Calculation of Anharmonic Effects for the Unimolecular Dissociation of CF3XCF2CH3 (X = Cl, Br) and CF3XCF2CD3 (X = Cl, Br)

Abstract The rate constants of the unimolecular dissociation of CF3XCF2CH3 /D3(X = Cl, Br) and 1,2-ClF (1,2-BrF) interchanging to give CF3CF2XCH3/D3 (X = Cl, Br) molecules and 2,3-FH (FD) elimination, were calculated using the RRKM theory. For the unimolecular reactions of CF3BrCF2CH3/D3, the anharmonic effect for the non deuterated case was more obvious. It has been also found that the isotope effects are ∼2–5 times in this study. The anharmonic effect of the reactions chlorinated hydrocarbons Cl-CF3CF2CH3/D3 are greater than that of brominated hydrocarbons Br-CF3CF2CH3/D3. Furthermore, the kinetics parameters of reaction mechanism for those reactions were given.