%0 Journal Article %1 Baasandorj:2010p3316 %A Baasandorj, Munkhbayar %A Knight, Gary %A Papadimitriou, Vassileios C %A Talukdar, Ranajit K %A Ravishankara, A. R %A Burkholder, James B %D 2010 %J Journal of Physical Chemistry A %K Atmospheric Chemistry, Constants, Equation, Kinetics Low-Pressures, Master Oh Radicals, Rate Reactions, Spectra, Temperature, Thermal Unimolecular Vinyl-Chloride, %N 13 %P 4619--4633 %R 10.1021/jp100527z %T Rate Coefficients for the Gas-Phase Reaction of the Hydroxyl Radical with CH2 = CHF and CH2 = CF2 %U http://pubs.acs.org/doi/abs/10.1021/jp100527z %V 114 %X Rate coefficients, k, for the gas-phase reaction of the OH radical with CH2 = CHF (k(1)) and CH2 = CF2 (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 Tom 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 2 sigma (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 (OH)-O-18 and OD rate coefficient measurements with CH2 = CHF and CH2 = CF2 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 CH2 = CHF and CH2 = CF2 due to loss by reaction with OH are approximately 2 and 4 days, respectively. Infrared absorption spectra of CH2 = CHF and CH2 = CF2 were measured, and global warming potentials (GWP) values of 0.7 for CH2 = CHF and 0.9 for CH2 = CF2 were obtained for the 100 year time horizon.

@article{Baasandorj:2010p3316, abstract = {Rate coefficients, k, for the gas-phase reaction of the OH radical with CH2 = CHF (k(1)) and CH2 = CF2 (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 Tom 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 2 sigma (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 (OH)-O-18 and OD rate coefficient measurements with CH2 = CHF and CH2 = CF2 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 CH2 = CHF and CH2 = CF2 due to loss by reaction with OH are approximately 2 and 4 days, respectively. Infrared absorption spectra of CH2 = CHF and CH2 = CF2 were measured, and global warming potentials (GWP) values of 0.7 for CH2 = CHF and 0.9 for CH2 = CF2 were obtained for the 100 year time horizon.}, added-at = {2010-06-22T19:38:37.000+0200}, affiliation = {Natl Ocean {\&} Atmospher Adm, Earth Syst Res Lab, Div Chem Sci, Boulder, CO 80305 USA}, author = {Baasandorj, Munkhbayar and Knight, Gary and Papadimitriou, Vassileios C and Talukdar, Ranajit K and Ravishankara, A. R and Burkholder, James B}, biburl = {https://www.bibsonomy.org/bibtex/255043b3cd53d6d3d6084f8114c51f17c/gsmith}, date-added = {2010-04-29 13:28:29 -0400}, date-modified = {2010-06-21 15:20:04 -0400}, doi = {10.1021/jp100527z}, interhash = {ab80f291530a1ea72d215d2dc601043c}, intrahash = {55043b3cd53d6d3d6084f8114c51f17c}, journal = {Journal of Physical Chemistry A}, keywords = {Atmospheric Chemistry, Constants, Equation, Kinetics Low-Pressures, Master Oh Radicals, Rate Reactions, Spectra, Temperature, Thermal Unimolecular Vinyl-Chloride,}, language = {English}, local-url = {file://localhost/Users/geoffreysmith/Documents/Papers/Journal%20of%20Physical%20Chemistry%20A/2010/Journal%20of%20Physical%20Chemistry%20A,%20114,%204619-4633%202010.pdf}, month = Jan, number = 13, pages = {4619--4633}, pmid = {000276096800019}, rating = {0}, timestamp = {2010-06-22T19:39:20.000+0200}, title = {Rate Coefficients for the Gas-Phase Reaction of the Hydroxyl Radical with CH2 = CHF and CH2 = CF2}, uri = {papers://E88B624E-D406-46FF-9D95-BB9C1AAE3FDC/Paper/p3316}, url = {http://pubs.acs.org/doi/abs/10.1021/jp100527z}, volume = 114, year = 2010 }