On the application of Koutecky–Levich analysis to electrochemical processes involving metal complexes. 1. Theoretical background

The applicability of the Koutecky–Levich (KL) approach for the processes occurring in the systems of labile metal complexes is considered. According to the analysis of simulated RDE voltammograms, the use of classical KL relationships is possible if the predominant complexes are involved in the charge transfer process. In the opposite case, corrections to the initial voltametric data, taking into account the surface distribution of complexes and ligands, are required. The rationale and methodology for correction functions are presented. Inaccuracies in the estimation of kinetic and diffusion characteristics arising from ignoring the peculiarities of mass transfer of chemically interacting particles are analysed.