Kinetics of the thermal decomposition of CH2F2

Abstract

Kinetics of the thermal decomposition reaction CH2F2 → CHF + HF was studied by laser absorption measurements in a shock tube. The rate constants were determined by analyzing temporal profiles of HF produced in pyrolysis of CH2F2 over the temperature range 1577–2214 K at pressure of ∼100 kPa in Ar bath. The results were well reproduced by master equation analysis based on RRKM theory and classical trajectory calculations, which gave the following rate constant expressions: k∞ = 2.34 × 1015 exp(−41,550 K/T) s−1, k0 = 5.33 × 1025 (T/K)−8.635 exp(−44,190 K/T) cm3 molecule−1 s−1, and Fcent = 0.13.