Oxidation mechanism of aromatic peroxy and bicyclic radicals from OH-toluene reactions. Academic Article

abstract

• Theoretical calculations have been performed to investigate mechanistic features of OH-initiated oxidation reactions of toluene. Aromatic peroxy radicals arising from initial OH and subsequent O(2) additions to the toluene ring are shown to cyclize to form bicyclic radicals rather than undergoing reaction with NO under atmospheric conditions. Isomerization of bicyclic radicals to more stable epoxide radicals possesses significantly higher barriers and, hence, has slower rates than O(2) addition to form bicyclic peroxy radicals. At each OH attachment site, only one isomeric pathway via the bicyclic peroxy radical is accessible to lead to ring cleavage. The study provides thermochemical and kinetic data for quantitative assessment of the photochemical production potential of ozone and formation of toxic products and secondary organic aerosol from toluene oxidation.

authors

• Zhang, Renyi

published proceedings

• J Am Chem Soc

author list (cited authors)

• Suh, I., Zhang, R., Molina, L. T., & Molina, M. J.

citation count

• 160

complete list of authors

• Suh, Inseon||Zhang, Renyi||Molina, Luisa T||Molina, Mario J

publication date

• October 2003

publisher

• American Chemical Society (ACS)  Publisher

published in

• Journal of the American Chemical Society  Journal

keywords

• 0306 Physical Chemistry (incl. Structural)

PubMed Central ID

• 14531710

Digital Object Identifier (DOI)

• 10.1021/ja0350280

start page

• 12655

end page

• 12665

volume

• 125

issue

• 41

URL

• http%3A%2F%2Fdx.doi.org%2F10.1021%2Fja0350280