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The pyrolysis kinetics of ethyl esters in the gas phase. The alkyl substituent effect at the acyl carbon

✍ Scribed by Gabriel Chuchani; Ignacio Martin

Publisher: John Wiley and Sons
Year: 1983
Tongue: English
Weight: 214 KB
Volume: 15
Category: Article
ISSN: 0538-8066
DOI: 10.1002/kin.550150505

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✦ Synopsis

The gas-phase elimination of ethyl 3-methylbutanoate and ethyl 3,3-dimethylbutanoate has been studied, in a static system, over the temperature range of 36O42O0C and in the pressure range of 71-286 torr. The reactions are homogeneous, unimolecular, and follow a first-order rate law. The temperature dependence of the rate coefficients is given by the following Arrhenius equations: for ethyl 3-methylbutanoate, log k l (s-l) = (12.70 f 0.36) -(202.5 f 4.4) kJ/mo1/2.303RT, and for ethyl 3,3-dimethylbutanoate, log k l (9-l) = (13.04 f 0.08) -(207.1 f 1.0) kJ/mo1/2.303RT. Alkyl substituents at the acyl carbon of ethyl esters yield very close values in rates. Consequently it is rather difficult to offer some conclusion concerning the effect of these substituents.

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