ISSN:
1588-2837
Keywords:
Pyrolysis
;
homogeneous kinetics
Source:
Springer Online Journal Archives 1860-2000
Topics:
Chemistry and Pharmacology
Notes:
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)δ+...δ-CH2COOCH2CH3 bond is rate determining.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1007/BF02076139
