Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases p. 1087 - 1094 (1985)
Update date:2022-08-25
Topics:
Frey, H. Monty
Pidgeon, Ivy M.
The thermal decomposition of oxetan-2-one has been investigated in the gas phase in the temperature range 262-322 deg C.The reaction, which yields ethylene and carbon dioxide, is homogeneous and obeys first-ordr kinetics.There is a minor heterogenous isomerization to yield acrylic acid.The decomposition is almost certainly a unimolecular process, which in the pressure range studied, -1 against p-0.61 yielded the Arrhenius equation log k/s-1 = 14.86 +/- 0.30 - 180.46 +/- 3.20 kJ mol -1 / RT ln 10.Theoretical (RRKM) calculations are close to the experimental fall-off curves on the basis of the strong-collision assumption or with <ΔE>d (stepladder model)>/= 24 kJ mol-1, from which it is hardly distinguishable.Certainly it is necessary to assume very efficient intermolecular energy transfer.Comparison with the result from other studies suggests a concerted decomposition via an activated complex with zwitterionic character rather similar to those involved in cyclobutanone decompositions.
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