Theory of square-wave voltammetry of electrode reaction followed by the dimerization of product

The influence of charge transfer kinetics and the rate of chemical reaction on square-wave voltammograms of electrode reaction followed by the dimerization of product is analyzed theoretically. The net peak potential is a linear function of the logarithm of reactant concentration if electrode reaction is reversible and the dimerization is either reversible, or totally irreversible. For the oxidation, the slopes of these relationships are −0.030 V and −0.022 V, respectively. Under the influence of electrode kinetics the linearity is lost. The relationship between net peak potential and the logarithm of frequency is linear either if electrode reaction is irreversible and the dimerization is reversible, or if electrode reaction is reversible and the dimerization is irreversible.

► Net peak potential depends on the logarithm of reactant concentration. ► Generally, this relationship is a curve tending to an asymptote. ► The relationship that is linear indicates that electrode reaction is reversible.