Disproportionation–combination ratios of difluoroamino-radicals with isopropyl and with t-butyl radicals

Abstract

Di-isopropyl and methyl t-butyl ketones were photolysed separately in the gas phase between 296–485 K in the presence to tetrafluorohydrazine.

The disproportionation–combination ratios of isopropyl and t-butyl radicals with difluoroamino-radicals were found to be: Δ(NF₂, i-C₃H₇)=(0·0535 ± 0·005) exp [+(595 ± 300)/RT]Δ(NF₂, t-C₄H₉)=(1·98 ± 0·20) exp [–(9140 ± 330)/RT], where R= 8·31 J mol^–1 K^–1. From the previously measured rate of combination of isopropyl radicals with difluoroamino-radicals, the rate of disproportionation was calculated to be: log k(ml mol^–1s^–1)= 9·09 – 5880/2·3RT.