Cyclic multipulse voltammetric techniques. Part I: Kinetics of electrode processes

A comparative, theoretical and experimental, analysis of reversible and kinetically controlled electrode reactions by cyclic multi pulse voltammetry (CMPV), cyclic differential multi pulse voltammetry (CDMPV) and cyclic square-wave voltammetry (CSWV) is presented. The cyclic multipulse voltammetric techniques enable faster and more complete characterization of the electrode processes, comparing with classical multipulse voltammetric techniques. Electron transfer coefficients (α and β), i.e. symmetry of the electron transfer reaction can be estimated by visual inspection of the proper cyclic multipulse voltammogram. Their values, as well as the standard rate constant of a simple electrode reaction Ox + ne− ⇄ Red, can be determined from the slopes of linear dependences of characteristic (half wave or peak) cathodic and anodic potentials on the logarithm of pulse duration in CMPV and CDMPV, or logarithm of frequency in CSWV. The criteria for recognition of kinetically controlled electrode reactions by cyclic multipulse voltammetric techniques are given.