Dissertation/Thesis Abstract

Experimental and theoretical studies of the kinetics of the hydroxyl radical (OH)-initiated oxidation of volatile organic compounds
by Liljegren, Jennifer A., Ph.D., Indiana University, 2013, 233; 3602969
Abstract (Summary)

This research investigates the kinetics of the hydroxyl radical (OH)-initiated oxidation of several volatile organic compounds (VOCs) including ethanol, 3-methylfuran, and methyl ethyl ketone (2-butanone). Oxidation by OH is the dominant loss process for many biogenic and anthropogenic VOCs, making ambient concentrations of OH and the rate constants of OH + VOC reactions useful for determining the lifetime of various VOCs in the atmosphere. The rate constants of OH + VOC reactions are important for improving the accuracy of input parameters used in urban and regional air quality models which can be used to inform the development of air quality control strategies. The absolute rate constants for the reaction of OH with ethanol, 3- methylfuran, and methyl ethyl ketone (2-butanone) and, in some cases, their deuterated isotopomers have been measured as a function of pressure and temperature using discharge-flow techniques coupled with laser-induced fluorescence detection of OH. Theoretical studies of the potential energy surface for the various pathways in the OH + ethanol and OH + methyl ethyl ketone (2-butanone) reactions indicate a mechanism involving hydrogen-abstraction through a hydrogen-bonded pre-reactive complex. The experimental measurements of the rate constants and the kinetic isotope effect have been used in conjunction with the results of the theoretical studies to improve our understanding of the kinetics of these reactions.

Indexing (document details)
Advisor: Stevens, Philip S.
Commitee: Hites, Ronald A., Raff, Jonathan, Royer, Todd V., White, Jeffrey R.
School: Indiana University
Department: Environmental Science
School Location: United States -- Indiana
Source: DAI-B 75/03(E), Dissertation Abstracts International
Source Type: DISSERTATION
Subjects: Atmospheric Chemistry, Chemistry, Environmental science
Keywords: Atmospheric chemistry, Hydroxyl radical, Kinetics, Oxidation, Ozone, Voc, Volatile organic compounds
Publication Number: 3602969
ISBN: 978-1-303-56673-8
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