AbstractThe kinetics of the reaction of O + CH3OCH3were investigated using fast‐flow apparatus equipped with ESR and mass‐spectrometric detection. The concentration of O(3P) atoms to CH3OCH3was varied over an unusually large range. The rate constant for reaction\documentclass{article}\pagestyle{empty}\begin{document}$${\rm O} + {\rm CH}_{\rm 3} {\rm OCH}_3 \to {\rm OH} + {\rm CH}_{\rm 2} {\rm OCH}_{\rm 3} $$\end{document}was found to bek= (5.0 ± 1.0) × 1012exp [(−2850 ± 200/RT)] cm3mole−1sec−1. The reaction O + CH3OH was studied using ESR detection. Based on an assumed stoichiometry of two oxygen atoms consumed per molecule of CH3OH which reacts, we obtain a value ofk= (1.70 ± 0.66) × 1012exp [(−2,280 ± 200/RT)] cm3mole−1sec−1for the reaction\documentclass{article}\pagestyle{empty}\begin{document}$${\rm O} + {\rm CH}_{\rm 3} {\rm OH} \to {\rm OH} + {\rm CH}_{\rm 2} {\rm OH}$$\end{document}The results obtained in this study are compared with the results from other workers on these reactions. The observation of essentially equal activation energies in these two reactions is indicative of approximately equal CH bond strengths in CH3OCH3and CH3OH. This is in agreement with recent measurements