Potentiostatic voltammetry and microelectrodes in the at spherical electrodes presence of product

An explicit analytical solution for the complete anodic-cathodic I-E-t response of a reversible electrode process in presence/absence of amalgamation under potentiostatic conditions is presented. To obtain this solution we have taken into account the electrode curvature, using in the case of amalgamation, Koutecky's approximation (i.e. the finite electrode volume has not been considered). Explicit expressions for the concentration profiles and the surface concentrations have been also deduced. All the results are applicable to electrodes of any radius including ultramicroelectrodes when both species are soluble in the electrolytic solution for any value of the ratio D-O/D-R. When amalgamation takes place, analytical results were compared with the numerical ones deduced by using the rigorous condition of null net flux in the electrode centre, pointing out that Koutecky's approximation remains valid even for electrode radius and time values at which the diffusion layer reaches the electrode centre. For high electrode sphericities the I-t Curves present it cross-linking for applied potential values higher than the equilibrium potential which is the cause of the appearance of a peak near to the anodic limit of the I-E curve. (c) 2008 Elsevier B.V. All rights reserved.