Kinetics and mechanism of degradation of p-chloronitrobenzene in water by ozonation

Abstract

The kinetics and mechanism of p-chloronitrobenzene ( pCNB) degradation by ozone were investigated. With reference compounds, nitrobenzene (NB) and chlorobenzene (CB), reaction rate constants of pCNB with O 3 and OH were measured by means of competition kinetics (mixtures of pCNB and NB, or pCNB and CB), with the rate constants being, 1.6 L mol −1 s −1, 2.6 × 10 9 L mol −1 s −1, respectively. During the ozonation process of pCNB, an increase of chloride and nitrate ions in the water sample solution was observed, which is consistent with the decrease in pCNB concentration. But the total organic carbon (TOC) removal rate is not consistent with the pCNB elimination rate indicating only part of pCNB was mineralized and thus presumably some intermediate products were formed. The pCNB degradation intermediate products were analyzed by gas chromatography–mass spectrometry (GC–MS), liquid chromatography–mass spectrometry (LC–MS), high performance liquid chromatography (HPLC) and ion chromatography (IC). The main intermediate products were phenol, p-chlorophenol, p-nitrophenol, 2-chloro-5-nitrophenol, 5-chloro-2-nitrophenol, 5-nitro-catechol, para-benzoquinone, 5-nitro-1,2,3-trihydroxy phenol, trihydroxy semiquinone, glycolic acid, oxalic acid, hydroxybutanoic acid, mesoxalic acid, tartrouic acid, malonic acid, maleic acid, hydroxymalonic acid, tartaric acid, malic acid, ketoglutaric acid and muconic acid. From the identified reaction products, a possible degradation pathway for the ozonation of pCNB has been proposed.