Alkoxy radicals are important intermediates in the photooxidation of volatile organic compounds due to their large impact on both ozone formation and gas-particle partitioning of eventual stable products. Methoxy radical (CH3O�) is the prototype for all alkoxy radicals.The absolute rate constants kNO2(T) for reaction of CH3O� and CD3O� with NO2 will be measured using laser flash photolysis to generate radicals and laser-induced fluorescence for time-resolved detection. Preliminary work has demonstrated that our apparatus gives reasonable results for kNO2 at pressures up to 700 Torr. This will be the first direct measurement of kNO2 for CD3O�. The relative rate constants kNO2/kO2(T) will be measured in an environmental chamber with FTIR detection. This combination will enable the first determination of kO2(T) for CH3O� and CD3O� for T < 298 K.The results will also help validate theoretical methods for studying alkoxy + O2 reactions, which are challenging for quantum chemistry.

Kinetic study of the reactions of methoxy radical with NO<sub>2</sub> and O<sub>2</sub> and their deuterium kinetic isotope effects

244th National Meeting (2012)

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Kinetic study of the reactions of methoxy radical with NO2 and O2 and their deuterium kinetic isotope effects

Kinetic study of the reactions of methoxy radical with NO₂ and O₂ and their deuterium kinetic isotope effects