Mechanism and kinetics of cyanogen chloride formation from the chlorination of glycine

Glycine is an important precursor of cyanogen chloride (CNCl)--a disinfection byproduct (DBP) found in chlorinated drinking water. To model CNCl formation from glycine during chlorination, the mechanism and kinetics of the reaction between glycine and free chlorine were investigated. Kinetic experiments indicated that CNCI formation was limited by either the decay rates of N,N-dichloroglycine or a proposed intermediate, N-chloroiminocarboxylate, CIN=CHCO2-. Only the anionic form of N,N-dichloroglycine, NCl2CH2CO2-, however, decays to form CNCl, while the protonated neutral species forms N-chloromethylimine. At pH > 6, glycine-nitrogen is stoichiometrically converted to CNCI, while conversion decreases at lower pH due to the formation of N-chloromethylimine. Under conditions relevant to drinking water treatment, i.e., at pH 6 to 8 and with free chlorine in excess, a simplified rate expression for the concentration of glycine-nitrogen converted to CNCl, CNCl]f, applies: dt/dCNCl]f = k2*Cl2-Gly](T,o)exp(-k2*t) where Cl2-Gly]T,o is the initial concentration of total N,N-dichloroglycine, k2* is the first-order decay constant for CIN=CHCO2-, k2*(s(-1)) = 10(12)(+/-4) exp(-1.0(+/-0.3) x 10(4)/T), and T is the absolute temperature in K. Kinetic expressions for dCNCl]/dt when free chlorine is in excess, however, must also account for the significant decay of CNCl by hypochlorite-catalyzed hydrolysis, which has been characterized in previous studies. Although CNCl formation is independent of the free chlorine concentration, higher chlorine concentrations promote its hydrolysis.