Prediction of electrophoretic mobilities. 4. Multiply charged aromatic carboxylates in capillary zone electrophoresis

The electrophoretic mobilites of aromatic carboxylates and sulfonates at zero ionic strength were correlated with models incorporating both hydrodynamic and dielectric friction. The hydrodynamic friction was predicted using either the Hückel spherical ion model or the Perrin ellipsoidal model. Dielectric friction is the charge-induced drag caused by the reorientation of the solvent dipoles in response to the analyte charge. Based on the Hubbard-Onsager and Zwanzig expressions, the dielectric friction is related to z2/V. Expressions incorporating both the hydrodynamic and dielectric frictional terms successfully predicted infinite-dilution mobilities to within 4.4%. The influence of dielectric friction ranged from 3-8% of the overall drag for singly charged analytes to 39% of the total frictional drag for 1,2,4,5-benzenetetracarboxylate.