Document Type


Date of Award

Spring 5-31-1996

Degree Name

Master of Science in Environmental Science - (M.S.)


Chemical Engineering, Chemistry and Environmental Science

First Advisor

Joseph W. Bozzelli

Second Advisor

Richard B. Trattner

Third Advisor

Tsan-Horng Lay


A reaction mechanism consisting of 248 elementary reactions and 138 species has been developed to model experimental systems - decomposition of 2,2,3,3 tetramethylbutane in the presence of oxygen and oxidation of isobutene. This elementary reaction mechanism based on two important reaction systems: tert-butyl radical with O2 and allylic isobutenyl radical with O2, plus their subsystems, such as isobutene + HO2, isobutene + OH and allylic isobuteny1hydroxy + O2. Thermochernical kinetic parameters are developed for each elementary reaction and a chemical activation kinetic analysis using quantum RiceRamsperger-Kassel (QRRK) theory for k(E) and modified strong collision analysis for falloff is used to calculate Vs as function of pressure and temperature. All reactions in the mechanism incorporate reverse reaction rates calculated from thermodynamic parameters and microscopic reversibility. Results show that several important equilibria are achieved with product formation effected by slow (bleed) reaction out of the equilibrium system. In tert-butyl radical with O2 system it shows a near 200 to 1 dominance of the isobutene + HO2 channel over formation of the 2,2-dimethyloxirane + OH at 60 torr. Rate constants and detailed reaction paths for formation of important products: acetone, methacrolein, and epoxides, and formation of five-member and the four-member cyclic intermediates are determined in allylic isobutenyl radical with O2 system. Predictions are in good agreement with experimental data.



To view the content in your browser, please download Adobe Reader or, alternately,
you may Download the file to your hard drive.

NOTE: The latest versions of Adobe Reader do not support viewing PDF files within Firefox on Mac OS and if you are using a modern (Intel) Mac, there is no official plugin for viewing PDF files within the browser window.