Reaction Mechanism for Chlorination of Urea

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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.