Kinetics of hydrogen abstraction by difluoroamino radicals from n-propyl formate and the n-propoxycarbonyl radical decomposition

Abstract

The kinetics of the formyl hydrogen abstraction by difluoroamino radicals from n-propyl formate, using tetrafluorohydrazine as a thermal source of these radicals, has been studied between 398 and 463 K. The rate equation for this abstraction was given by log[k/(ml mol^–1 s^–1)]=(8.48 ± 0.88)–(77800 ± 7200)/2.3RT where R= 8.314 J mol^–1 K^–1. The decomposition reaction of the resulting n-propoxycarbonyl radical was also studied. No pressure dependence on this decomposition of the radical was observed in this temperature range and in the pressure range 11–76 Torr. The rate equation was given by log(k/s^–1)=(14.11 ± 0.89)–(53000 ± 7300)/2.3RT where R= 8.314 J mol^–1 K^–1.