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 (k(1)), i-C4F9OCH3 (k(2)), n-C4F9OC(O)H (k(3)), and i-C4F9OC(O)H (k(4)) with OH radicals were studied in an 11.5-dm(3) environmental reaction chamber. k(1) and k(2) were determined to be (1.44 +/- 0.33) x 10(-12) exp[-(1450 +/- 70)/T] and (1.59 +/- 0.41) x 10(-12) exp[-(1470 +/- 80)/T] cm(3) molecule(-1) s(-1) at 253-328 K. At 298 K, k(3) and k(4) were deduced to be (1.71 +/- 0.32) x 10(-14) and (1.67 +/- 0.19) x 10(-14) cm(3) 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)(2)CFC(O)F, CF3C(O)F, and COF2. (C) 2011 Elsevier B. V. All rights reserved.