Theoretical model of voltammetry of selective dissolution of an alloy with accounting the effects of equilibrium solid-phase adsorption and surface roughness
Abstract
The problem of unsteady-state diffusion was numerically solved for potentiodynamic polarisation during the anodic selective dissolution of a binary homogeneous alloy. We considered the fractal and statistically irregular roughness of the electrode surface and the equilibrium solid-phase adsorption of the alloy’s system components. The concentration profiles of the electrochemically active component of the alloy, anodic polarisation curves, and roughness function were calculated. We determined that the effect of surface segregation does not affect the shape of the anodic voltammetry, does not change the criterion of diffusion kinetics, and is mathematically reduced to a change in the current strength proportional to the function of solid-phase adsorption. We revealed the role of fractal and statistically irregular roughness of the electrode in the criterion dependence of the maximum current strength on the potential scan rate. The voltammetry response depends linearly on the surface roughness factor at relatively high or very low potential scan rates. This dependence is caused by a significant change of the diffusion front from repeating the surface profile to a nearly flat shape. In these cases, the parabolic criterion of diffusion kinetics of voltammetry is not changed. The time dependences of the roughness function for surfaces with different roughness factors and fractal dimensions were obtained. We determined that an increase in these morphological parameters, as well as a decrease in the potential scan rate, increases the probability of the Randles-Sevcik dependence curvature. The obtained data can be used to develop a method of controlling the composition of alloy coatings, including those obtained by chemical or electrochemical deposition, as well as to estimate the roughness factors and fractal dimensions of their surface using unsteady-state electrochemical measurements.
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