The gas-phase reaction of Cl atom with 2,2,2-trifluoroethylacrylate (k1), 1,1,1,3,3,3-hexafluoroisopropylacrylate (k2), 2,2,2-trifluoroethylmethacrylate (k3) and 1,1,1,3,3,3-hexafluoroisopropylmethacrylate (k4), have been investigated at 298 K and 1 atm using the relative method by gas chromatography coupled with flame ionization detection (GC-FID). The values obtained are (in cm3 molecule−1 s−1): k1(Cl+CH2=CHC(O)OCH2CF3) = (2.41 ± 0.57) × 10−10, k2(Cl+CH2=CHC(O)OCH(CF3)2) = (1.39 ± 0.34) × 10−10, k3(Cl+CH2=C(CH3)C(O)OCH2CF3) = (2.22 ± 0.45) × 10−10, and k4(Cl +CH2=C(CH3)C(O)OCH(CF3)2 = (2.44 ± 0.52) × 10−10. Products identification studies were performed by solid-phase microextraction (SPME) method, with on-fiber products derivatization using o-(2,3,4,5,6-pentafluorobenzyl) hydroxylamine hydrochloride, coupled with gas chromatography with mass spectrometry detection (GC-MS). Chloroacetone, trifluoroacetaldehyde and formaldehyde were observed as degradation products and a general mechanism is proposed. Additionally, reactivity trends and atmospheric implications are discussed. Significant ozone photochemical potentials (POCP) and acidification potentials lead to local and or regional impact of the esters under study although is expected to a have a minor impact on global warming and climate change.
Atmospheric Environment – Elsevier
Published: Apr 1, 2018
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