Shock wave and modeling study of the thermal decomposition reactions of pentafluoroethane and 2-H-heptafluoropropane

Abstract

The thermal decomposition reactions of CF₃CF₂H and CF₃CFHCF₃ have been studied in shock waves by monitoring the appearance of CF₂ radicals. Temperatures in the range 1400–2000 K and Ar bath gas concentrations in the range (2–10) × 10⁻⁵ mol cm⁻³ were employed. It is shown that the reactions are initiated by C–C bond fission and not by HF elimination. Differing conclusions in the literature about the primary decomposition products, such as deduced from experiments at very low pressures, are attributed to unimolecular falloff effects. By increasing the initial reactant concentrations in Ar from 60 to 1000 ppm, a retardation of CF₂ formation was observed while the final CF₂ yields remained close to two CF₂ per C₂F₅H or three CF₂ per C₃F₇H decomposed. This is explained by secondary bimolecular reactions which lead to comparably stable transient species like CF₃H, releasing CF₂ at a slower rate. Quantum-chemical calculations and kinetic modeling help to identify the reaction pathways and provide estimates of rate constants for a series of primary and secondary reactions in the decomposition mechanism.