Theory of cyclic voltammetry at the mercury film electrode: Reversible case with substrate initially present in the mercury phase

The theory of cyclic voltammetry has been developed for a case describing the behaviour of a reversible system at the mercury film electrode with a metal present initially in the mercury phase. Theoretical results are presented in the form of a simple equation coupled with a set of the calculated current function values. In addition, several simple relationships are given for the parameters characterizing the cyclic curves. The rapid exhaustion of the metal from the mercury film and the generation of the metal ions into the solution free of metal ions offer better conditions for the resolution of adjacent peaks than those existing in cyclic voltammetry at the HMDE and at the MFE with substrate present initially in solution. Theoretical predictions were compared with experimental results obtained for lead and thallium at the silver-based mercury film electrode.