The rate coefficients for gas-phase reaction of trifluoroacetic acid (TFA) with two Criegee intermediates, formaldehyde oxide and acetone oxide, decrease with increasing temperature in the range 240-340 K. The rate coefficients k(CH OO + CF COOH)=(3.4±0.3)×10 cm s and k((CH ) COO + CF COOH)=(6.1±0.2)×10 cm s at 294 K exceed estimates for collision-limited values, suggesting rate enhancement by capture mechanisms because of the large permanent dipole moments of the two reactants. The observed temperature dependence is attributed to competitive stabilization of a pre-reactive complex. Fits to a model incorporating this complex formation give k [cm s ]=(3.8±2.6)×10 T exp((1620±180)/T) + 2.5×10 and k [cm s ]=(4.9±4.1)×10 T exp((1620±230)/T) + 5.2×10 for the CH OO + CF COOH and (CH ) COO + CF COOH reactions, respectively. The consequences are explored for removal of TFA from the atmosphere by reaction with biogenic Criegee intermediates.
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| http://dx.doi.org/10.1002/anie.201703700 | DOI Listing |
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