Rate coefficients, k, for the gas-phase reaction of the OH radical with CH(2)=CHF (k(1)) and CH(2)=CF(2) (k(2)) were measured under pseudo-first-order conditions in OH using pulsed laser photolysis to produce OH and laser-induced fluorescence (PLP-LIF) to detect it. Rate coefficients were measured over a range of temperature (220-373 K) and bath gas pressure (20-600 Torr; He, N(2)). The rate coefficients were found to be independent of pressure. The measured rate coefficient for reaction 1 at room temperature was k(1)(296 K) = (5.18 +/- 0.50) x 10(-12) cm(3) molecule(-1) s(-1), independent of pressure, and the temperature dependence is given by the Arrhenius expression k(1)(T) = (1.75 +/- 0.20) x 10(-12) exp[(316 +/- 25)/T] cm(3) molecule(-1) s(-1); the rate coefficients for reaction 2 were k(2)(296 K) = (2.79 +/- 0.25) x 10(-12) cm(3) molecule(-1) s(-1) and k(2)(T) = (1.75 +/- 0.20) x 10(-12) exp[(140 +/- 20)/T] cm(3) molecule(-1) s(-1). The quoted uncertainties are 2sigma (95% confidence level) and include estimated systematic errors. The fall-off parameters for reaction 2 of k(infinity) = 3 x 10(-12) cm(3) molecule(-1) s(-1) and k(0)(296 K) = 1.8 x 10(-28) cm(6) molecule(-2) s(-1) with F(c) = 0.6 reproduce the room temperature data obtained in this study combined with the low pressure rate coefficient data from Howard (J. Chem. Phys. 1976, 65, 4771). OH radical formation was observed for reactions 1 and 2 in the presence of O(2), and the mechanism was investigated using (18)OH and OD rate coefficient measurements with CH(2)=CHF and CH(2)=CF(2) over a range of temperature (260-373 K) and pressure (20-100 Torr, He). Quantum chemical calculations using density functional theory (DFT) were used to determine the geometries and energies of the reactants and adducts formed in reactions 1 and 2 and the peroxy radicals formed following the addition of O(2). The atmospheric lifetimes of CH(2)=CHF and CH(2)=CF(2) due to loss by reaction with OH are approximately 2 and 4 days, respectively. Infrared absorption spectra of CH(2)=CHF and CH(2)=CF(2) were measured, and global warming potentials (GWP) values of 0.7 for CH(2)=CHF and 0.9 for CH(2)=CF(2) were obtained for the 100 year time horizon.

Rate coefficients for the reaction between HO2 and ClO radicals were obtained using the discharge-flow/mass-spectrometry technique at total pressures of 1.1−1.7 Torr of He, and between 298 and 215 K. The room-temperature rate constant, determined using seven different combinations of HO2 and ClO precursors, was found to be (7.1 ± 1.8) × 10-12 (±2σ) cm3 s-1. The temperature-dependent overall reaction rate coefficient is described by k (3) (298−215 K) = (7.1 ± 0.4) × 10-12 exp(−16 ± 17/T) cm3 s-1. The previous observation of a strong negative temperature dependence in the title reaction below 298 K was not observed, resulting in a significantly lower rate coefficient at stratospheric temperatures. HOCl was the only product of the reaction, and an upper limit of 1% for the branching ratio for the formation of O3 and HCl was obtained at the low pressures of these experiments.