Felix Rosas, Angiebelk Monsalve, Maria M. Tosta
Jun 1, 2005
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Influential Citations
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Journal
International Journal of Chemical Kinetics
Abstract
The kinetics of the gas-phase elimination of the title compounds has been determined in a static reaction system over the temperature range of 340-420°C and pressure range of 45-96 Torr. The reactions proved to be homogeneous, unimolecular, and obey a first-order rate law. The estimated rate coefficients are represented by the following Arrhenius expressions: Ethyl 1-piperidine carboxylate log k 1 (s - 1 ) = (12.61 ′ 0.11) - (191.1 ′ 1.4)k] mor - 1 (2.303 RT) - 1 , r =0.9999 Ethyl pipecolinate logk 1 (s - 1 ) = (12.87 ′ 0.16) - (204.3 ′ 2.1) kJ mol - 1 (2.303 RT) - 1 , r = 0.9998 Ethyl I-methyl pipecolinate logk 1 (s - 1 ) = (13.34 ′ 0.32) - (209.4 ′ 4.0)kJmol - 1 (2.303 RT) - 1 , r =0.9992 The first step of decomposition of these esters is the formation of the corresponding carboxylic acids and ethylene. The acid intermediate undergoes a very fast decarboxylation process. The mechanism of this elimination reactions is suggested on the basis of the kinetic and thermodynamic parameters.