Rate of decomposition of hexafluoroazomethane and the absolute rate of recombination of trifluoromethyl radical at higher temperatures

The unimolecular homogeneous decomposition of hexafluoroazomethane was studied in a VLPP apparatus in the temperature range 720–1050 K and is consistent with the following Arrhenius parameters: at 900 K, where the A factor was assumed to be the same as for 2,2′-azoisobutane. The homogeneous rate of recombination of ·CF₃ radicals at temperatures around 1000 K was also studied under VLPP conditions and was found to be in the fall-off region, corresponding to k/k^∞ = 8.5 × 10^?3 when a rotational transition-state model was used. This model predicts an essentially constant value of k_r^∞ of 10^9.7 over the temperature range 300–1000 K.