International Journal of Chemical Kinetics p. 268 - 275 (2007)
Update date:2022-08-24
Topics:
Reyes, Andreina
Dominguez, Rosa M.
Tosta, Maria
Herize, Armando
Chuchani, Gabriel
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 log k1(CO2)(s-1) = (13.43±0.25)-(213.1±3.3) kJ mol-1 (2.303 RT) -1, r = 0.9996 log k2(CO) (s-1) = (14.06±0.54) - (232.9±7.0) kJ mol-1 (2.303 RT) -1, r = 0.9986 log kt(overall) (s-1) = (13.72±0.25) - (216.1±3.3) kJ mol-1 (2.303 RT) -1, r = 0.9997 Ethyl 2-oxo-propionate log k1 (s -1) = (13.03±0.15) - (205.1±2.0) kJ mol-1 (2.303 RT)-1, r = 0.9998 Ethyl 3-methyl-2-oxo-butyrate log k 1 (s-1) = (12.58±0.31)-(198.4±4.1) kJ mol-1 (2.303 RT)-1, r = 0.9994 The mechanisms of these elimination reactions are described in terms of concerted cyclic transition state structures.
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