G. Chuchani, I. Martín, A. Rotinov
Sep 1, 1995
Citations
0
Influential Citations
12
Citations
Journal
International Journal of Chemical Kinetics
Abstract
The elimination kinetics of the title compounds have been examined over the temperature range of 270–320°C and pressure range of 19–117 torr. The reactions, carried out in seasoned vessels, with the free-radical suppressor toluene always present, are homogeneous, unimolecular, and follow a first-order rate law. The products of 2-hydroxy-2-methylbutyric acid are 2-butanone, CO, and H2O; while of 2-ethyl-2-hydroxybutyric acid are 3-pentanone, CO, and H2O. The rate coefficient is expressed by the following Arrhenius equation: for 2-hydroxy-2-methylbutyric acid, log k1(s−1 = (12.87 ± 0.19) − (171.2 ± 2.1) kJ mol−1 (2.303 RT)−1; and for 2-ethyl 2-hydroxybutyric acid, log k1s−1) = (12.13 ± 0.34) − (159.4 ± 3.7) kJ mol−1 (2.303 RT)−1. Augmentation of alkyl bulkiness at the 2-position of the 2-hydroxycarboxylic acids showed an increase in the rate of dehydration. The electron release of alkyl groups, rather than steric acceleration, appears to enhance the pyrolysis decomposition of these substrates. These reactions are believed to proceed through a semi-polar five-membered cyclic transition type of mechanism. © 1995 John Wiley & Sons, Inc.