FTIR studies of the kinetics and mechanism for the reaction of Cl atom with formylchloride

The rate constant for the reaction Cl + CHClO → HCl + CClO was determined from relative decay rates of CHClO and CH3Cl inthe photolysis of mixtures containing Cl2 (∼1 torr), CH3Cl (∼1 torr), and O2 (∼0.1 torr) in 700 torr N2. In such mixtures CHClO was generated in situ as a principal product prior to complete consumption of O2. The value of k(Cl + CHClO)/k(Cl + CH3Cl) = 1.6 ± 0.2(3σ) combined with the literature value of k(Cl + CH3Cl) = 4.9 × 10−13 cm3/molecule sec gives k(Cl + CHClO) = 7.8 × 10−13 cm3/molecule sec at 298 ± 2 K, in excellent agreement with a previous value of (7.9 ± 1.5) × 10−13 cm3/molecule sec determined by Sanhueza and Heicklen [J. Phys. Chem., 79, 7 (1975)]. Thus this reaction is approximately 100 times slower than the corresponding reactions of aldehydes and alkanes with comparable CH bond energies (≤95 kcal/mol).