Kinetic study of the reactions between chloramine disinfectants and hydrogen peroxide: Temperature dependence and reaction mechanism

The temperature-dependent kinetics for the reaction between hydrogen peroxide and chloramine water disinfectants (NH2Cl, NHCl2, and NCl3) have been determined using stopped flow-UV/Vis spectrophotometry. Rate constants for the mono- and dichloramine-peroxide reaction were on the order of 10-2 M-1 s(-1) and 10(-5) M-1 s(-1), respectively. The reaction of trichloramine with peroxide was negligibly slow compared to its thermal and photolytically-induced decomposition. Arrhenius expressions of ln(KH202-NH2Cl) = (17.3 +/- 1.5)-(51 500 +/- 3700)/RT and ln(k(H202-NHCl2)) = (18.2 +/- 1.9)-(75800 +/- 5100)/RT were obtained for the mono- and dichloramine peroxide reaction over the temperature ranges 11.4-37.9 and 35.0-55.0 degrees C, respectively. Both monochloramine and hydrogen peroxide were first-order in the rate-limiting kinetic step and concomitant measurements made using a chloride ion selective electrode showed that the chloride was produced quantitatively. These data will aid water utilities in predicting chloramine concentrations (and thus disinfection potential) throughout the water distribution system. (C) 2013 Elsevier Ltd. All rights reserved.