THEORY OF CYCLIC VOLTAMMETRY FOR ELECTRODEPOSITION AND DISSOLUTION

A theory of cyclic voltammetry has been given, which includes the quantitative expressions of voltammogram for the following three reactions: (i) electrodeposition and dissolution on metal of the same kind, (ii) electrodeposition and dissolution on a foreign substrate, (iii) electrode reactions of complex ions. In each case, both the reversible and irreversible behavior is described. Generally, the peak reflecting back reaction of irreversible system is almost unnoticeable and has not been analyzed so far. However, by this newly developed theory, it turned out that the peak can appear at the potential far from the peak potential of the forward reaction. In some cases, the potential difference can be more than 1(V). By analysing of back and forward reaction peaks together, transfer coefficient alpha, numbers of electron n, reversibility parameter LAMBDA = K-degrees / square root D o nF-nu/RT, where k-degree, D o and nu-are standard rate constant, diffusion coefficient and scan rate of potential sweep, respectively, and standard potential E-degree can be determined separately.