A theory is developed of square-wave voltammetry of the system in which both the reactant and the product of a simple electrode reaction are initially present in the electrolytic solution. A net response of fast and reversible electrode reaction depends on the sum of concentrations of reactant and product. Under this condition the ratio of maxima and minima of the components of net response can be used for the calculation of the ratio of concentrations of reactant and product. If the electrode reaction is kinetically controlled, the net response may split in two peaks. The potentials of these peaks can be used for the determination of transfer coefficients.

Chemistry