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Very low pressure pyrolysis of phenyl acetate
Author(s) -
Ghibaudi E.,
Colussi A. J.
Publication year - 1984
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550161211
Subject(s) - chemistry , ketene , arrhenius equation , decomposition , radical , pyrolysis , phenol , kinetics , homolysis , fission , medicinal chemistry , thermal decomposition , atmospheric temperature range , photochemistry , activation energy , organic chemistry , thermodynamics , physics , quantum mechanics , neutron
The kinetics of the unimolecular decomposition of phenyl acetate into phenol and ketene, reaction (1):\documentclass{article}\pagestyle{empty}\begin{document}$${\rm PhOCOCH}_3 \buildrel 1\over\rightarrow{\rm PhOH} + {\rm CH}_2 = {\rm C} = {\rm O}$$\end{document}has been studied under very low‐pressure conditions between 950 and 1120 K. In this range alternative processes such as the Fries rearrangement to o ‐hydroxyacetophenone or bond fission into phenoxyl and acetyl radicals are not observed. Based on present and previous evidence a novel four‐center transition state is proposed for reaction (1) which corresponds to the high‐pressure Arrhenius expression log ( k 1 , s −1 ) = 12.8 – 56.2/θ, θ = 4.575 × 10 −3 T kcal/mol.