High-Temperature Fluorocarbon Chemistry Revisited

The thermal dissociation reactions of C₂F₄ and C₂F₆ were studied in shock waves over the temperature range 1000-4000 K using UV absorption spectroscopy. Absorption cross sections of C₂F₄, CF₂, CF, and C₂ were derived and related to quantum-chemically modeled oscillator strengths. After confirming earlier results for the dissociation rates of C₂F₄, CF₃, and CF₂, the kinetics of secondary reactions were investigated. For example, the reaction CF₂ + CF₂ → CF + CF₃ was identified. Its rate constant of 10¹⁰ cm³ mol^-1 s^-1 near 2400 K is markedly larger than the limiting high-pressure rate constant of the dimerization CF₂ + CF₂ → C₂F₄, suggesting that the reaction follows a different path. When the measurements of the thermal dissociation CF₂ (+Ar) → CF + F (+Ar) are extended to temperatures above 2500 K, the formation of C₂ radicals was shown to involve the reaction CF + CF → C₂F + F (modeled rate constant 8.0 × 10¹² (T/3500 K)^1.0 exp(-4400 K/T) cm³ mol^-1 s^-1) and the subsequent dissociation C₂F (+Ar) → C₂ + F + (Ar) (modeled limiting low-pressure rate constant 3.0 × 10¹⁶ (T/3500 K)^-4.0 exp(-56880 K/T) cm³ mol^-1 s^-1). This mechanism was validated by monitoring the dissociation of C₂ at temperatures close to 4000 K. Temperature- and pressure-dependences of rate constants of reactions involved in the system were modeled by quantum-chemistry based rate theory.