Simulation of a non-stationary electrochemical process on rough electrodes under mixed kinetic-diffusion control
Abstract
Objectives: In this work, the effect of electrode surface roughness on the rate of a transient electrochemical process under mixed transport-kinetic control is established. A mathematical model of the electrochemical process occurring on an electrode with a rough surface and characterized by a different ratio of the rate constant of the charge transfer stage and the coefficient of non-stationary bulk diffusion is constructed.
Experimental: Using the numerical method of finite element modeling, chronoamperograms of a transient electrochemical process were obtained under conditions of mixed transport and kinetic control on electrodes with different surface profiles defined by harmonic and fractal functions. The transient “roughness function - time” curves are calculated and the boundaries of the transition region are determined, within which it varies from the roughness factor to unity. It is found that the shape of the chronoamperogram depends in a complex way both on the geometric characteristics of the rough surface and on the ratio of the diffusion-kinetic parameters of the process. With relatively short durations, the gross process rate is equal to the charge transfer rate at a given potential and is proportional to the roughness factor. With relatively long durations, the chronoamperogram transforms into a current decay curve of the diffusion-controlled process, while the effect of roughness is nonlinear in this case and manifests itself only with relatively short process durations. Under these conditions, the thickness of the diffusion layer is much smaller than the size of the irregularities, and the rate of the process on the rough electrode is proportional to the true surface area and roughness factor.
Conclusions: The position of the transition region depends on the value of the rate constant of the charge transfer: in the case of a slow kinetic stage, the transition manifests itself over increasingly long periods and gradually widens, while depending on the geometric shape of the irregularity.
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