Evolution of the Bromate Electrolyte Composition in the Course of Its Electroreduction inside a Membrane–Electrode Assembly with a Proton-Exchange Membrane

The passage of cathodic current through the acidized aqueous bromate solution (catholyte) leads to a negative shift of the average oxidation degree of Br atoms. It means a distribution of Br-containing species in various oxidation states between −1 and +5, which are mutually transformed via numerous protonation/deprotonation, chemical, and redox/electrochemical steps. This process is also accompanied by the change in the proton (H(+)) concentration, both due to the participation of H(+) ions in these steps and due to the H(+) flux through the cation-exchange membrane separating the cathodic and anodic compartments. Variations of the composition of the catholyte concentrations of all these components has been analyzed for various initial concentrations of sulfuric acid, c(A)(0) (0.015–0.3 M), and two values of the total concentrations of Br atoms inside the system, c(tot) (0.1 or 1.0 M of Br atoms), as functions of the average Br-atom oxidation degree, x, under the condition of the thermodynamic equilibrium of the above transformations. It is shown that during the exhaustion of the redox capacity of the catholyte (x pass from 5 to −1), the pH value passes through a maximum. Its height and the corresponding average oxidation state of bromine atoms depend on the initial bromate/acid ratio. The constructed algorithm can be used to select the initial acid content in the bromate catholyte, which is optimal from the point of view of preventing the formation of liquid bromine at the maximum content of electroactive compounds.