Kinetics and Mechanism of (CF3)2CHOCH3 Reaction with OH Radicals in an Environmental Reaction Chamber

The atmospheric chemistry of (CF3)2CHOCH3, a possible HCFC/HFC alternative, was studied using a smog chamber/FT-IR technique. OH radicals were prepared by the photolysis of ozone in a 200-Torr H2O/O3/O2 gas mixture held in an 11.5-dm3 temperature-controlled chamber. The rate constant, k 1, for the reaction of (CF3)2CHOCH3 with OH radicals was determined to be (1.40 ± 0.28) × 10-12 exp[(−550 ± 60)/T] cm3 molecule-1 s-1 by means of a relative rate method at 253−328 K. The value of k 1 at 298 K was (2.25 ± 0.04) × 10-13 cm3 molecule-1 s-1. The random errors are reported with ±2 standard deviations, and potential systematic errors of 15% could increase k 1. In considering OH-radical reactions, we estimated the tropospheric lifetime of (CF3)2CHOCH3 to be 2.0 months using the rate constant at 288 K. The degradation mechanism of (CF3)2CHOCH3 initiated by OH radicals was also investigated using FT-IR spectroscopy at 298 K. Products (CF3)2CHOC(O)H, CF3C(OH)2CF3, CF3C(O)OCH3, and COF2 were identified and quantified. The branching ratio, k 1a/k 1b, was estimated to be 2.1:1 for reactions (CF3)2CHOCH3 + OH → (CF3)2CHOCH2 •+ H2O (k 1a) and (CF3)2CHOCH3 + OH → (CF3)2C•OCH3 + H2O (k 1b).