Investigation Of The Role Of Bicyclic Peroxy Radicals In The Oxidation Mechanism Of Toluene

Abstract

The products of the primary OH-initiated oxidation of toluene were investigated using the turbulent flow chemical ionization mass spectrometry technique under different oxygen, NO, and initial OH radical concentrations as well as a range of total pressures. The bicyclic peroxy radical intermediate, a key proposed intermediate species in the Master Chemical Mechanism (MCM) for the atmospheric oxidation of toluene, was detected for the first time. The toluene oxidation mechanism was shown to have a strong oxygen concentration dependence, presumably due to the central role of the bicyclic peroxy radical in determining the stable product distribution at atmospheric oxygen concentrations. The results also suggest a potential role for bicyclic peroxy radical + HO2 reactions at high HO2/NO ratios. These reactions are postulated to be a source of the inconsistencies between environmental chamber results and predictions from the MCM.

Publisher

American Chemical Society

Publication Date

10-1-2010

Publication Title

Journal of Physical Chemistry A

Department

Chemistry and Biochemistry

Document Type

Article

DOI

https://dx.doi.org/10.1021/jp105467e

Keywords

Ring-retaining products, Oh-initiated oxidation, Gas-phase reaction, Atmospheric oxidation, Aromatic-hydrocarbons, Hydroxyl radicals, Rate-constant, Benzene, Photooxidation, Xylene

Language

English

Format

text

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