Date of Graduation
Fall 12-31-2024
Document Type
Thesis
Degree Name
Master of Science in Chemistry
College/School
College of Arts and Sciences
Department/Program
Chemistry
First Advisor
Dr. Giovanni Meloni
Second Advisor
Dr. Amrita Bhattacharyya
Third Advisor
Dr. Herman Nikolayevskiy
Abstract
This thesis presents the reaction of hydroxyacetone, a common volatile organic compound (VOC), with chlorine radicals in the presence of oxygen. Chapter one explores VOCs and their specific reactions and how tetraoxide intermediates could be formed from them. Chapter two analyses the experimental and computational methods used and the key theoretical concepts behind these methods. Experimental data was collected using multiplexed photoionization mass spectrometry at the Advanced Light Source Chemical Transformations Beamline, Lawrence Berkeley National laboratory. This data is combined with theoretical data using the CBS-QB3 composite method to determine the key reaction intermediates and mechanisms.
The main chapter of this thesis (chapter 3) determines the photoionization cross section of hydroxyacetone, with the branching fractions of the main products observed determined. With the aim of understanding the complete reaction mechanism, key reaction intermediates are identified and characterized, with a key focus on tetraoxide intermediates (also known as Russell intermediates). These are potentially key intermediates in the formation of some oxidized species during oxidation reactions, including combustion. Theoretical data shows formation and decomposition of the major product, methylglyoxal, could occur through tetraoxide intermediates. The formation of the acetic acid as a product is consistent with the decomposition of a linear trioxide intermediate which shows an appearance in the mass spectrum. This trioxide may be formed rapidly from the decomposition of a tetraoxide intermediate and poses a new mechanistic pathway to be considered for the decomposition of tetraoxide intermediates.
Recommended Citation
Buck, Edward, "The Radical Oxidation of Hydroxyacetone: An Insight into the Reaction Mechanism and Potential Tetraoxide Intermediates" (2024). Master's Theses. 1595.
https://repository.usfca.edu/thes/1595
