Modeling of electrode polarization for electrolytic cells with a limited ionic adsorption.

Dilute electrolytic cells filled with chlorobenzene containing small amounts of tetrabutylammonium tetraphenylborate show anomalous dielectric dispersions in low-frequency regions. We propose a new model for electrode polarization in order to analyze the dielectric behavior of the dilute electrolytic cells. The model comprises two capacitive components: One is the space-charge polarization accompanied with a specific ionic adsorption on electrodes, and the other is the electrode capacitance which is brought about by an electronic spillover from the electrode surface. This model can primarily explain the anomalous frequency-dependent dielectric behavior of the electrolytic cells not only with low electrolyte concentrations, but also with high concentrations and can correctly describe the characteristics of the electrode polarization reflected in the dielectric spectra.