Shock wave and modeling study of the reaction CF₄ (+M) ⇔ CF₃ + F (+M)

The thermal decomposition of CF₄ (+Ar) → CF₃ + F (+Ar) was studied in shock waves over the temperature range 2000–3000 K varying the bath gas concentration [Ar] between 4 × 10⁻⁶ and 9 × 10⁻⁵ mol cm⁻³. It is shown that the reaction corresponds to the intermediate range of the falloff curve. By combination with room temperature data for the reverse reaction CF₃ + F (+He) → CF₄ (+He) and applying unimolecular rate theory, falloff curves over the temperature range 300–6000 K are modeled. A comparison with the reaction system CH₄ (+M) ⇔ CH₃ + H (+M) is made.