Mathematical Interpretation of Aqueous‐phase Ozone Decomposition Rates
Publication: Journal of Environmental Engineering
Volume 115, Issue 3
Abstract
Experimental data and hypothetical process behavior are analyzed in an attempt to elucidate the kinetics of aqueous phase ozone decomposition reactions. Three commonly accepted mathematical techniques (integral, differential, van't Hoff) for the analysis of rate data are employed. The results indicate that when single‐order dependencies are used to model autocatalytic reactions, timevariable behavior of the rate constant and order is exhibited. This can partially explain existing controversy within the scientific community regarding the apparent order of ozone decomposition reactions. A simple autocatalytic rate expression is developed that accurately describes the decomposition rate data. The conclusions from the work have implications not only for development of an understanding of ozone decomposition kinetics, but for the analysis of rate data derived from nonelementary reactions in general.
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References
1.
Bader, J., and Hoigne, H. (1981). “Determination of ozone in water by the indigo method.” Water Res., 15, 449.
2.
Benson, S. W. (1960). The foundation of chemical kinetics. McGraw‐Hill Book Co., New York, N.Y.
3.
Buhler, R. E., Staehelin, J., and Hoigne, J. (1984). “Ozone decomposition in water studied by pulse radiolysis. 1. and as intermediates.” J. Phys. Chem., 88, 2560.
4.
Butt, J. B. (1980). Reaction kinetics and reactor design. Prentice‐Hall, Englewood Cliffs, N.J.
5.
Carberry, J. J. (1976). Chemical and catalytic reaction engineering. McGraw‐Hill Book Co., New York, N.Y.
6.
Chang, B. (1978). “A model study of ozone‐sparged vessels for the removal of organics from water,” thesis presented to the University of Illinois, at Champaign‐Urbana, Ill., in partial fulfillment of the requirements for the degree of Doctor of Philosophy.
7.
Chrostowski, P. C. (1981). Physical‐chemical mechanisms of reaction at ozone with aquatic humic substances, thesis presented to Drexel University, at Philadelphia, Penn., in partial fulfillment of the requirements for the degree of Doctor of Philosophy.
8.
Dawson, B. E. (1973). Kinetics and mechanisms of reactions. Methuen Publishing Co., London, Eng.
9.
Edwards, J. O. (1964). Inorganic reaction mechanisms, Benjamin Publishing Co., New York, N.Y.
10.
Endrenyi, L. (1981). Kinetic data analysis. Plenum Press, New York, N.Y.
11.
Flamm, D., and Anderson, S. (1975). “Iodate formation and decomposition in iodometric analysis of ozone.” Environ. Sci. Tech., 9, 660.
12.
Flamm, D. (1977). “Analysis of ozone at low concentrations with boric acid buffered KI.” Environ. Sci. Tech., 11, 978.
13.
Fogler, H. S. (1986). Elements of chemical reaction engineering. Prentice‐Hall, Englewood Cliffs, N.J.
14.
Forni, L., Bahnemann, D., and Hart, E. J. (1982). “Mechanism of hydroxide ion initiated decomposition of ozone in aqueous solution.” J. Phys. Chem., 86, 255.
15.
Frost, A. A., and Pearson, R. G. (1961). Kinetics and mechanisms. John Wiley and Sons, New York, N.Y.
16.
Fujikawa, E., Grasso, D., and Weber, Jr., W. J. (1986). “Ozone decomposition and mass transfer rates in treatment systems.” Annual WPCF Conference, Los Angeles, Calif.
17.
Grasso, D. (1987). Ozonation dynamics in water treatment: Antocatalytic decomposition, mass transfer, and impact on particle stability, thesis presented to the University of Michigan, at Ann Arbor, Mich., in partial fulfillment of the requirements for the degree of Doctor of Philosophy.
18.
Gurol, M. (1980). “Kinetic behavior of ozone in aqueous solution: Decomposition and reaction with phenol,” thesis presented to the University of North Carolina, at Chapel Hill, N.C., in partial fulfillment of the requirements for the degree of Doctor of Philosophy.
19.
Gurol, M., and Singer, P. C. (1982). “Kinetics of ozone decomposition: A dynamic approach.” Envir. Sci. and Tech., 16, 377.
