The use of microelectrodes for voltammetric investigations of the complexation equilibria at very low concentrations of supporting electrolyte allows the risk of competitive complexation or contamination to be avoided, makes the activities of the species involved closer to their concentrations (which facilitates comparisons with the spectroscopic results) and finally, allows the concentrations of the species to be varied over a broader range. This paper presents the calculations of the steady-state currents for a wide range of complexes that are inert on the experimental time scale, and reports the influence of the concentration of the electroinactive ionic species on the limiting currents. Also, for a number of cases the variation of halfwave potential with the ligand concentration, resulting from changes in the ohmic drop, is given. It is assumed that only one species (the complex or the uncomplexed form) is electroactive; if this is the complex, it may or may not change the number of ligands. The theoretical results were obtained either employing the Myland-Oldham theory extended in this paper or by digital simulation. The results of calculations show that the magnitude of the changes in the steady-state limiting current on complexation depends on the type of complexation equilibrium, the type of the change in the reactant charge number in the electrode process, and the complex formation constant. In a number of situations migrational effects are negligibly small and no special treatment is necessary, despite the lack of supporting electrolyte. In other cases, where migration is significant, the relations between the measured steady-state limiting current and the complex formation constant ß are given in the form of fitted equations that can be used to obtain ß from appropriate experimental data.
Palys, M. J., Stojek, Z., Bos, M., & van der Linden, W. E. (1997). Voltammetric investigation of the complexation equilibria in the presence of a low level of supporting electrolyte: Part 1: Steady-state current-potential curves for inert complexes. Analytica chimica acta, 337(1), 5-28. https://doi.org/10.1016/S0003-2670(96)00288-7