Reaction mechanism for chlorination of urea.
Experiments were conducted to elucidate the mechanism of the reaction between free chlorine and urea. In combination with findings of previous investigations, the results of these experiments indicate a process by which urea undergoes multiple N-chlorination steps. The first of these steps results in the formation of N-chlorourea; this step appears to require Cl₂ to proceed and is the overall rate-limiting step in the reaction for conditions that correspond to most swimming pools. N-Chlorourea then appears to undergo further chlorine substitution; the fully N-chlorinated urea molecule is hypothesized to undergo hydrolysis and additional chlorination to yield NCl₃ as an intermediate. NCl₃ is hydrolyzed to yield NH₂Cl and NHCl₂, with subsequent decay to stable end products, including N₂ and NO₃⁻. Conversion of urea-N to nitrate is pH-dependent. The pattern of nitrate yield is believed to be attributable to the fact that when urea serves as the source of reduced-N, entry into the reactions that describe chlorination of ammoniacal nitrogen is through NCl₃, whereas when NH₃ is the source of reduced-N, entry to these reactions is through NH₂Cl.
Blatchley
Ernest R
ER
School of Civil Engineering and Division of Environmental & Ecological Engineering, Purdue University, West Lafayette, Indiana 47907-2051, USA. blatch@purdue.edu
Cheng
Mingming
M
D054879:Halogenation; D007700:Kinetics; D013551:Swimming Pools; D014508:Urea / Q000737:chemistry*; D014867:Water / Q000737:chemistry; D018508:Water Purification
D014867:Water; D014508:Urea