20.
Haag, W. R., and Hoigne, J. (1984). “Kinetics and products of the reactions of ozone with various forms of chlorine and bromine in water.” Ozone Sci. Engrg., 6, 103.
21.
Hewes, C. G., and Davidson, R. R. (1971). “Kinetics of ozone decomposition and reaction with organics in water.” AIChE J., 17, 141.
22.
Hoigne, J. (1982). “Mechanisms, rates, and selectivities of oxidations of organic compounds initiated by the ozonation of water.” Handbook of Ozone Technology and Application, R. G. Rice and A. Netzer, eds., Ann Arbor Science, Ann Arbor, Mich.
23.
Hoigne, J., and Bader, H. (1985). “Rate constants of reactions of ozone with organic and inorganic compounds in water. III‐inorganic compounds and radicals.” Water Res., 17, 173.
24.
Hoigne, J., Staehelin, J., and Buhler, R. (1983). “Rates of reaction and decomposition of ozone in water: A few reasons for many misconceptions.” Sixth Ozone World Congress, Int. Ozone Association, Washington, D.C.
25.
Holcman, J., et al. (1982). “Formation of ozone in the reaction between the ozonide radical ion, and the carbonate radical ion, in aqueous alkaline solutions.” J. Phys. Chem., 86, 2069.
26.
Kuo, C. H., et al. (1977). “Absorption and decomposition of ozone in aqueous solutions.” AIChE Symposium Series, 73(166).
27.
Levenspiel, O., Weinstein, N. J., and Li, J. C. R. (1956). “A numerical solution to dimensional analysis.” Ind. Engrg. Chem., 48, 324.
28.
Perrich, J., et al. (1977). “Ozone disinfection and oxidation in a model ozone contacting reactor.” AIChE Symposium Series, 73, 225.
29.
Sehested, K., et al. (1984). “Formation of ozone in the reaction of OH with and the decay of the ozonide ion radical at pH 10–13.” J. Phys. Chem., 88, 269.
30.
Sheffer, S., and Esterson, G. L. (1982). “Mass transfer and reaction kinetics in the ozone/tap water system.” Water Res., 16, 383.
31.
Staehelin, J., and Hoigne, J. (1982). “Decomposition of ozone in water: Rate of initiation by hydroxide ions and hydrogen peroxide.” Environ. Sci. Tech., 16, 676.
32.
Staehelin, J., and Hoigne, J. (1985). “Decomposition of ozone in water in the presence of organic solutes acting as promoters and inhibitors of radical chain reactions.” Environ. Sci. Tech., 19, 1206.
33.
Swinborne, E. S. (1971). Analysis of Kinetic Data. Nelson Publishing Co., London, Eng.
34.
Sykes, A. G. (1966). Kinetics of Inorganic Reactions. Pergamon Press, London, Eng.
35.
Tomiyasu, H., Fukutomi, H., and Gordon, G. (1985). “Kinetics and mechanism of ozone decomposition in basic aqueous solution,” Inorg. Chem., 24, 2962.
36.
Walpole, R. E., and Myers, R. H. (1972). Probability and statistics for engineers and scientists. Macmillan, New York, N.Y.
37.
Weber, W. J., Jr. (1972). Physicochemical processes for water quality control. Wiley‐Interscience, New York, N.Y.
38.
Weston, R. E., and Schwarz, H. A. (1972). Chemical kinetics, Prentice‐Hall, Englewood Cliffs, N.J.
39.
Whitlow, J. E., and Roth, J. A. (1986). “Heterogeneous ozonation kinetics of pollutants in wastewater.” Proc., AIChE Summer Meeting, Boston, Mass.
40.
urteri, C., and Gurol, M. D. (1988). “Ozone consumption in natural waters: Effects of background organic matter, pH, and carbonate species.” Ozone Sci. Engrg., 10(3).
Information & Authors
Information
Published In
Journal of Environmental Engineering
Volume 115 • Issue 3 • June 1989
Pages: 541 - 559
Copyright
Copyright © 1989 ASCE.
History
Published online: Jun 1, 1989
Published in print: Jun 1989
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