Atmospheric chemistry of (Z)-CF3CH═CHCF3: OH radical reaction rate coefficient and global warming potential. 2011

Munkhbayar Baasandorj, and A R Ravishankara, and James B Burkholder
Earth System Research Laboratory, Chemical Sciences Division, National Oceanic and Atmospheric Administration, 325 Broadway, Boulder, Colorado 80305-3328, USA.

Rate coefficients, k, for the gas-phase reaction of the OH radical with (Z)-CF(3)CH═CHCF(3) (cis-1,1,1,4,4,4-hexafluoro-2-butene) were measured under pseudo-first-order conditions in OH using pulsed laser photolysis (PLP) to produce OH and laser-induced fluorescence (LIF) to detect it. Rate coefficients were measured over a range of temperatures (212-374 K) and bath gas pressures (20-200 Torr; He, N(2)) and found to be independent of pressure over this range of conditions. The rate coefficient has a non-Arrhenius behavior that is well-described by the expression k(1)(T) = (5.73 ± 0.60) × 10(-19) × T(2) × exp[(678 ± 10)/T] cm(3) molecule(-1) s(-1) where k(1)(296 K) was measured to be (4.91 ± 0.50) × 10(-13) cm(3) molecule(-1) s(-1) and the uncertainties are at the 2σ level and include estimated systematic errors. Rate coefficients for the analogous OD radical reaction were determined over a range of temperatures (262-374 K) at 100 Torr (He) to be k(2)(T) = (4.81 ± 0.20) × 10(-19) × T(2) × exp[(776 ± 15)/T], with k(2)(296 K) = (5.73 ± 0.50) × 10(-13) cm(3) molecule(-1) s(-1). OH radical rate coefficients were also measured at 296, 345, and 375 K using a relative rate technique and found to be in good agreement with the PLP-LIF results. A room-temperature rate coefficient for the O(3) + (Z)-CF(3)CH═CHCF(3) reaction was measured using an absolute method with O(3) in excess to be <6 × 10(-21) cm(3) molecule(-1) s(-1). The atmospheric lifetime of (Z)-CF(3)CH═CHCF(3) due to loss by OH reaction was estimated to be ~20 days. Infrared absorption spectra of (Z)-CF(3)CH═CHCF(3) measured in this work were used to determine a (Z)-CF(3)CH═CHCF(3) global warming potential (GWP) of ~9 for the 100 year time horizon. A comparison of the OH reactivity of (Z)-CF(3)CH═CHCF(3) with other unsaturated fluorinated compounds is presented.

UI MeSH Term Description Entries
D011312 Pressure A type of stress exerted uniformly in all directions. Its measure is the force exerted per unit area. (McGraw-Hill Dictionary of Scientific and Technical Terms, 6th ed) Pressures
D006845 Hydrocarbons, Fluorinated Inert liquid or gaseous halocarbon compounds in which FLUORINE replaces some or all HYDROGEN atoms. Fluorinated Hydrocarbons
D001272 Atmosphere The gaseous envelope surrounding a planet or similar body. (From Random House Unabridged Dictionary, 2d ed) Atmospheres
D013696 Temperature The property of objects that determines the direction of heat flow when they are placed in direct thermal contact. The temperature is the energy of microscopic motions (vibrational and translational) of the particles of atoms. Temperatures
D015394 Molecular Structure The location of the atoms, groups or ions relative to one another in a molecule, as well as the number, type and location of covalent bonds. Structure, Molecular,Molecular Structures,Structures, Molecular
D017665 Hydroxyl Radical The univalent radical OH. Hydroxyl radical is a potent oxidizing agent.
D057232 Global Warming Increase in the temperature of the atmosphere near the Earth's surface and in the troposphere, which can contribute to changes in global climate patterns. Warming, Global

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