Role of halogen(i) cation-transfer mechanisms in water chlorination in the presence of bromide ion

Bromide ion is rapidly converted to HOBr via BrCl by reaction with HOCl. The subsequent slow reactions of (HOCl, OCl−)/(HOBr, OBr−) mixtures are monitored directly by multiwavelength UV–vis absorbance methods and simultaneously by ion chromatographic measurement of ClO2−, ClO3−, and BrO3− (p[H+] 5.6–7.6). A first-order loss of HOCl is observed which is catalyzed by trace concentrations of Br− and BrCl. Chlorite ion forms first and is subsequently oxidized to ClO3−. The loss of HOBr is slower and is second-order in HOBr, so that BrO3− formation takes longer than ClO3− formation. Under the conditions of this work, the relative yield of BrO3− increases with increase in pH. The decomposition of HOCl by bromide proceeds primarily by a series of halogen(I) cation-transfer reactions with subsequent halide release. The presence of HOCl increases the BrO3− yield three-fold from HOBr decay alone.