Abstract
The oxidation of methanol in a flow reactor has been studied experimentally under diluted, fuelβlean conditions at 650β1350 K, over a wide range of O~2~ concentrations (1%β16%), and with and without the presence of nitric oxide. The reaction is initiated above 900 K, with the oxidation rate decreasing slightly with the increasing O~2~ concentration. Addition of NO results in a mutually promoted oxidation of CH~3~OH and NO in the 750β1100 K range. The experimental results are interpreted in terms of a revised chemical kinetic model. Owing to the high sensitivity of the mutual sensitization of CH~3~OH and NO oxidation to the partitioning of CH~3~O and CH~2~OH, the CH~3~OH + OH branching fraction could be estimated as Ξ± = 0.10 Β± 0.05 at 990 K. Combined with lowβtemperature measurements, this value implies a branching fraction that is largely independent of temperature. It is in good agreement with recent theoretical estimates, but considerably lower than values employed in previous modeling studies. Modeling predictions with the present chemical kinetic model is in quantitative agreement with experimental results below 1100 K, but at higher temperatures and high O~2~ concentration the model underpredicts the oxidation rate. Β© 2008 Wiley Periodicals, Inc. Int J Chem Kinet 40: 423β441, 2008