Kinetics and Mechanism of the Reaction of Fluorine Atoms with Pentafluoropropionic Acid

The kinetics of the reaction between fluorine atoms and pentafluoropropionic acid has been studied experimentally at T = 262–343 K. The overall reaction rate constant decreases with temperature: k 1(T) = 6.1 × 10–13 exp(+1166 K)/T) cm3 molecule–1 s–1. The potential energy surface of the reaction has been studied using quantum chemistry. The results were used in transition state theory calculations of the temperature dependences of the rate constants of the two channels of the reaction. The abstraction channel ultimately producing HF, C2F5, and CO2 is dominant at the experimental temperatures; the addition–elimination channel producing C2F5 and CF(O)OH becomes important above 1000 K.