The thermal methyl-radical exchange reaction, CH4 + CD4 → CH3D + CD3H, has been studied in a static system at temperatures from 880 to 1103 K, with equimolar mixtures at a pressure of 440 Torr. The exchange occurs by a methyl-radical chain mechanism, propagated by the reactions CH3 + CD4 → CH3D + CD3, and CH3 + CD4 → CH3H + CD3. Values of an average rate constant for these reactions have been estimated; kx = 1.42 × 106 ℓ mol−1 s−1 at 995 K. Comparison with shock tube data and photochemical measurements, at higher and lower temperatures respectively, indicates pronounced non-Arrhenius behaviour.
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