Evolution of Anolyte Composition in the Oxidative Electrolysis of Sodium Bromide in a Sulfuric Acid Medium

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The oxidation of a 10 mM aqueous solution of sodium bromide in a sulfuric acid medium on the surface of a platinum electrode in a cell with separated spaces was studied. The process is important in view of the use of the bromine–bromide redox couple in redox flow batteries. The study was performed by cyclic voltammetry, potentiostatic chronoamperometry with optical absorption spectrum recording, and measurements of the potential of the redox reference electrode. A numerical procedure for processing the experimental spectra of the solution was developed to separate them into the spectrum of molecular bromine and the residual signal. The latter was attributed to the absorption of the tribromide anion based on the literature data. The experimental dependences of the Br₂ and Br₃^- concentrations for the oxidative electrolysis of the NaBr solution in the sulfuric acid medium agreed well with the theoretical predictions. The current efficiency of bromine formation was evaluated.