Gas-phase thermal unimolecular decomposition of oxetan
Abstract
The gas phase pyrolysis of oxetan has been re-investigated at temperatures from 693 to 753 K and at initial pressures from 53.3 to 15 598 N m–2(0.40 to 117.0 Torr). At high pressures the pyrolysis to give ethylene and formaldehyde is a homogeneous unimolecular process with a rate-constant given by log10(k∞/s–1)=(15.71 ± 0.31)–(263 696 ± 3510)J mol–1/2.303RT.
Unimolecular fall-off has been observed at two temperatures, and the half-pressure is approximately 133.3 N m–2(1 Torr) at 737.5 K. Calculations based on the RRKM treatment and also on the Forst method give fall-off curves in good agreement with experiment at the half-pressure.
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