Electrode process of mobile ions in generating space-charge polarization.

Abstract

Macroscopic dipole moments formed in electrolytic cells influence dielectric properties of the cells, and their magnitudes can be quantified by dielectric spectroscopy. We analyze the dielectric spectra observed for dilute electrolytic cells in low-frequency regions from two perspectives: space-charge polarization and diffuse double layers on the electrodes. The difference between the two polarization phenomena is characterized by the effective dielectric constant and the kinetic parameter introduced in the Poisson-Nernst-Planck model. The analytical results indicate that the generation of space-charge polarization is attributed to the kinetic process of mobile ions replacing solvent molecules on the electrode surface. This is an experimental confirmation of the formation process of macroscopic dipole moment due to space-charge polarization and its practical contribution to the dielectric constant of material.