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- Title
Kinetics of the homogeneous, unimolecular elimination reactions of ethyl oxamate, ethyl N,N-dimethyloxamate and ethyl oxanilate in the gas phase.
- Authors
Chacin, Esker V.; Tosta, María; Herize, Armando; Domínguez, Rosa M.; Alvarado, Ysaias; Chuchani, Gabriel
- Abstract
The gas-phase elimination kinetics of the title compounds were determined over the temperature range 350–430°C and pressure range 35–240 Torr (1 Torr = 133.3 Pa). The reactions, which were carried out in a static reactor system, seasoned with allyl bromide and in the presence of a free radical inhibitor, are homogeneous, unimolecular and obey a first-order rate law. The temperature dependences of the overall rate coefficients are given by the following Arrhenius equations: for ethyl oxamate, log [k1 (s-1)] = (13.28 ± 0.20) – (203.7 ± 2.5) kJ mol-1 (2.303RT)-1, for ethyl N,N-dimethyloxamate, log [k1 (s-1)] = (13.06 ± 0.34) – (206.8 ± 4.4) kJ mol-1(2.303RT)-1, and for ethyl oxanilate, log [k1 (s-1)]= (13.86 ± 0.12)–(207.4 ± 1.5) kJ mol-1(2.303RT)-1. The overall rates, the partial rates and the kinetic and thermodynamic parameters of these eliminations are presented and discussed. These reactions appear to proceed through moderately polar cyclic transition states. Copyright © 2004 John Wiley & Sons, Ltd.
- Subjects
GASES; DYNAMICS; BROMIDES; FREE radicals; ARRHENIUS equation; THERMODYNAMICS
- Publication
Journal of Physical Organic Chemistry, 2005, Vol 18, Issue 6, p539
- ISSN
0894-3230
- Publication type
Article
- DOI
10.1002/poc.894