A theory of square-wave voltammetry of surface-active, electroinactive compounds

A potential-dependent adsorption of electroinactive species on the surface of working electrode is investigated theoretically for square-wave voltammetry (SWV). It is demonstrated that the tensammetric peak originates from the difference in surface coverage during the forward and backward series of pulses of SWV signal. Linear dependence of SWV net peak current on SW frequency, as well as of SWV net peak potential on dimensionless bulk concentration of reactant and Frumkin coefficient is predicted by the model.