
Abstract Simplified chemical-kinetic mechanisms are sought that can provide agreement with measured shock-tube autoignition times and counterflow critical ignition conditions for methanol (CH 3 OH) oxidation. Existing detailed chemistry over-predicts measured counterflow ignition temperatures by 100 K or more. It was found that the elementary step CH 3 OH + HO 2 → CH 2 OH + H 2 O 2 most strongly affects the predictions. Increasing the pre-factor in the Arrhenius expression for the rate of this step from different available literature values by a factor ranging from 2 to 13, namely to 8 × 10 13 cm 3 /(mol s), within existing uncertainty, produces agreement of predictions with experiment. Using this revised rate, unimportant steps are deleted from the San Diego mechanism to obtain a set of 26 irreversible elementary steps (augmented to 27 by including fuel dissociation to CH 3 + OH for high-temperature shock-tube conditions) that predict ignition nearly as well as the detailed mechanism. In this mechanism, the intermediate species CH 2 OH, CH 3 O, HCO, H, O, and OH accurately obey steady states, while the intermediates CH 2 O, HO 2 , H 2 O 2 , CO, and H 2 do not. The result is a six-step overall reduced mechanism that describes ignition well at the lower temperatures. At higher temperatures, the aforementioned fuel decomposition becomes important, increasing the six-step mechanism to a seven-step mechanism. Expressions for the reaction rates, branching ratios, and steady-state species concentrations in the six-step reduced mechanism are given to facilitate future methanol ignition computations. Higher alcohols, which are less dependent on HO 2 attack in ignition, are indicated to nevertheless possibly benefit from an increase of the rate of the corresponding step.
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