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.

The possibility of calculation of volt-ampere curves in reversed electrode precess on flat electrodes for any values of Н and -0 parameters without demensions characterasing the nature of electrode process, electrode parameters, form and velocity of potential change within the time compared with real time of making experiment is shown. The magnitude Н shows the affect of relationship of electrochemical reaction rate defined by velocity of potential change, diffusion conditioned by interaction between molecules in the solutions (metallic, liquid) and a square of film thickness of electrode (anode process) or electrolyte (cathode process). The magnitude -0 shows the influence of relationship of electrochemical reaction rates depending on equilibrium potential.