Collect. Czech. Chem. Commun. 2005, 70, 133-153

Further Applications of Cyclic Voltammetry with Spherical Electrodes

Marién M. Moreno and Ángela Molina*

Departamento de Química Física, Facultad de Química, Universidad de Murcia, Espinardo, Murcia 30100, Spain


In this work we show analytical and easily manageable explicit equations corresponding to the application of any multipulse potential sequence to planar, spherical and cylindrical electrodes. We apply these expressions to study reversible charge transfer electrode processes in cyclic voltammetry with spherical electrodes, by considering that both members of the redox pair are initially present in solution, and showing that a conventional symmetrical sweep can be used under these conditions. These expressions allow study in depth fundamental aspects of cyclic voltammetry with spherical electrodes. Thus, in the cyclic voltammograms obtained for simple reversible processes with conventional spherical electrodes at different sweep rates, characteristic common points of non zero current (isopoints) appear from which unknown thermodynamic parameters of these systems can be easily determined. From these equations it can be predicted and demonstrated that there are important analogies of the I/E behavior between a simple reversible charge transfer reaction and a first-order catalytic process when any single or multipulse voltammetric transient techniques are applied.

Keywords: Cyclic voltammetry; Spherical electrodes; Catalytic mechanism; Multipulse potential sequence; Reversible charge transfer processes; Electrochemistry.

References: 22 live references.