Anode current on gold in mixed thiosulfate-sulfite electrolytes

The anodic current in individual and mixed thiosulfate-sulfite solutions was studied by means of voltammetry on a fresh gold RDE surface. An unexpected result was obtained: a new additional current maximum appears on the anodic voltammogram in mixed solutions; it is not observed in the individual solutions of sodium thiosulfate and sulfite. The reasons for, and mechanism associated with, this phenomenon require separate and detailed investigation. It is shown that the rate of the anodic process in sulfite solutions is limited by diffusion of discharging particles, while the rate of the anodic process in thiosulfate solutions is limited by slow (in comparison with diffusion) heterogeneous reactions. In mixed solutions, the presence of thiosulfate causes partial passivation of the electrode, while the presence of sulfite causes its partial depassivation. It is stressed that the initial stages of oxygen evolution on gold have opposite effects on anodic currents in sulfite and thiosulfate solutions. (C) 2014 Elsevier Ltd. All rights reserved.