Abstract
Absolute rate coefficient measurements have been carried out for the reactions of Cl atoms with propene and a series of 3-halopropenes, at room temperature (298 ± 2) K using a newly constructed laser photolysis-resonance fluorescence (PLP-RF) system. The rate coefficients obtained (in units of cm3 molecule−1 s−1) are: propene (1.40± 0.24) ×10−10, 3-fluoropropene (4.92 ± 0.42) ×10−11, 3-chloropropene (7.47 ± 1.50) × 10−11, 3-bromopropene (1.23± 0.14) ×10−10 and 3-iodopropene (1.29± 0.15) ×10−10. In order to test this new system, the reactions of Cl atoms with acetone and isoprene have also been studied and compared with data previously reported. The rate coefficients determined at room temperature for these last two reactions are (2.93 ± 0.20) ×10−12 cm3 molecule−1 s− 1 and (3.64± 0.20)×10−10 cm3 molecule−1 s−1, respectively. The measured values were independent of pressure over the range 20–200 Torr. The influence of the different halogen atoms substituents on the reactivity of these alkenes with Cl atoms as well as the atmospheric implications of these measurements are studied and discussed for the first time in this work and compared with the reactivity with NO3 and OH radicals.
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Aird, R.W. S., Canosa-Mas, C. E., Cook, D. J., Marston, G., Monks, P. S., Wayne, R. P., and Ljungstrom, E., 1992: Kinetics of the reactions of the nitrate radical with a series of halogenobutenes. A study of the effect of substituents on the rate of addition of NO3 to alkenes, J. Chem. Soc. Faraday Trans. 88, 1093–1099.
Atkinson, R., Aschmann, S. M., and Goodman, M. A., 1987: Kinetics of the gas-phase reactions of NO3 radicals with a series of alkynes, haloalkenes, and unsaturated aldehydes, Int. J. Chem. Kinet. 19, 299–307.
Atkinson, R., 1997a: Gas phase tropospheric chemistry of volatile organic compounds, 1. Alkanes and alkenes, J. Phys. Chem. Ref. Data 26, 215–290.
Atkinson, R., Baulch, D. L., Cox, R. A., Hampson, Jr., R. F., Kerr, J. A., Rossi, M. J., and Troe, J., 1997b: Evaluated kinetic, photochemical and heterogeneous data for atmospheric chemistry: Supplement V, IUPAC subcommittee on gas kinetic data evaluation for atmospheric chemistry, J. Phys. Chem. Ref. Data 26, 521–1011.
Bedjanian, Y., Laverdet, G., and Le Bras, G., 1998: Low-pressure study of the reaction of Cl atoms with isoprene, J. Phys. Chem. A. 102(6), 953–959.
DeMore, W. B., Sander, S. P., Gold en, D. M., Hampson, R. F., Kurylo, M. J., Howard, C. J., Ravishankara, A. R., Kolb, C. E., and Molina, M. J., 1997: Chemical Kinetics and Photochemical Data for Use in Stratospheric Modeling, Evaluation No. 12, JPL Publication No. 97-4; Jet propulsion Laboratory, Pasadena, CA.
Finlayson-Pitts, B. J., 1993: Chlorine atoms as a potential tropospheric oxidant in the marine boundary layer, Research on Chemical Intermediates 19, 235–249.
Goliff, W. S. and Rowland, F. S., 1997: Methyl chloride formation by gas phase thermal chlorine atom reaction with methyl iodide and methyl bromide, Geophys. Res. Lett. 24, 3029–3032.
Graedel, T. E. and Keene, W. C., 1995: Tropospheric budget of reactive chlorine [Review], Glob. Biogeochem. Cycles 9(1), 47–77.
Grosjean, E. and Grosjean, D., 1996: Rate constants for the gas-phase reaction of ozone with 1, 1-disubstituted alkenes, Int. J. Chem. Kinet 28, 911–918.
Jenkin, M. E., Murrells, T. P., Shalliker, S. J., and Hayman, G. D., 1993: Kinetics and product study of the self-reactions of allyl and allyl peroxy radicals at 296 K, J. Chem. Soc. Faraday Trans. 89, 433–446.
Jobson, B. T., Niki, H., Yokouchi, Y., Bottenheim, J., Hopper, F., and Leaitch, R., 1994: Measurements of C2-C6 hydrocarbons during the polar sunrise 1992 experiment-evidence for Cl atom and Br atom, J. Geophys. Res.-Atmos. 99, 25,355–25,368.
Kaiser, E. W. and Wallington, T. J., 1996: Pressure dependence of the reaction Cl + C3H6, J. Phys. Chem. 100, 9788–9793.
Keene, W. C., Pszenny, A. A. P., Jacobs, D. J., Duce, R. A., Galloway, J. N., Schultz-Tokos, J. J., Sieering, H., and Boatman, J. F. 1990: The geochemical cycling of reactive chlorine through the marine troposphere, Glob. Biogeochem. Cycles 4, 407–430.
Le Calve S., Hitier, D., Le Bras, G., and Mellouki, A., 1998: Kinetic studies of OH reactions with a series of ketones, J. Phys. Chem. A. 102(24), 4579–4584.
