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

Abstract

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.