Date of Award

5-11-2015

Degree Type

Dissertation

Degree Name

Doctor of Philosophy (PhD)

Department

Chemistry

First Advisor

Alfons Baumstark

Second Advisor

Suazette Mooring

Third Advisor

Markus Germann

Abstract

Kinetic studies determining the second order rate constants for the monoepoxidation of cyclic dienes, 1,3-cyclohexadiene and 1,3-cyclooctadiene, and the epoxidation of cis-/trans-2-hexenes by dimethyldioxirane (DMDO) were carried out using UV methodology. Consistent with published results, the kinetics of cis-/trans-2-hexenes by DMDO showed greater reactivity of the cis-isomer compared to that of the trans-compound. Molecular modeling studies for the epoxidation of a series of cis-/trans-alkenes, by DMDO were carried out using the DFT approach. The mechanism of epoxidation by DMDO was modeled by determining the transition state geometry and calculating the electronic activation energies and relative reactivities. The calculations were consistent with a concerted, electrophilic, exothermic process with a spiro-transition state for all cases. Kinetic studies for the monoepoxidation of the cyclic dienes showed a greater reactivity for 1,3-cyclohexadiene compared to that for 1,3-cyclooctadiene. The DFT method was employed to successfully model the transition state for the monoepoxidation of the cyclic dienes by DMDO and successfully predict the relative reactivities.

Student misconceptions, at the high school and/or middle school level involving energy changes and chemical reactions have been prevalently noted in literature (by ACS and AAAS). Two examples of these misconceptions are: 1) heat is always needed to initiate a chemical reaction and 2) all chemical reactions create or destroy energy. In order to address these types of misconceptions, an educational module detailing the influence of energy changes on chemical reactions has been developed in conjunction with the Bio-bus program for middle and high school students. Visual aids and hands-on activities were developed in the module to potentially help students overcome/deal with the common misconceptions. Surveys were designed to access the situations (determine the extent of the misconceptions) and the effectiveness of the educational module, before and immediately after the module and one-month later to determine retention. The educational module has been presented to approximately 100 high school students from underrepresented communities. Pre-survey data confirmed the presence of the common misconceptions reported in the literature. Data from the post-survey indicated the new instructional module enhanced the student’s interest of science and expanded their content knowledge and laboratory skills. The post-survey data (immediately following the module) showed a significant difference in two out of five misconceptions when compared to the pre-survey data. However, this significance decreased when the 1-month post-survey data were compared to the pre-survey data.

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