Homogeneous,unimolecular gas‐phase elimination kinetics of ethyl esters of glyoxylic, 2‐oxo‐propanoic,and 3‐methyl‐2‐oxo‐butanoic acids |
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| Authors: | Andreina Reyes Rosa M Dominguez Maria Tosta Armando Herize Gabriel Chuchani |
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| Institution: | 1. Centro de Química, Instituto Venezolano de Investigaciones Científicas (IVIC), Apartado 21827, Caracas 1020‐A, Venezuela;2. Centro de Química, Instituto Venezolano de Investigaciones Científicas (IVIC), Apartado 21827, Caracas 1020‐A, VenezuelaCentro de Química, Instituto Venezolano de Investigaciones Científicas (IVIC), Apartado 21827, Caracas 1020‐A, Venezuela |
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| 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]( "equation image") Ethyl 2‐oxo‐propionate ![equation image]( "equation image") Ethyl 3‐methyl‐2‐oxo‐butyrate ![equation image]( "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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