Ozone is a heavily monitored pollutant. Ozone is not directly emitted into the atmosphere, but rather the product of chemical reactions. Ground level ozone occurs when nitrogen oxides (NOx) and volatile organic compounds (VOCs) react with each other in the presence of sunlight. The primary precursors of ozone are anthropogenically emitted, and as a result, tropospheric ozone has cost millions of dollars in damages and has hurt the health of countless people. This dissertation is a collection of work that aims to provide insight into atmospheric reactions that result in tropospheric ozone and the instrumentation to study such reactions. While these reactions are well studied, this research is novel in its attempt to understand water vapor's influence in tropospheric ozone reactions. As the troposphere continues to get warmer and wetter from global climate change, water vapor will play a larger role in tropospheric reactions, which in turn may perturb the global reactions. Work is presented on the self-reaction of β-hydroxyethyl peroxy radical (β-HEP), an ozone precursor, and the increase in reaction rate catalyzed by water vapor. β-HEP serves as a model system for understanding the roles of water vapor in perturbing the kinetics and product branching ratio of ozone forming reactions. The self-reaction rate coefficient of β-HEP was investigated between 274-296 K with 1.0 × 1015 to 2.5 × 1017 molecules cm-3 of water vapor at 200 Torr total pressure by slow-flow laser flash photolysis coupled with UV time-resolved spectroscopy and long-path, wavelength-modulated, diode-laser spectroscopy. The overall rate constant is expressed as the product of temperature-dependent and water vapor-dependent terms giving k(T,H2O) = 7.8 × 10-14(e8.2 (±2.5) kJ/RT )(1 + 1.4 × 10-34 × e92 (±11) kJ/RT [H2O]). The results suggest that formation of a β-HEP-H2O complex is responsible for the observed water vapor enhancement of the self-reaction rate coefficient. A new discharge flow mass-spectrometer was engineered in collaboration with the California Institute of Technology and NASA's Jet Propulsion Laboratory. This instrument allows for rapid study of water vapor influence on the kinetics of atmospheric reactions. This instrument will be used in further studying the β-HEP + NO reaction as a function of water vapor concentration.



College and Department

Physical and Mathematical Sciences; Chemistry and Biochemistry



Date Submitted


Document Type





discharge flow mass-spectrometer, atmospheric kinetics, ozone, β-hydroxyethyl peroxy