Marston, G., Monks, P. S., Canosa-Mas, C. E., and Wayne, R. P., 1993: Correlations between rate parameters and calculated molecular properties in the reactions of the nitrate radical with alkenes, J. Chem. Soc. Faraday Trans. 89, 3899–3905.
Martínez, E., Cabañas, B., Aranda, A., Martin, P., and Wayne, R. P., 1996a: Kinetic study of the reactions of NO3 with 3-chloropropene, 3-bromopropene and 3-iodopropene using LIF detection, J. Chem. Soc. Faraday Trans. 92, 4385–4389.
Martínez, E., Cabañas, B., Aranda, A., Martin, P., and Wayne, R. P., 1996b: Temperature dependence of the reactions of the nitrate radical with the dichloroalkenes followed by LIF detection, J. Chem. Soc. Faraday Trans. 92, 53–58.
Martínez, E., Cabañas, B., Aranda A., Martin, P., and Salgado, S., 1997: A temperature dependence study of the gas-phase reaction of the nitrate radical with 3-fluoropropene followed by laser induced fluorescence detection, Int. J. Chem. Kinet. 29, 927–932.
Notario, A., Mellouki, A., and Le Bras, G., 1997: Kinetic of Cl atom reactions with butadienes including isoprene, Chem. Phys. Lett. 281, 421–425.
Notario, A., Mellouki, A., and Le Bras, G., 2000: Rate constants for the gas-phase reactions of chlorine atoms with a series of ketones, Int. J. Chem. Kinet. 32, 62–66.
Olsson, B. E. R., Hallquist, M., Ljungstrom, E., and Davidsson I., 1997: A kinetic study of chlorine radical reactions with ketones by laser photolysis technique, Int. J. Chem. Kinet. 29, 195–201.
Pszenny, A. A. P., Keene, W. C., Jacob, D. J., Fan, S., Maben, J. R., Zetwo, M. P., Springer-Young, M., and Galloway J. N., 1993: Evidence of inorganic chlorine gases other than hydrogen chloride in marine surface air, Geophys. Res. Lett. 20, 699–702.
Ragains, M. L. and Finlayson-Pitts, B. J., 1997: Kinetics and mechanism of the reaction of Cl atoms with 2-methyl-1,3-butadiene (isoprene) at 298 K, J. Phys. Chem. A. 101, 1509–1517.
Singh, H. B. and Kasting, J. F., 1988: Chlorine-hydrocarbon photochemistry in the marine troposphere and lower stratosphere, J. Atmos. Chem. 7, 261–285.
Spicer, C. W., Chapman, E. G., Finlayson-Pitts, B. J., Plastridge, R. A., Hubbe, J. M., Fast, J. D., and Berkowitz, C. M., 1998: Unexpectedly high concentrations of molecular chlorine in coastal air, Nature 394, 353–356.
Stutz, J., Ezell, M. J., Ezell, A. A., and Finlayson-Pitts, B. J., 1998: Rate constants and kinetic isotope effects in the reactions of atomic chlorine with n-butane and simple alkenes at room temperature, J. Phys. Chem. A. 102(44), 8510–8519.
Timonen, R. S. and Gutman, D., 1986: Kinetics of the reactions of methyl, ethyl, isopropyl, and tert-butyl radicals with molecular chlorine, J. Phys. Chem. 90, 2987–2991.
Timonen, R. S., Russell, J. J., Sarzynski, D., and Gutman, D., 1987: Kinetics of the reactions of unsaturated hydrocarbon free radicals (vinyl, allyl, and propargyl) with molecular chlorine, J. Phys. Chem. 91, 1873–1877.
Tsang, W., 1991: Chemical kinetic data base for combustion chemistry. Part V. Propene, J. Phys. Chem. Ref. Data 20, 221–273.
Tuazon, E. C., Atkinson, R., and Aschmann, S. M., 1990: Kinetics and products of the gas-phase reactions of the OH radical and O3 with allyl chloride and benzyl chloride at room temperature, Int. J. Chem. Kinet. 22, 981–986.
Wallington, T. J., Andino, J. M., Ball, J. C., and Japar, S. M., 1990: Fourier transform infrared studies of the reaction of Cl atoms with PAN, PPN, CH3OOH, HCOOH, CH3COCH3 and CH3COC2H5 at 295 K, J. Atmos. Chem. 10, 301–307.1
Wallington, T. J., Guschin, A., and Hurley, M. D., 1998: A kinetic study of chlorine radical reactions with ketones by laser-photolysis technique, Int. J. Chem. Kinet. 304), 309–310.
Wayne, R. P., Barnes, I., Biggs, P., Burrows, J. P., Canosa-Mas, C. E., Hjorth, J., Le Bras, G., Moortgat, G. K., Perner, D., Poulet, G., Restelli, G., and Sidebottom, H., 1991: The nitrate radical: physics, chemistry and the atmosphere, Atmos. Environ. 25A, 1–206.
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Albaladejo, J., Notario, A., Cuevas, C.A. et al. A Pulsed Laser Photolysis-Resonance Fluorescence Kinetic Study of the Atmospheric Cl Atom-Initiated Oxidation of Propene and a Series of 3-Halopropenes at Room Temperature. Journal of Atmospheric Chemistry 45, 35–50 (2003). https://doi.org/10.1023/A:1024073012242
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DOI: https://doi.org/10.1023/A:1024073012242