Mathematical Model of the Catalytic Effect of Chromium(VI) on Hypochlorite Disproportionation in Chlorate Electrolysis

The effect of chromium(VI) on the kinetics of disproportionation of hypochlorous acid and hypochlorite was established in the solution for the electrolytic production of chlorate. The hexavalent chromium species Cr2O7 2-, HCrO4 - and CrO4 2- present in the solution catalyze the disproportionation reaction. In both the absence and presence of chromium(VI), disproportionation is a third-order reaction with respect to HClO and ClO-P, and a first-order reaction with respect to the hexavalent chromium species. In the presence of chromium(VI) ions, four parallel reactions probably take place in the solution i.e. uncatalyzed disproportionation and three parallel reactions catalyzed by Cr2O7 2-, HCrO4 - and CrO4 2-ions. Most likely, the hexavalent chromium species do not change the sequence of elementary reactions in the disproportionation mechanism but only speed up the rate-determining step through interaction with its reactants. In the chlorate production process, as chromium(VI) concentration increases, the optimum pH which ensures the maximum rate of disproportionation is shifted to an acid environment. This is due to an increase in the concentration of the catalytically most active species HCrO4 - with increasing acidity of the solution. A mathematical model of the kinetics of the chromium(VI)-catalyzed disproportionation of hypochlorite and hypochlorous acid into chlorate was set up. Good agreement was obtained between theoretical and experimental data. © 2018 The Electrochemical Society. This is the peer-reviewed version of the paper: Spasojević, M., Marković, D., Trišović, T., Spasojević, M., 2018. Mathematical model of the catalytic effect of chromium(VI) on hypochlorite disproportionation in chlorate electrolysis. Journal of the Electrochemical Society 165, E8–E19. [https://doi.org/10.1149/2.0291802jes]