Kinetics and mechanism of gas-phase reactions of n-C4F9OCH3, i-C4F9OCH3, n-C4F9OC(O)H, and i-C4F9OC(O)H with OH radicals in an environmental reaction chamber at 253–328 K

The rate constants of the reactions of n-C4F9OCH3 (k1), i-C4F9OCH3 (k2), n-C4F9OC(O)H (k3), and i-C4F9OC(O)H (k4) with OH radicals were studied in an 11.5-dm3 environmental reaction chamber. k1 and k2 were determined to be (1.44 ± 0.33) × 10–12 exp[–(1450 ± 70)/T] and (1.59 ± 0.41) × 10–12 exp[–(1470 ± 80)/T] cm3 molecule–1 s–1 at 253–328 K. At 298 K, k3 and k4 were deduced to be (1.71 ± 0.32) × 10–14 and (1.67 ± 0.19) × 10–14 cm3 molecule–1 s–1. The observed products of the reaction of n-C4F9OCH3 with OH radicals were n-C4F9OC(O)H, CF3CF2CF2C(O)F, and COF2, and those for the reaction of i-C4F9OCH3 were i-C4F9OC(O)H, (CF3)2CFC(O)F, CF3C(O)F, and COF2.