Methylparaben chlorination in the presence of bromide ions and ammonia: kinetic study and modeling

The impacts of chlorination on methylparaben (MP) removal, as well as of bromide and ammonia on the MP elimination kinetics, were studied. Bromide and ammonia react with chlorine and are promptly transformed into bromine and chloramines, respectively. Rate constants of chlorine, bromine, and monochloramine with MP were determined under different pH conditions. At pH 8.5, the apparent second-order rate constants of MP reactions with chlorine and bromine were found to be 3.37(±0.50) × 10¹ and 2.37 (±0.11) × 10⁶ M^-1.s^-1 for k_Chlorine/MP and k_Bromine/MP, respectively, yet there was low reactivity with monochloramine ([Formula: see text] = 0.045 M^-1.s^-1). Regarding chlorination and bromination, in order to gain further insight into the observed pH-dependence of the reaction, the elementary reactions were considered and the corresponding second-order rate constants were calculated. The experimental and modeled values were quite consistent under these conditions. Then, chlorination experiments with different bromide and/or ammonia concentrations were performed to assess the impact of inorganic water content on MP elimination and a kinetic model was designed to assess MP degradation. Under these conditions, MP degradation was found to be enhanced in the presence of bromide whereas it was inhibited in the presence of ammonia, and the overall impact was pH dependent.