Steady-state voltammetry for the reduction of labile metal complexes in the absence and presence of different concentrations of supporting electrolyte1

Steady-state voltammetry for the reduction of labile complexes of lead, cadmium and mercury, in the absence of deliberately added supporting electrolyte and with different concentrations of supporting electrolyte, has been studied at mercury (lead and cadmium) and platinum disc (mercury) microelectrodes. The effects of ionic strength and nature of an inert electrolyte on the migrational component, which usually adds to diffusion in the mass transport in solutions with low electrolyte, have been examined. The results obtained have demonstrated that the ratio of limiting current at different concentrations of supporting electrolyte to diffusive limiting current I_lm/I_ld, depended not only on the charge of the free ion, but also on the amount of labile complexes formed between the metal ion with ligands which may arise from the counter-ion accompanying the metal in its starting salt, from small amounts of supporting electrolyte and from the autoprotolysis of water, i.e., OH^?. Moreover, the I_lm/I_ld ratio is affected by the background electrolyte, which is almost unavoidable in water, and by the hydrolysis of the metal ion which yields protons. A comprehensive theoretical equation, based on already known treatments, has been also derived to predict the limiting current ratios in the presence of all the effects cited above.