Thermal chemiluminescence from γ-irradiated polytetrafluoroethylene and its emission mechanism: kinetic analysis and bond dissociation energy of fluoroperoxide group

Temperature dependence of the time evolution of chemiluminescence intensity from γ-irradiated polytetrafluoroethylene was examined by heating isothermally in the range of 150 and 200 °C. Kinetic analysis was carried out to estimate the rate constants, from which the dissociation energy of the OO bond in the fluoroperoxide group was determined to be 97 ± 4 kJ mol−1, being consistent with the corresponding value for small fluorocarbon model systems obtained by quantum chemical calculations. This strongly supports the emission mechanism [CF(OOF)CF2 → COCF2 + OF2 + hν] proposed in our previous paper to explain chemiluminescence from the γ-irradiated polytetrafluoroethylene.