TY - JOUR
T1 - Mechanism and kinetics of cyanogen chloride formation from the chlorination of glycine
AU - Na, Chongzheng
AU - Olson, Terese M.
PY - 2006/3/1
Y1 - 2006/3/1
N2 - 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 CNCl formation was limited by either the decay rates of N,N-dichloroglycine or a proposed intermediate, N-chloroiminocarboxylate, ClN=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 CNCl, 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: d[CNCl]f/dt = k2*[Cl2-Gly] T,oexp(-k2*t) where [Cl2-Gly] T,o is the initial concentration of total N,N-dichloroglycine, k 2* is the first-order decay constant for ClN=CHCO 2-, k2*(s-1) = 10 12(±4) exp(-1.0(±0.3) × 104/T), and T is the absolute temperature in K. Kinetic expressions for d[CNCl]/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.
AB - 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 CNCl formation was limited by either the decay rates of N,N-dichloroglycine or a proposed intermediate, N-chloroiminocarboxylate, ClN=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 CNCl, 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: d[CNCl]f/dt = k2*[Cl2-Gly] T,oexp(-k2*t) where [Cl2-Gly] T,o is the initial concentration of total N,N-dichloroglycine, k 2* is the first-order decay constant for ClN=CHCO 2-, k2*(s-1) = 10 12(±4) exp(-1.0(±0.3) × 104/T), and T is the absolute temperature in K. Kinetic expressions for d[CNCl]/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.
UR - http://www.scopus.com/inward/record.url?scp=33644869073&partnerID=8YFLogxK
U2 - 10.1021/es0512273
DO - 10.1021/es0512273
M3 - Article
C2 - 16568758
AN - SCOPUS:33644869073
VL - 40
SP - 1469
EP - 1477
JO - Environmental Science and Technology
JF - Environmental Science and Technology
SN - 0013-936X
IS - 5
ER -