Abstract
Kinetics of the isomerisation and unimolecular degradation of n-octyl radicals have been studied with the reaction class transition state theory (RC-TST) method. To explore the kinetics of the 1,7-H migration reactions family, the accurate high-pressure limits of the rate constants for the reference reaction of this class (1-heptyl → 1-heptyl) have been calculated. Finally, both the achievements reported in this paper and previous developments are employed to obtain theoretical branching ratios of intramolecular H-transfers and unimolecular degradations of all possible n-octyl radicals; the results are in satisfactory agreement when compared to experiment. The application of the rates obtained to the simulation of a simple reactor is also reported.
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