Test of Hubbard–Onsager’s dielectric friction theory for ion migration in mixed solvents. II. Dioxane–water systems

Hubbard–Onsager’s (HO) dielectric friction theory for the limiting ionic conductance is tested for various monovalent ions in solvent mixtures of dioxane and water by taking the residual friction coefficient which is defined as the overall friction coefficient subtracted by the Stokes friction coefficient for slip. The HO theory combined with the bulk solvent properties is successful in predicting the ion size and solvent composition dependencies of the residual friction coefficients Δζ for the alkali metal and halide ions except in the dioxane-rich region. The HO theory works much better than the early dielectric friction theory by Zwanzig because the effect of the coupling of the viscous and dielectric frictions on the velocity field is neglected in the latter theory. It turns out that the HO theory serves an important theoretical framework for the interpretation of the limiting ionic conductances experimentally obtained.