Solute–solvent interactions in micellar electrokinetic chromatography: Selectivity of lithium dodecyl sulfate–lithium perfluorooctanesulfonate mixed-micellar buffers

The solvation parameter model has been applied to the characterization of micellar electrokinetic chromatographic (MEKC) systems with mixtures of lithium dodecyl sulfate and lithium perfluorooctanesulfonate as surfactant. The variation in MEKC surfactant composition results in changes in the coefficients of the correlation equation, which in turns leads to information on solute–solvent and solute–micelle interactions. Lithium perfluorooctanesulfonate is more dipolar and hydrogen bond acidic but less polarizable and hydrogen bond basic than lithium dodecyl sulfate. Therefore mixtures of lithium dodecyl sulfate and lithium perfluorooctanesulfonate cover a very wide range of polarity and hydrogen bond properties, which in turn results in important selectivity changes for analytes with different solute properties.