Introduction of effective dielectric constant to the Poisson-Nernst-Planck model.

The Poisson-Nernst-Planck (PNP) model has been widely used for analyzing impedance or dielectric spectra observed for dilute electrolytic cells. In the analysis, the behavior of mobile ions in the cell under an external electric field has been explained by a conductive nature regardless of ionic concentrations. However, if the cell has parallel-plate blocking electrodes, the mobile ions may also play a role as a dielectric medium in the cell by the effect of space-charge polarization when the ionic concentration is sufficiently low. Thus the mobile ions confined between the blocking electrodes can have conductive and dielectric natures simultaneously, and their intensities are affected by the ionic concentration and the adsorption of solvent molecules on the electrodes. The balance of the conductive and dielectric natures is quantitatively determined by introducing an effective dielectric constant to the PNP model in the data analysis. The generalized PNP model with the effective dielectric constant successfully explains the anomalous frequency-dependent dielectric behaviors brought about by the mobile ions in dilute electrolytic cells, for which the conventional PNP model fails in interpretation.