Thermal Decomposition of Nitromethane and Reaction between CH3 and NO2

The thermal decomposition of gaseous nitromethane and the subsequent bimolecular reaction between CH3 and NO2 have been experimentally studied using time-resolved cavity-enhanced absorption spectroscopy behind reflected shock waves in the temperature range 1336-1827 K and at a pressure of 100 kPa. Temporal evolution of NO2 was observed following the pyrolysis of nitromethane (diluted to 80-140 ppm in argon) by monitoring the absorption around 400 nm. The primary objectives of the current work were to evaluate the rate constant for the CH3 + NO2 reaction (k(2) ) and to examine the contribution of the roaming isomerization pathway in nitromethane decomposition. The resultant rate constant can be expressed as k(2) = (9.3 +/- 1.8) x 10(-10)(T/K)(-0.5) cm(3) molecule(-1) s(-1), which is in reasonable agreement with available literature data. The decomposition of nitromethane was found to predominantly proceed with the C-N bond fission process with the branching fraction of 0.97 +/- 0.06. Therefore, the upper limit of the branching fraction for the roaming pathway was evaluated to be 0.09.