Investigation Of The Role Of Bicyclic Peroxy Radicals In The Oxidation Mechanism Of Toluene
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.
Birdsall, Adam W., John F. Andreoni, and Matthew J. Elrod. 2010. "Investigation Of The Role Of Bicyclic Peroxy Radicals In The Oxidation Mechanism Of Toluene." Journal Of Physical Chemistry A 114(39): 10655-10663.
American Chemical Society
Journal of Physical Chemistry A
Chemistry and Biochemistry
Ring-retaining products, Oh-initiated oxidation, Gas-phase reaction, Atmospheric oxidation, Aromatic-hydrocarbons, Hydroxyl radicals, Rate-constant, Benzene, Photooxidation, Xylene