Space-charge polarization of a dilute electrolytic cell in the presence of diffuse double layers

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The frequency dependence of the complex dielectric constant due to space-charge polarization is analyzed for a dilute electrolytic cell with blocking electrodes in the presence of diffuse double layers. If the diffuse double layer is not generated by an external voltage application but induced by a contact potential difference between the electrode and electrolytic solution, the dielectric constant in Poisson’s equation does not include the contribution of the space-charge polarization. The space-charge polarization is measured by applying an external field. The external voltage source supplies positive and negative charges to the electrodes to keep the potential difference between the electrodes constant in the measurement. Accordingly, the dielectric constant in Poisson’s equation has to include the contribution of the space-charge polarization to take account of the external charges in the data analysis. An electrode polarization model developed with this concept can well explain the frequency-dependent behavior of the complex dielectric constant observed for the dilute electrolytic cell with the specific adsorption of ions to the electrodes.