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Methyl Methacrylate In The Atmosphere: Oh- And Cl-Initiated Oxidation In The Gas Phase

  • M. B. Blanco
  • M. A. Teruel*
  • I. Bejan
  • I. Barnes*
  • P. Wiesen
Part of the NATO Science for Peace and Security Series C: Environmental Security book series (NAPSC)

Rate coefficients for the reactions of OH radicals and Cl atoms with methyl methacrylate have been determined at 298 ± 2 K and 760 ± 10 Torr in two different photoreactors: a 405 l Duran glass and a 1,080 l quartz glass reaction chamber, coupled with in situ FTIR spectroscopy. Values of kOH = (0.43 ± 0.05) × 10−10 and kCl = (2.86 ± 1.37) × 10−10 in units of cm3 molecule−1 s−1 were obtained. Methyl pyruvate, formaldehyde and carbon monoxide were determined as products in the reaction of methyl methacrylate with OH radicals in accordance with OH radical addition to the less substituted carbon of the double bond. The atmospheric implications of the reactions have been assessed based on the calculated lifetime of methyl methacrylate.

Keywords

Methyl methacrylate Cl atoms OH radicals kinetic simulation chamber troposphere 

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References

  1. Arsene, C., Bougiatioti, A., Kanakidou, M., Bonsang, B. and Mihalopoulos, N., 2007, Tropospheric OH and Cl levels deduced from non-methane hydrocarbon measurements in a marine site, Atmos. Chem. Phys. 7:4661 – 4673.CrossRefGoogle Scholar
  2. Atkinson, R., 1986, Kinetics and mechanisms of the gas-phase reactions of hydroxyl radical with organic compounds under atmospheric conditions, Chem. Rev. 86:69 – 201.CrossRefGoogle Scholar
  3. Barnes, I., Bastian, V., Becker, K. H., Fink, E. H. and Zabel, F., 1982, Studies of organic substances toward hydroxyl radicals under atmospheric conditions, Atmos. Environ. 16:545 – 550.CrossRefGoogle Scholar
  4. Barnes, I., Becker, K. H. and Mihalopoulos, N., 1994, An FT-IR product study of the photo-oxidation of dimethyl disulfide, J. Atmos. Chem. 18:267 – 289.CrossRefGoogle Scholar
  5. Blanco, M. B., Taccone, R. A., Lane, S. I. and Teruel, M. A, 2006, On the OH-initiated degradation of methacrylates in the troposphere: Gas-phase kinetics and formation of pyruvates, Chem. Phys. Lett. 429:389 – 394.CrossRefGoogle Scholar
  6. Coquet, S. and Ariya, P. A., 2000, Kinetics of the gas-phase reactions of Cl atom with selected C2-C5 unsaturated hydrocarbons at 283 < T < 323 K, Int. J. Chem. Kinet. 32:478 – 484.CrossRefGoogle Scholar
  7. Ezell, M. J., Wang, W., Ezell, A. A., Soskin, G. and Finlayson-Pitts, B. J., 2002, Kinetics of reactions of chlorine atoms with a series of alkenes at 1 atm and 298 K: Structure and reactivity, Phys. Chem. Chem. Phys. 4:5813 – 5820.CrossRefGoogle Scholar
  8. Finlayson-Pitts, B. J., 1993, Chlorine atoms as a potential tropospheric oxidant in the marine boundary layer, Res. Chem. Intermed. 19:235 – 249.CrossRefGoogle Scholar
  9. Heard, E. H., 2006, Analytical Techniques for Atmospheric Measurement, Blackwell, Oxford.Google Scholar
  10. Howard, P. H., 1990, Handbook of Environmental Fate and Exposure for Organic Chemicals, Lewis Publishers, Chelsea, Michigan, pp. 216 – 221.Google Scholar
  11. Mellouki, A., Le Bras, G. and Sidebottom, H., 2003, Kinetics and mechanisms of the oxidation of oxygenated organic compounds in the gas phase, Chem. Rev. 103:5077 – 5096.CrossRefGoogle Scholar
  12. 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.CrossRefGoogle Scholar
  13. Teruel, M., Lane, S., Mellouki, A., Solignac, G. and Le Bras, G., 2006, OH reaction rate constants and UV absorption cross-sections of unsaturated esters, Atmos. Environ. 40(20):3764 – 3772.CrossRefGoogle Scholar
  14. Spicer, C. W., Chapman, E. G., Finlayson-Pitts, B. J., Plastidge, R. A., Hubbe, J. M., Fast, J. D. and Berkowitz, C. M., 1998, Observations of molecular chlorine in coastal air, Nature 394:353 – 356.CrossRefGoogle Scholar

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© Springer Science + Business Media B.V 2008

Authors and Affiliations

  • M. B. Blanco
    • 1
  • M. A. Teruel*
    • 1
  • I. Bejan
    • 2
  • I. Barnes*
    • 2
  • P. Wiesen
    • 2
  1. 1.Instituto de Investigaciones en Fisicoquí mica, I.N.F.I.Q.C., Dpto de Fisicoquímica, Facultad de Ciencias Quí micasUniversidad Nacional de Có rdobaCiudad UniversitariaArgentina
  2. 2.Bergische Universitaet Wuppertal, Physikalische Chemie/FB CWuppertalGermany

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