Electron affinity of SF6 and perfluoromethylcyclohexane. The unusual kinetics of electron transfer reactions A−+B=A+B−, where A=SF6 or perfluorinated cyclo-alkanes

Measurements of the equilibria (1): A−+B=A+B− with a pulsed electron high pressure mass spectrometer lead to ΔG01, ΔH01, and ΔS01. Equilibria involving SF6 as A and perfluoromethylcyclohexane C7F14 provide electron affinities E.A.(SF6)=1.05±0.1 eV and E.A.(C7F14)=1.06±0.15 eV. The kinetics of reactions (1) involving the above two compounds were studied. The rate constants kf for SF−6 +B=SF6+B− were found to increase with exothermicity of the reaction. The temperature dependence for kf was determined. B compounds leading to high exothermicities were associated with kf at the collision limit and essentially no temperature dependence. B of progressively lower electron affinity led to kf below the collision limit and negative temperature dependence, while B with the lowest E.A. but still leading to exothermic reaction produced lowest kf with positive temperature dependence. A model is provided explaining the above behavior. The known large change of geometry between SF−6 and SF6 introduces an internal barrier in the reaction coordinate for the reactions (1) involving SF6.