We analyze in which experimental conditions the concept of electrical impedance is useful for an electrolytic cell. The analysis is performed by solving numerically the differential equations governing the phenomenon of the redistribution of the ions in the presence of an external electric field and comparing the results with the ones obtained by solving the linear approximation of these equations. The control parameter in our study is the amplitude of the applied voltage, assumed a simple harmonic function of the time. We show that the bulk distribution of ions close to the electrodes differs from the one obtained by means of the linear analysis already for small amplitudes of the applied voltage. Nevertheless, the concept of electrical impedance remains valid. For larger amplitudes, the current in the circuit is no longer harmonic at the same frequency of the applied voltage. Therefore the concept of electrical impedance is no longer meaningful.
We analyze the influence of the adsorption of ions at the interfaces on the transient phenomena occurring in an electrolytic cell submitted to a steplike external voltage. In the limit of small amplitude of the applied voltage, where the equation of the problem can be linearized, we obtain an analytical solution for the bulk and surface densities of ions and for the electrical potential. We also obtain, in this limit, the relaxation time for the transient phenomena.
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