Abstract
The low-frequency diffusion-migration impedance and the effect of non-linearity on the validity of impedance measurements of electrochemical cells constituted by a binary electrolyte solution placed between two asymmetric boundaries, i.e., the cation being the electroactive species at one electrode and the anion the electroactive species at the other, has been examined in detail. Ionic transport processes are prescribed from the Nernst-Planck flux equations, the electrical neutrality condition in the electrolyte solution and the Donnan equilibrium relations at the electrode-solution reversible interfaces. An analytical expression in closed form for the impedance of such a system has been rearranged to include asymmetric electrolytes. The properties of the impedance, with special emphasis in the characteristic frequency of the impedance plots, are analyzed and discussed. An original study of the harmonic response for the current electric of an asymmetric cell to a perturbing sine potential has been also reported. The higher-order harmonics, the total harmonic distortion, the first harmonic impedance and the waveforms, are originally studied by using the network simulation method. New results emerge in relation with the features of the first harmonic impedance and the waveforms under non-linear conditions.
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