Effects of Inorganic Aerosols on the Gas-Phase Reactions of the Hydroxyl Radical with Selected Aliphatic Alkanes

  • Oh, Sewon (Division of Civil and Environmental Engineering, Sangmyung University) ;
  • Andino, Jean M. (Department of Environmental Engineering Sciences, University of Florida)
  • Published : 2003.09.01

Abstract

Effects of inorganic aerosols on the kinetics of the hydroxyl radical reactions with selected aliphatic alkanes have been investigated using the relative rate technique. The relative rates in the absence and presence of aerosols were determined for n-butane, n-pentane, n-hexane, n-octane, and n-decane. P-xylene was used as a reference compound. Inorganic aerosols including (NH$_4$)$_2$SO$_4$, NH$_4$NO$_3$, and NaCl aerosols at two different aerosol concentrations that are typical of polluted urban conditions were tested. Total surface areas of aerosols were 1400 (Condition I) and 3400 $\mu$$m^2$ cm$^{-3}$ (Condition II). Significant changes in the relative rates in the presence of the inorganic aerosols were not observed for the n-butanel/$.$OH, n-pentanel/$.$OH, n-hexanel/$.$OH, n-octanel/$.$OH, and n-decanel/$.$OH reactions versus p-xylenel/$.$OH reaction. These results suggest that the promoting effects depend on the semiconducting property of the aerosols and the nature of the organic compounds.

Keywords

References

  1. Atkinson, R. (1989) Kinetics and mechanisms of the gas-phase reactions of the hydroxyl radical with organic compounds, Journal of Physical and Chemical Reference Data Monograph, 1, 1-246
  2. Atkinson, R. (1994) Gas-phase tropospheric chemistry of organic compounds, Journal of Physical and Chemical Reference Data Monograph, 2, 1-216
  3. Atkinson, R. (1997) Gas-phase tropospheric chemistry of organic compounds: 1. Alkanes and alkenes. Journal of Physical and Chemical Reference Data, 26, 215-290
  4. Atkinson, R. (2000) Atmospheric chemistry of VOCs and N$O_{x}$' Atmospheric Environment, 34, 2063-2101
  5. Atkinson, R., W.P.L. Carter, A.M. Winer, and J.N. Jr. Pitts (1981) An experimental protocol for the determination of OH radical rate constants with organics using methyl nitrite photolysis as an OH radical source, Journal of the Air Pollution Control Association, 31, 1090-1092
  6. Behnke, W., W. Hollander, W. Koch, F Nolting, and C. Zetzsch (1988) A smog chamber for studies of the photochemical degradation of chemicals in the presence of aerosols, Atmospheric Environment, 22, 1113-1120
  7. Behnke, W., F. Nolting, and C. Zetzsch (1987) A smog chamber study on the impact of aerosols on the photodegradation of chemicals in the troposphere, Journal of Aerosol Science, 18, 65-71
  8. Dean, J.A. (1992) Lange's Handbook of Chemistry, 14th Edition, McGraw-Hili, New York, NY.
  9. Dodge, M.C. (2000) Chemical oxidant mechanism for air quality modeling: critical review, Atmospheric Environment, 34, 2103-2130
  10. Graedel, T.E., D.T. Hawkins, and L.D. Claxton (1986) Atmospheric Chemical Compounds, Academic Press, Orlando, FL.
  11. Inoue, Y., S. Sugio, J. Andzelm, and N. Nakamura (1998) A density functional study of the receptor-ligand interaction: stabilization energy in ammonium salt -aromatic interactions, Journal of Physical Chemistry A, 102, 646-648
  12. Lurmann, FW. and H.H. Main (1992) Analysis of the Ambient VOC Data Collected in the Southern California Air Quality Study; Final Report to the California Air Resources Board Contract A832-130, Sacramento, CA.
  13. Oh, S. and J.M. Andino (2000) Effects of ammonium sulfate aerosols on the gas-phase reactions of the hydroxyl radical with organic compounds, Atmospheric Environment, 34, 2901-2908
  14. Oh, S. and J.M. Andino (2001) Kinetics of the gas-phase reactions of hydroxyl radicals with C1-C6 aliphatic alcohols in the presence of ammonium sulfate aerosols, International Journal of Chemical Kinetics, 33, 422-430
  15. Oh, S. and J.M. Andino (2002) Laboratory studies of the impact of aerosol composition on the heterogeneous oxidation of l-propanol, Atmospheric Environment, 36, 149-156
  16. Seinfeld, J.H. (1988) Ozone air quality models: a critical review, JAPCA-The International Journal of Air Pollution Control and Hazardous Waste Management, 38, 616-645
  17. Seinfeld, J.H., J.M. Andino, FM. Bowman, H.J. Forstner, and S. Pandis (1994) Tropospheric chemistry, Advances in Chemical Engineering, 19, 325-407
  18. Willeke, K. and K.T. Whitby (1975) Atmospheric aerosols: size distribution interpretation, Journal of the Air Pollution Control Association, 25, 529-534