Temperature‐Dependence of the Rates of Reaction of Trifluoroacetic Acid with Criegee Intermediates

Abstract

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(CH₂ OO + CF₃ COOH)=(3.4±0.3)×10^-10 cm³ s^-1 and k((CH₃ )₂ COO + CF₃ COOH)=(6.1±0.2)×10^-10 cm³ s^-1 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 [cm³ s^-1 ]=(3.8±2.6)×10^-18 T² exp((1620±180)/T) + 2.5×10^-10 and k [cm³ s^-1 ]=(4.9±4.1)×10^-18 T² exp((1620±230)/T) + 5.2×10^-10 for the CH₂ OO + CF₃ COOH and (CH₃ )₂ COO + CF₃ COOH reactions, respectively. The consequences are explored for removal of TFA from the atmosphere by reaction with biogenic Criegee intermediates.