Ozonation of 2,6-, 3,4-, and 3,5-Dichlorophenol Isomers within Aqueous Solutions
Publication: Journal of Environmental Engineering
Volume 130, Issue 4
Abstract
The kinetics and mechanisms associated with the ozonation of 2,6-, 3,4-, and 3,5-dichlorophenols (DCPs) in aqueous solutions were studied. It was found that 2 moles of ozone are required for the initial degradation of 1 mole of DCP. The overall reaction between ozone and a DCP was found to be second order (first order per reactant). The overall reaction rate constants of all three DCPs increased with pH because of increased dissociation of the dichlorophenol molecules to dichlorophenoxide ions. Due to its high dissociation constant, 2,6-DCP is most reactive of the three with ozone with the overall reaction rate constants varying from to within the pH range of 2.0–4.0. Various chlorobenzenediols, chlorocyclohexadienediones, ketones, esters, and carboxylic acids were identified as intermediate and final ozonation products using gas chromatography/mass spectrometry analysis. The initial electrophilic addition of ozone at the ortho and para positions of the molecular and ionic forms is proposed as the likely mechanism for DCP ozonation.
Get full access to this article
View all available purchase options and get full access to this article.
References
Antonio, L., and Giampaolo, M.(1989). “pH variation during phenol biodegradation in mixed cultures of microorganisms.” Water Res., 23, 1335.
Bae, B., Autenrieth, R. L., and Bonner, J. S.(1995). “Kinetics of multiple phenolic compounds degradation with a mixed culture in a continuous-flow reactor.” Water Environ. Res., 67(2), 215.
Bailey, P. S. (1973). “Reactivity of ozone with various organic functional groups important to water purification.” Proc., 1st Int. Symp. on Ozone for Water and Wastewater Treatment, Washington, D.C., 101.
Birge, W. J., et al. (1979). “Toxicity of organic chemicals to embryo-larval stages of fish.” Rep. No. EPA-560/11-79-007, Cincinnati.
Dean, J. A. (1997). Lange’s handbook of chemistry, 14th Ed., McGraw-Hill, New York.
Decoret, C., Royer, J., Legube, B., and Dore, M.(1984). “Experimental and theoretical studies of the mechanism of the initial attack of ozone on some aromatics in aqueous medium.” Environ. Technol. Lett., 5, 207–218.
Espenson, J. H. (1981). Chemical kinetics and reaction mechanisms, 1st Ed., McGraw-Hill, New York.
Farhataziz, A., and Ross, B. (1977).“Selected specific rates of reactions of transients from water in aqueous solution: III. Hydroxyl radical and perhydroxyl radical and their radical ions,” U.S. Dept. of Commerce, National Bureau of Standards, Washington, D.C.
Gilbert, E. (1976). “Ozonolysis of chlorophenols and maleic acid in aqueous solution.” Proc., 2nd Int. Symp. on Ozone Technology, International Ozone Institute, Montréal, 253.
Gilbert, E. (1978). “Reactions of ozne with organic compounds in dilute aqueous solution: Identification of their oxidation products.” Ozone/chlorine dioxide oxidation products of organic materials, R. G. Rice and J. A. Cotruvo, eds., International Ozone Association, Cleveland, 227.
Hoigne, J., and Bader, H.(1976). “The role of hydroxyl radical reactions in ozonation processes in aqueous solutions.” Water Res., 10, 377–386.
Hoigne, J., and Bader, H.(1983). “Rate constants of reactions of ozone with organic and inorganic compounds in water—II. Dissociating organic compounds.” Water Res., 17, 175.
Huang, C. P., Dong, C., and Tang, Z.(1993). “Advanced chemical oxidation: Its present role and potential future in hazardous waste treatment.” Waste Management, 13, 361.
Kuo, C. H., and Huang, C. H.(1995). “Aqueous phase ozonation of chlorophenols.” J. Hazard. Mater., 41, 31–45.
Langlais, B., Reckhow, D. A., and Brink, D. R. (1991). Ozone in water treatment, Lewis, Boca Raton, Fla.
Li, K. Y. (1977). Dissertation, Mississippi State Univ. Mississippi State, Miss.
Li, K. Y., Weeks, J. L., and Kuo, C. H.(1979). “A kinetic study of ozone–phenol reaction in aqueous solutions.” AIChEJ, 25, 583.
McMurry, J. (1992). Organic chemistry, 3rd Ed., Brooks/Cole.
Minero, C., et al. (1995). “Formation of condensation products in advanced oxidation technologies: The photocatalytic degradation of dichlorophenols on ” Environ. Sci. Technol., 29, 2226.
Puhakka, J. A., Melin, E., Jarvinen, K., Tuhkanen, T., and Shieh, W. K.(1991). “Oxic fluidized bed treatment of dichlorophenols.” Water Sci. Technol., 24(3/4), 171.
Qiu, Y., Zappi, M. E., Kuo, C.-H., and Fleming, E. C.(1999). “Kinetic and mechanistic study of ozonation of dichlorophenols in aqueous solutions.” J. Environ. Eng., 125(5), 441–450.
Telford, M.(1974). “Blood glucose in crayfish. II. Variations induced by artificial stress.” Comp. Biochem. Physiol., 48A, 555.
Trapido, M., Veressinina, Y., Hentunen, J. K., and Hirvonen, A.(1997). “Ozonation of chlorophenols: kinetics, by-products and toxicity.” Environ. Technol., 18, 325.
U.S. Environmental Protection Agency (EPA). (1980a). “Ambient water quality criteria for chlorinated phenols.” Rep. No. EPA 440/5-80-032, Cincinnati.
U.S. Environmental Protection Agency (EPA). (1980b). “Ambient water quality criteria for 2,4-dichlorophenols.” Rep. No. EPA 440/5-80-042, Cincinnati.
Verschueren, K. (1983). Handbook of environmental data on organic chemicals, Van Nostrand Reinhold, New York.
Zheng, Y., and Kuo, C. K.(1996). “Kinetics and mechanism of the reaction between ozone and o-cresol in aqueous solutions.” Chem. Eng. Commun., 145, 33.
Information & Authors
Information
Published In
Copyright
Copyright © 2004 American Society of Civil Engineers.
History
Received: Aug 17, 2000
Accepted: Jul 24, 2002
Published online: Mar 15, 2004
Published in print: Apr 2004
Authors
Metrics & Citations
Metrics
Citations
Download citation
If you have the appropriate software installed, you can download article citation data to the citation manager of your choice. Simply select your manager software from the list below and click Download.