Premium
The effect of ring size on the gas phase elimination kinetics of cycloalkyl acetates
Author(s) -
Chuchani Gabriel,
Martin Ignacio,
Rotinov Alexandra,
Dominguez Rosa M.,
Morris David G.,
Shepherd Alistair G.
Publication year - 1988
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.550200207
Subject(s) - chemistry , cyclohexene , ring (chemistry) , torr , kinetics , ring size , homogeneous , activation energy , atmospheric temperature range , gas phase , phase (matter) , organic chemistry , thermodynamics , catalysis , quantum mechanics , physics
Abstract The rates of elimination of seven cycloalkyl acetates containing between 5 and 15 ring carbons have been determined in a static system over a temperature range 280–370°C and a pressure range 35–234 torr. The unimolecular reactions, carried out in the presence of the inhibitor cyclohexene, are homogeneous in seasoned vessels and follow a first‐order rate law. The rate coefficients are exemplified by that found for cyclopentyl acetate:\documentclass{article}\pagestyle{empty}\begin{document}$$\log {\rm}k_1 ({\rm s}^{{\rm - 1}}) = (12.68 \pm 0.14) - (179.8 \pm 1.5){\rm \,kJ\,mol}^{{\rm - 1}} {\rm (2}{\rm .303}RT)^{- 1}$$\end{document} The sequence of relative rates is analogous to that found in most solution reactions of these compounds. The contribution of ring strain to energy barriers of these compounds is described.