Unified treatment of the potentiostatic reduction on an expanding mercury electrode of complexes at any concentration ratio of reacting species

Abstract

The article describes a general treatment of voltammetry of equilibrium complexation reactions at an electrode expanding in accord with any power law, the stationary electrode and the dropping mercury electrode being special cases. Reversible, irreversible and quasireversible electrode reactions are embraced by the treatment. A general expression for the current—voltage characteristic was derived, which was applied to the case of the polarographic reduction of complex ion, where either the simple or complex ion is electrochemically active. An equation accounting for the surface concentration of all reacting species is derived, the solution of which under appropriate conditions gives the equations of Lingane, Matsuda and Ayabe, etc. Correlations of potential, current and wave shape with complexing agent concentration are presented and discussed. A criterion for the splitting of the polarographic wave in the absence of excess of the complexing agent is proposed. Experimental results of several papers are discussed in the light of these criteria and a satisfactory agreement between the results and the predictions is established.