Direct measurement and analysis of cyclohexadienyl oxidation

The oxidation of cyclohexadienyl radical (c-C₆H₇) and similar resonantly stabilized radicals are important in an astonishing array of processes in nature. Cyclohexadienyl radical has been postulated to be significant in a variety of processes that involve the atmospheric formation of benzene. In biology, there are specific enzymes that promote the formation of benzene-like intermediates from cyclohexadienyl radicals, called cyclohexadienyl dehydratases. In combustion processes, cyclohexadienyl radical is a possible link to the formation of soot and other large polyaromatic hydrocarbons (PAH's). Thus, the cyclohexadienyl radical moiety is important in many chemical processes, and its detailed study is of interest in many areas. In this work, cyclohexadienyl radical is studied both computationally and experimentally in the liquid and gas phases. The cyclohexadienyl radical is created using laser-flash photolysis. The UV absorption bands of the radical are probed and it's relative concentration over time measured in non-polar solvents in both the presence and absence of oxygen. Several analytical and numerical models of the chemistry were constructed to explain a puzzling discrepancy in the reported liquid and gas phase reaction rates.

Department dc:contributor.department

Massachusetts Institute of Technology. Dept. of Chemical Engineering.

Grantor dc:publisher

Massachusetts Institute of Technology

Year dc:date.issued

2005

Author dc:creator

• Taylor, James Wagner

Advisor dc:contributor.advisor

• William H. Green.

• Chemical Engineering.

Statement dc:rights

• M.I.T. theses are protected by copyright. They may be viewed from this source for any purpose, but reproduction or distribution in any format is prohibited without written permission. See provided URL for inquiries about permission.

Licence dc:rights.uri

• http://dspace.mit.edu/handle/1721.1/7582

Language dc:language.iso

eng

Handle dc:identifier.uri

http://hdl.handle.net/1721.1/33716

OAI identifier oai:identifier

oai:dspace.mit.edu:1721.1/33716