addition, the selected solvation of the stationary phase in contact with the mobile phase makes an important contribution to system selectivity. System maps are developed to provide insight into the contribution of individual intermolecular interactions to the retention mechanism for a wide range of mobile phase compositions. Correlation diagrams constructed from the system constants facilitate the comparison of selectivity for different layers with the same mobile phase composition or different mobile phase compositions for the same layer. These visual tools provide an objective mechanism for the evaluation of differences in selectivity and the identification of systems of equivalent selectivity.

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    Colin F. Poole

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Poole, C.F. Applications of the solvation parameter model in thin-layer chromatography. JPC-J Planar Chromat 35, 207–227 (2022). https://doi.org/10.1007/s00764-022-00156-6

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