The effect of partial charge transfer on the electrochemical turbulent noise

Abstract

Theoretical analysis of the effect of electrode potential on the spectral density of random alternating current emerged in electrochemical cell under the action of turbulent pulsations of the electrolyte solution velocity is carried out. An impedance model of metal electrode dissolution reaction, including two adsorption stages, is suggested, with allowance for the oxidized ion diffusion in electrolyte solution. It is known that in terms of the Ershler-Randles model, at low frequencies the experimentally measured slope of bilogarithmic frequency dependence of spectral density equals 3, which is characteristic of the diffusion control; at high frequencies the slope equals 4, which is characteristic of the kinetic control. It is shown that for the model of impedance of the two-stage adsorption oxidation process, in the middle segment of the spectrum the local slope must decrease down to 2, provided the first oxidation stage, which proceeds within the inner electrical double layer, is slow; the local slope must increase up to 6 (or 5, for diffusion control), provided the second oxidation stage (the partially oxidized ion desorption to solution) is slow. The “height” and “width” of the slope local changes appeared explicitly depending on the parameters of the partial charge transfer. This makes the turbulent noise method somewhat superior to the impedance method in the studying of the above-specified reaction type.