Abstract

Kinetics of the gas-phase reactions of •OH radicals with a series of fluoroesters were studied for the first time at 298 ± 3 K and atmospheric pressure. Relative rate coefficients were determined by in situ FTIR spectroscopy in nitrogen and GC-FID in air to monitor the decay of reactants and references. The following coefficient values (in 10−12 cm3/(molecule•sec)) were obtained for ethyl fluoroacetate (EFA), ethyl 4,4,4-trifluorobutyrate (ETB), and butyl fluoroacetate (BFA), respectively: k1 (EFA + OH) = 1.15 ± 0.25 by FTIR and 1.34 ± 0.23 by GC-FID; k2 (ETB + OH) = 1.61 ± 0.36 by FTIR and 2.02 ± 0.30 by GC-FID; k3 (BFA + OH) = 2.24 ± 0.37 by FTIR. Reactivity trends were developed and correlated with the number of CH3 and F substituents in the fluoroester, and structure-activity relationships (SARs) calculations were performed. In addition, the tropospheric lifetimes of EFA, ETB, and BFA upon degradation by OH radicals were calculated to be 9, 6, and 5 days, respectively, indicating that these fluorinated compounds could have a possible regional effect from the emission source. Relatively small photochemical ozone creation potentials of 9, 7, and 19 were estimated for EFA, ETB, and BFA, respectively. The Global Warming Potentials (GWPs) for EFA, ETB, and BFA were calculated for different time horizons. For a 20-year time horizon, the GWPs were 1.393, 0.063, and 0.062, respectively. In the case of a 100-year time horizon, the GWPs were 0.379, 0.017, and 0.017, and for a 500-year time horizon, the GWPs were 0.108, 0.005, and 0.005 for EFA, ETB, and BFA.

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