Theory of the reversible electrode process in case of cyclic voltammetry at finite thickness film electrode

In this report the theory of the reversible process of amalgam formation and dissolution reaction at a mercury film electrode of different thickness is developed using an additional boundary condition approach for asymmetrical diffusion. The profile of the entire voltammetric peak is simulated using a wide range of values of the parameter H=lσ/D (where l is the film thickness, σ = nFW/RT, D is diffusion coefficient, n is number of electrons, W is scan rate, and F and R are the Faraday and Universal gas constants, respectively) from 20 to 0.001. In addition the influence of the initial potential Ei and the switching potential Eλ is included in the calculations. The dependence of the anodic and cathodic peak currents, peak potentials and half-height-full-widths on the initial potential, Ei, and the value of lnH, are described using approximate equations; the dependence of the ratio of peak currents and peak-to-peak separation on the switching potential Eλ and value of lnH, using cyclic voltammetry are also described.