Enhanced oxidation of urea by pH swing during chlorination: pH-dependent reaction mechanism

Urea reacts with chlorine to form chlorinated ureas (chloroureas), and fully chlorinated urea (tetrachlorourea) is further hydrolyzed into CO₂ and chloramines. This study found that the oxidative degradation of urea by chlorination was enhanced by the pH swing, wherein the reaction proceeded under an acidic pH (e.g., pH = 3) in the first stage, and the solution pH was subsequently increased to a neutral or alkaline value (e.g., pH > 7) in the second-stage reaction. The degradation rate of urea by pH-swing chlorination increased with increasing chlorine dose and pH during the second-stage reaction. The pH-swing chlorination was based on the opposite pH dependence of sub-processes comprising urea chlorination. The formation of monochlorourea was favored under acidic pH conditions; however, the subsequent conversion into di- and trichloroureas was favored under neutral or alkaline pH conditions. The deprotonation of monochlorourea (pK_a = 9.7 ± 1.1) and dichlorourea (pK_a = 5.1 ± 1.4) was suggested to be responsible for the accelerated reaction in the second stage under increased pH conditions. pH-swing chlorination was also effective in degrading urea at low concentrations (micromolar levels). In addition, the total nitrogen concentration significantly decreased during the degradation of urea because of the volatilization of chloramines and the release of other gaseous nitrogen compounds.