The Influence of Dielectric Decrement on Electrokinetics

We treat the dielectric decrement induced by excess ion polarization as a source of ion specificity and explore its impact on electrokinetics. We employ a modified Poisson-Nernst-Planck (PNP) equations accounting for the dielectric decrement. The dielectric decrement is determined by the excess ion polarization parameter α and when α = 0 the standard PNP model is recovered. Our model shows that ions saturate at large zeta potentials (ζ). Because of ion saturation, a condensed counterion layer forms adjacent to the charged surface, introducing a new length scale, the thickness of the condensed layer (l ). For the electro-osmotic mobility, the dielectric decrement weakens the electro-osmotic flow owing to the decrease of the dielectric permittivity. At large ζ, when α ≠ 0, the electro-osmotic mobility is found to be proportional to ζ/2, in contrast to ζ predicted by the standard PNP model. This is attributed to ion saturation at large ζ. In terms of the electrophoretic mobility M , we carry out both an asymptotic analysis in the thin-double-layer limit and solve the full modified PNP model to compute M . Our analysis reveals that the impact of the dielectric decrement is intriguing. At small and moderate ζ, the dielectric decrement decreases M with an increasing α. At large ζ, it is well known that the surface conduction becomes significant and plays an important role in determining M . It is observed that the dielectric decrement effectively reduces the surface conduction. Hence in stark contrast, M increases as α increases. Our predictions of the contrast dependence of the mobility on α at different zeta potentials qualitatively agree with experimental results on the dependence of the mobility among ions and provide a possible explanation for such ion specificity. Finally, the comparisons between the thin-double-layer asymptotic analysis and the full simulations of the modified PNP model suggest that at large ζ the validity of the thin-double-layer approximation is determined by l rather than the traditional Debye length.