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Type of Document	Dissertation
Author	Lesko, Timothy Michael
URN	etd-04262004-184449
Persistent URL	http://resolver.caltech.edu/CaltechETD:etd-04262004-184449
Title	Chemical effects of acoustic cavitation
Degree	PhD
Option	Chemistry
Advisory Committee	Advisor Name Title Vincent McKoy Committee Chair Jacqueline Barton Committee Member Michael Hoffmann Committee Member Nathan Lewis Committee Member
Keywords	hydrogen peroxide ozonolysis sonolytic degradation ultrasonic irradiation radicals peroxone
Date of Defense	2004-04-21
Availability	unrestricted
Abstract A novel high-frequency, high-power, pilot-plant scale sonochemical reactor was developed and used to study the degradation of organic pollutants in aqueous solutions. The degradation rates of trichloroethylene, dichloromethane, and phenol were found to exceed those of similar frequency, small-scale bench reactors by factors ranging from 2.5 to 7. Experiments with 10 micromolar methyl orange in the large reactor operating at different total volumes exhibited a linear dependence between the observed sonolytic rate constants and the applied power density. Likewise, steady-state OH-radical (aq) in each reactor were calculated and shown to correlate with the applied power density in the vessel. The sonochemical decomposition of phenol was further studied in a bench-scale ultrasound reactor combination with ozonolysis. The addition of ozone during sonication did not affect the first-order degradation rate constants of phenol compared to the linear combination of separate sonication and ozonation experiments. However, enhancement of the degradation rates of the total organic carbon (TOC) by 43% was observed for sonolytic ozonation compared to the separate sonication and ozonolysis experiments. The synergistic action of O3 (aq) and ultrasound enhanced oxalate degradation rates 16-fold compared to the simple linear addition of the two independent systems. Several degradation pathways are considered which may account for the rate enhancements observed when ultrasonic irradiation is applied concurrently with ozonolysis. In addition, the decomposition of aqueous ozone in the presence of hydrogen peroxide was investigated. H2O2 enhances the reactivity of O3 (aq) by reactions that remain obscure. Several free-radical degradation mechanisms for O3 decomposition correctly predict the ozone-decay kinetics in pure water but vastly overestimate reaction rates in the presence of H2O2. Results from solvent deuteration experiments in neat water are compatible with a chain-process driven by electron transfer and/or O-transfer processes. However, the large kinetic isotope effect (KIE) found in the O3/H2O2 system provides compelling evidence for an elementary reaction (O3 + HO2-) involving H-O2- bond cleavage and does not support appreciable radical production from the O3 + HO2-reaction. The magnitude of the observed KIE is consistent with a hydride transfer process yielding a closed-shell trioxide HO3-, the conjugate anion of H2O3.
Files	Filename       Size       Approximate Download Time (Hours:Minutes:Seconds)     28.8 Modem   56K Modem   ISDN (64 Kb)   ISDN (128 Kb)   Higher-speed Access    chapter0titlepages.pdf 40.22 Kb 00:00:11 00:00:05 00:00:05 00:00:02 < 00:00:01   chapter1overview.pdf 36.99 Kb 00:00:10 00:00:05 00:00:04 00:00:02 < 00:00:01   chapter2background.pdf 365.00 Kb 00:01:41 00:00:52 00:00:45 00:00:22 00:00:01   chapter3bigreactor.pdf 402.51 Kb 00:01:51 00:00:57 00:00:50 00:00:25 00:00:02   chapter4phenol.pdf 279.98 Kb 00:01:17 00:00:39 00:00:34 00:00:17 00:00:01   chapter5peroxone.pdf 276.47 Kb 00:01:16 00:00:39 00:00:34 00:00:17 00:00:01   chapter6oxalate.pdf 343.02 Kb 00:01:35 00:00:49 00:00:42 00:00:21 00:00:01   chapter7conclusions.pdf 29.84 Kb 00:00:08 00:00:04 00:00:03 00:00:01 < 00:00:01