Atmospheric Chemistry of (CF3)(2)CHOCH3, (CF3)(2)CHOCHO, and CF3C(O)OCH3

作者：Osterstrom Freja From; Wallington Timothy J^*; Andersen Mads P Sulbaek; Nielsen Ole John

来源：Journal of Physical Chemistry A, 2015, 119(42): 10540-10552.

DOI：10.1021/acs.jpca.5b08204

Smog chambers with in situ FTIR detection were used to measure rate coefficients in 700 Torr of air and 296 +/- 2 K of: k(Cl+(CF3)(2)CHOCH3) = (5.41 +/- 1.63) x 10(-12), k(Cl+(CF3)(2)CHOCHO) = (9.44 +/- 1.81) x 10(-15), k(Cl+CF3C(O)-OCH3) = (6.28 +/- 0.98) x 10(-14), k(OH+(CF3)(2)CHOCH3) = (1.86 +/- 0.41) x 10(-13), and k(OH+(CF3)(2)CHOCHO) = (2.08 +/- 0.63) x 10(-14) cm(3) molecule(-1) s(-1). The Cl atom initiated oxidation of (CF3)(2)CHOCH3 gives (CF3)(2)CHOCHO in a yield indistinguishable from 100%. The OH radical initiated oxidation of (CF3)(2)CHOCH3 gives the following products (molar yields): (CF3)(2)CHOCHO (76 +/- 8)%, CF3C(O)OCH3 (16 +/- 2)%, CF3C(O)CF3 (4 +/- 1)%, and C(O)F-2 (45 +/- 5)%. The primary oxidation product (CF3)(2)CHOCHO reacts with Cl atoms to give secondary products (molar yields): CF3C(O)CF3 (67 +/- 7)%, CF3C(O)OCHO (28 +/- 3)%, and C(O)F-2 (118 +/- 12)%. CF3C(O)OCH3 reacts with Cl atoms to give: CF3C(O)OCHO (80 +/- 8)% and C(O)F-2 (6 +/- 1)%. Atmospheric lifetimes of (CF3)(2)CHOCH3, (CF3)(2)CHOCHO, and CF3C(O)OCH3 were estimated to be 62 days, 1.5 years, and 220 days, respectively. The 100-year global warming potentials (GWPs) for (CF3)(2)CHOCH3, (CF3)(2)CHOCHO, and CF3C(O)OCH3 are estimated to be 6, 121, and 46, respectively. A comprehensive description of the atmospheric fate of (CF3)(2)CHOCH3 is presented.

• 出版日期2015-10-22