Date of Award

Spring 2021

Document Type

Thesis

Terms of Use

© 2021 Hyun Kyung Lee. All rights reserved. This work is freely available courtesy of the author. It may only be used for non-commercial, educational, and research purposes. For all other uses, including reproduction and distribution, please contact the copyright holder.

Degree Name

Bachelor of Arts

Department

Chemistry & Biochemistry Department

First Advisor

Thomas Alex Stephenson

Abstract

Alkenes are one of the major components of hydrocarbons in our atmosphere. One of the most common alkenes in our atmosphere is isoprene (2-methyl – 1,3 – butadiene). Currently, it is known that isoprene ozonolysis can lead to the production of Criegee intermediates CH2OO, methacrolein (MACR) oxide, and methyl vinyl ketone (MVK) oxide. In part, we were interested in studying one specific Criegee intermediate, MACR oxide. The competition between the isomerization reactions and the unimolecular reactions became the focus of our study. Rate constants for the relevant reactions were calculated by implementing RRKM theory and using Master Equation modeling to create a scheme for the system. The overall results show that the most favorable reaction of MACR oxide is the isomerization between the cis and trans conformations. Because the transition states between these conformations are relatively low compared to the other transition states in the reaction, the conversions are observed to happen much faster than the others. The next fastest reaction that takes place is the unimolecular decay reactions to the dioxiranes and the dioxole. The decay reactions involved barriers that were higher than the cis⇌trans conversion but still lower than the barrier between the anti⇌syn conversion. With dioxole being our most stable state, our main interest was if different conformers of MACR oxide will decay to this structure in an atmospherically relevant time frame. It was found that substantial fraction (80%) of MACR oxide cannot decompose to dioxole in the relevant time frame as the barrier for the conversion between anti and syn is too high. We saw that there was almost no anti⇌syn conversion in any of our calculations.

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