Volume 66, 1970

Reaction of deuterium atoms with methyl bromide studied by gas phase e.p.r. spectroscopy

Abstract

Gas-phase electron paramagnetic resonance spectroscopy has been used to study the reaction of deuterium atoms with methyl bromide in a discharge flow system in the 1-10 Torr pressure range at 297 K and between 297 and 480 K at 3.1 ± 0.1 Torr. The initial steps in the reaction are D + CH3Br = CH3+ DBr (7), D + DBr = D2+ Br (10), with k7= 5.41 ± 0.18 × 1013 exp(–17.9 ± 1.1 kJ mol –1/RT) cm3 mol–1 s–1, the total rate of disappearance of deuterium atoms being several times greater than k7 and inversely dependent on total pressure. This was due to a chain reaction in which the rate-determining step is diffusion of bromine atoms to the wall.

Methyl radicals are removed primarily at the surface in this system and the reactions D + CH3= CH3D*(4), CH3D*= CH2D + H (5), are relatively minor processes. From the kinetics of hydrogen atom production a value of k4= 7 × 1012 exp(–9.1 ± 1.5 kJ mol–1/RT)cm3 mol–1 s–1 is obtained.

Article information

Article type
Paper

Trans. Faraday Soc., 1970,66, 886-897

Reaction of deuterium atoms with methyl bromide studied by gas phase e.p.r. spectroscopy

P. B. Davies, B. A. Thrush and A. F. Tuck, Trans. Faraday Soc., 1970, 66, 886 DOI: 10.1039/TF9706600886

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