Homogeneous pyrolysis kinetics of ethyl 3-hydroxy-3-methylbutanoate in the gas phase |
| |
Authors: | Rosa M. Dominguez Gabriel Chuchani Jairo Quijano Luz Janeth Orozco Iliana Restrepo |
| |
Affiliation: | (1) Centro de Química, Instituto Venezolano de Investigaciones Científicas (I.V.I.C.), Apartado 21827, 1020-A Caracas, Venezuela;(2) Departamento de Química, Facultad de Ciencias, Universidad Nacional de Colombia, Apartado Aéreo 3840, Medellín, Colombia |
| |
Abstract: | The pyrolysis kinetics of ethyl 3-hydroxy-3-methylbutanoate have been examined over the temperature range of 286–330°C and pressure range of 29–108 Torr. In a seasoned vessel and in the presence of the free radical inhibitor cyclohexene or toluene the reaction is homogeneous, unimolecular and obeys a first-order rate law. The elimination products are mainly acetone and ethyl acetate, and very small amounts of ethyl 3-butenoate, acetic acid, ethylene and H2O. The rate coefficient is expressed by the following equation: log k1(s–1)=(12.39±0.46)–(174.5±5.2) kJ mol–1 (2.303RT)–1. The mechanism appears to proceed via a six-membered cyclic transition state, where polarization of the (CH3)C(OH)+...-CH2COOCH2CH3 bond is rate determining. |
| |
Keywords: | Pyrolysis homogeneous kinetics |
本文献已被 SpringerLink 等数据库收录! |
|