Abstract
The elimination kinetics of severaltert-butyl α-alkylacetates have been studied in a static reactor at temperatures between 240 and 290°C and pressures between 47 and 178 Torr. The reactions are homogeneous, unimolecular, and follow a first-order rate law. The rate coefficients are given by the Arrhenius equations: fortert-butyl butyrate, log k1 (s−1)=(12.77±0.37−(163.9±3.8) kJ/mol/2.303 RT; fortert-butyl isovalerate, log k1 (s−1)=(13.42±0.24)−(170.5±2.6) kJ/mol/2.303 RT fortert-butyltert-butylacetate, log k1(s−1)=(13.77±0.40)−(174.3±4.1) kJ/mol/2.303 RT. The alkyl substituents at the acyl carbon oftert-butyl esters lead to similar rates. Apparently, the gradual increase of alkyl bulkiness has a very insignificant influence on the pyrolysis rates.
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