The mechanism of monochloramine disproportionation under acidic conditions†
Monochloramine is a widely employed agent in water treatment technologies. However, its utilization has some drawbacks like the transformation of the active species into the undesired dichloramine. Although it is more pronounced in acidic solutions, the features of this reaction have still remained largely unexplored in the pH < 4 region. In this study the decomposition of monochloramine is examined under such conditions by using kinetic and computational methods. Fast kinetics measurements have convincingly showed that the disproportion into dicloramine is relatively fast and can be studied without any interference from side reactions. By varying the pH, the deprotonation constant of monochloramine has been determined by UV spectroscopy (Ka = 0.023 ± 0.005 M for I = 1.0 M NaClO4, and T = 25.0 °C). Dichloramine formation via monochloramine disproportion was found to follow second-order kinetics. The computations have provided the reaction mechanism and its free energy profile in accord with the proposed kinetic model. This involves the reaction between the protonated and unprotonated forms of monochloramine, with a rate constant k = 335.3 ± 11.8 M−1 s−1, corresponding to an activation free energy barrier of 14.1 kcal mol−1. The simulations predicted a barrier of 14.9 kcal mol−1 and revealed a key short-lived chlorine-bridged intermediate which yields dichloroamine and ammonium ion through a deprotonation-coupled chlorine shift.