Chemistry, Physical
; Physics, Atomic, Molecular & Chemical
WOS研究方向:
Chemistry
; Physics
英文摘要:
The rate coefficients, k, for the gas-phase reaction of the OH radical and Cl-atom with (E)- and (Z)-CF3CF=CFCF3 were measured using a relative rate technique over a range of temperature (240-375 K) and bath gas pressure (50-630 Torr, He). The obtained rate coefficients were found to be independent of pressure under these conditions. The obtained rate coefficients for the reaction of Cl-atom with (E)- and (Z)-CF3CF=CFCF3 at 296 K were k(1)(296 K) = (7.23 +/- 0.3) x 10(-12) cm(3) molecule(-1) s(-1) and k(2)(296 K) = (6.70 +/- 0.3) x 10(-12) cm(3) molecule(-1) s(-1), respectively, with the temperature dependence described by the Arrhenius expressions: k(1)(T) = (3.47 +/- 0.35) x 10(-12) exp[(210 +/- 25)/T] cm(3) molecule(-1) s(-1) and k(2)(T) = (3.37 +/- 0.35) x 10(-12) exp[(199 +/- 25)/T] cm(3) molecule(-1) s(-1). The rate coefficients for the OH radical reaction with (E)- and (Z)-CF3CF=CFCF3 were found to be k(3)(296-375 K) = (4.34 +/- 0.45) x 10(-13) cm(3) molecule(-1) s(-1) and k(4)(296-375 K) = (3.30 +/- 0.35) x 10(-13) cm(3) molecule(-1) s(-1), respectively. The quoted rate coefficient uncertainties are 2 sigma (95% confidence level) and include estimated systematic errors. The rate coefficients for the reaction of OH with a mixture of the two stereoisomers were determined using a pulsed laser photolysis-laser-induced fluorescence (PLP-LIF) technique for comparison with previous kinetic measurements using stereoisomer mixtures. The effective rate coefficient for the 0.7/0.3 (E)/(Z) stereoisomer sample was found to be nearly independent of temperature over the range 222-375 K with a value of (4.47 +/- 0.36) x 10(-13) cm(3) molecule(-1) s(-1). The atmospheric lifetimes for (E)- and (Z)-CF3CF=CFCF3 due to OH-reactive loss are estimated to be 25 and 35 days, respectively. The lifetime-corrected radiative efficiencies (W m(-2) ppb(-1)) and 100 year time horizon global warming potentials derived in this work are 0.05 and 1.2 for (E)-CF3CF=CFCF3 and 0.13 and 4.1 for (Z)-CF3CF=CFCF3. The photochemical ozone creation potentials for (E)- and (Z)-CF3CF=CFCF3 are estimated to be 2.5 and 2.1, respectively.
1.NOAA, Earth Syst Res Lab, Chem Sci Div, 325 Broadway, Boulder, CO 80305 USA 2.Univ Colorado, Cooperat Inst Res Environm Sci, Boulder, CO 80309 USA 3.Utah Div Air Qual, Salt Lake City, UT 84114 USA 4.Univ Crete, Dept Chem, Lab Photochem & Chem Kinet, Iraklion, Crete, Greece
Recommended Citation:
Baasandorj, Munkhbayar,Papadimitriou, Vassileios C.,Burkholder, James B.. Rate Coefficients for the Gas-Phase Reaction of (E)- and (Z)-CF3CF=CFCF3 with the OH Radical and Cl-Atom[J]. JOURNAL OF PHYSICAL CHEMISTRY A,2019-01-01,123(24):5051-5060