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Homogeneous, unimolecular gas-phase elimination kinetics of ethyl esters of glyoxylic, 2-oxo-propanoic, and 3-methyl-2-oxo-butanoic acids

✍ Scribed by Andreina Reyes; Rosa M. Dominguez; Maria Tosta; Armando Herize; Gabriel Chuchani

Publisher
John Wiley and Sons
Year
2007
Tongue
English
Weight
325 KB
Volume
39
Category
Article
ISSN
0538-8066

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✦ Synopsis

Abstract

The rates of elimination of several ethyl esters of 2‐oxo‐carboxylic acid were determined in a seasoned static reaction vessel over the temperature range 350–430°C and pressure range 33–240 Torr. The reactions, in the presence of a free‐radical inhibitor, are homogeneous, unimolecular, and follow a first‐order rate law. The overall and partial rate coefficients are expressed by the Arrhenius equation.

Ethyl glyoxalate

equation image

Ethyl 2‐oxo‐propionate

equation image

Ethyl 3‐methyl‐2‐oxo‐butyrate

equation image

The mechanisms of these elimination reactions are described in terms of concerted cyclic transition state structures. © 2007 Wiley Periodicals, Inc. Int J Chem Kinet 39: 268–275, 2007

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