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Kinetic and Mechanistic Study of Ozonation of Three Dichlorophenols in Aqueous Solutions
Authors:Yongqiang Qiu  Mark E Zappi  Chiang-Hai Kuo  Elizabeth C Fleming
Affiliation:1Member, ASCE,
21Dept. of Chemical Engrg., Mississippi State Univ., Mississippi State, MS 39762.
32Dept. of Chemical Engrg., Mississippi State Univ., Mississippi State, MS; corresponding author. E-mail: Zappi@Che.MsState.Edu
43Dept. of Chemical Engrg., Mississippi State Univ., Mississippi State, MS.
54Envir. Lab., U.S. Army Engrs. Waterways Experiment Station, 3909 Halls Ferry Rd., Vicksburg, MS 39180.
Abstract:This research investigates the kinetic parameters associated with the ozonation of 2,3-, 2,4-, and 2,5-dichlorophenols (DCPs) in aqueous solutions at 25°C. The overall ozonation kinetics of each DCP was found to be first order with respect to each reactant concentration (i.e., DCP and ozone). Among the three isomers studied, the ozonation of 2,5-DCP was the fastest with the overall rate constant varying from 68,500 to 7,750,000 M?1 s?1 within a pH range of 2.1 to 5.0. The overall rate constant increased with pH because of the increase in the degree of dissociation of the DCP molecules to dichlorophenoxide ions. The electrophilic addition of ozone at the ortho and para positions of the molecular and ionic forms of the DCPs was postulated to be the likely mechanism for the degradation of the DCPs to chlorobenzenediols, monochlorophenols, chlorocyclohexadienediones, ethylacetate, heptanone, carboxylic acids, and other by-products that were detected using gas chromatograph∕mass spectrometry analysis.
Keywords:
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