Direct detection of CF2 and computer modeling of its appearance in the fluorination of CH2F2

The branched chain reaction between CH2F2 and F2 is studied in a miniature tubular reactor having a diameter of 1.1 mm. The gases at the end of the tube expand into a low‐pressure chamber and are analyzed by molecular beam detection. The branching intermediate CF2 is detected directly at low ionization energies. An approximate quantitative reaction model for the fluorination of CH2F2 is proposed and discussed. The influence of the unknown rate constants in this scheme on the course of the reaction is examined. For the most reasonable set of rate constants the unknown rate constant for the branching reaction CF2 + F2 → CF3 + F at 550 K is found to be log k = 10.7 [cm3/mol·s].