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Primary Product Distribution from the Reaction of Hydroxyl Radicals with Toluene at ppb NOX Mixing Ratios

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Abstract

A study has been conducted to examine the OH-initiated degradation products of toluene in the presence of sub part-per-million levels of NOX. The experiments were conducted in a dynamic reactor to minimize the conversion of the aromatic compounds while allowing a sufficient mass of products to be collected for analysis. The major primary products detected in the toluene system (with molar yields) include glyoxal (0.238), methylglyoxal (0.167), o-cresol (0.120), benzaldehyde (0.06), 4-oxo-2-pentenal (0.03), and p-cresol (0.03). Six other reaction products, most being ring cleavage products, were measured at yields below 3%. Corrections for secondary OH reactions with the products were made where necessary. The formation of the cresol isomers was found to be invariant to the NO2 concentrations which indicates that under atmospheric conditions the initial hydroxycyclohexadienyl radical reaction with NO2 is a minor process and that most of the reaction occurs with O2. The product yields found in this study are expected to be representative of those that occur in the urban atmosphere at ambient NO2 concentrations.

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References

  • Atkinson, R., 1989: Kinetics and mechanism of the gas-phase reactions of the hydroxyl radical with organic compounds, J. Phys. Chem. Ref. Data, Monograph No. 1.

  • Atkinson, R., Carter, W. P. L, Darnall, K. R., Winer, A.M., and Pitts, Jr., J. N., 1980: A smog chamber and modeling study of the gas phase NOX-air photooxidation of toluene and the cresols, Int. J. Chem. Kinet. 12, 779–834.

    Google Scholar 

  • Atkinson, R., Aschmann, S. M., Carter, W. P. L., Winer, A. M., and Pitts, Jr., J. N., 1982: Alkyl nitrate formation from the reaction of a series of branched RO2 radicals with NO as a function of temperature and pressure, J. Phys. Chem. 86, 4563–4569.

    Google Scholar 

  • Atkinson, R. and Lloyd, A. C., 1984: Evaluation of kinetic and mechanistic data for modeling of photochemical smog, J. Chem. Phys. Ref. Data 13, 315–444.

    Google Scholar 

  • Atkinson, R., Aschmann, S. M., Arey, J., and Carter, W. P. L., 1989: Formation of ring-retaining products from the OH radical-initiated reactions of benzene and toluene, Int. J. Chem. Kinet. 21, 801–827.

    Google Scholar 

  • Atkinson, R. and Aschmann, S. M., 1994: Products of the gas-phase reactions of aromatic hydrocarbons: effect of NO2 concentration, Int. J. Chem. Kinet. 26, 929–944.

    Google Scholar 

  • Bandow, H., Washida, N., and Akimoto, H., 1985: Ring-cleavage reactions of aromatic hydrocarbons studied by FT-IR spectroscopy. I. Photooxidation of toluene and benzene in the NOX-air system, Bull. Chem. Soc. Japan 58, 2531–2540.

    Google Scholar 

  • Besemer, A. C., 1982: Formation of chemical compounds from irradiated mixtures of aromatic hydrocarbons and nitrogen oxides, Atmos. Environ. 16, 1599–1602.

    Google Scholar 

  • Bierbach, A., Barnes, I., Becker, K. H., and Wiesen, E., 1994: Atmospheric chemistry of unsaturated carbonyls: butenedial, 4-oxo-pentenal, 3-hexene-2, 5-dione, maleic anhydride, 3(2H)-furan-2-one, and 5-methyl-3( 2H)-furan-2-one, Environ. Sci. Technol. 28, 715–729.

    Google Scholar 

  • Cancilla, D. A., Chou, C. C., Barthel, R., and Que Hee, S. S., 1992: Characterization of the O-(2,3,4,5,6-perfluorobenzyl)-hydroxylamine hydrochloride (PFBOA) derivatives of some aliphatic mono-and dialdehydes and quantitative water analysis of these aldehydes, J. AOAC Int. 75, 842–854.

    Google Scholar 

  • Dumdei, B. E. and O'Brien, R. J., 1983: Toluene degradation products in simulated atmospheric conditions, Nature 311, 248–250.

    Google Scholar 

  • Dumdei, B. E., Kenney, D. V., Shepson, P. B., Kleindienst, T. E., Nero, C. M., Cupitt, L. T., and Claxton, L. D., 1988: MS/MS analysis of the products of toluene photooxidation and measurement of their mutagenicity, Environ. Sci. Technol. 22, 1493–1498.

    Google Scholar 

  • Gery, M. W., Fox, D. L., Jeffries, H. E., Stockburger, L., and Weathers, W. S., 1985: A continuous stirred tank reactor investigation of the gas-phase reaction of hydroxyl radicals and toluene, Int. J. Chem. Kinet. 17, 931–955.

    Google Scholar 

  • Hufford, D. L., Tarbell, D. S., and Koszalka, T. R., 1952: Maleic and fumaric dialdehydes, Δ4-tetrahydro-phthalaldehydes and related compounds, J. Amer. Chem. Soc. 74, 3014–3018.

    Google Scholar 

  • Kenley, R. A., Davenport, J. E., and Hendry, D. G., 1981: Gas-phase hydroxyl radical reactions. Products and pathways for the reaction of OH with aromatic hydrocarbons, J. Phys. Chem. 85, 2740–2746.

    Google Scholar 

  • Le Lacheur, R. M., Sonnenberg, L. B., Singer, P. C., Christman, R. F., and Charles, M. J., 1993: Identification of carbonyl compounds in environmental samples, Environ. Sci Technol. 27, 2745–2753.

    Google Scholar 

  • Shepson, P. B., Edney, E. O., and Corse, E. W., 1984: Ring fragmentation reactions on the photooxidation of toluene and o-xylene, J. Phys. Chem. 88, 4122–4126.

    Google Scholar 

  • Smith, D. F., Kleindienst, T. E., and Hudgens, E. E., 1989: Improved high performance liquid chromatographic method for artifact-free measurements of aldehydes in the presence of ozone using 2,4-dinitrophenylhydrazine, J. Chromatogr. 483,431–436.

    Google Scholar 

  • Smith, D. F., Kleindienst, T. E., Hudgens, E. E., and Bufalini, J. J., 1994: Measurement of organic atmospheric transformation products by gas chromatography, Int. J. Environ. Anal. Chem. 54, 265–281.

    Google Scholar 

  • Smith, D. F., McIver, C. D., and Kleindienst, T. E., 1995: Kinetics and mechanism of the atmospheric oxidation of tertiary-amyl methyl ether, Int. J. Chem. Kinet. 26, 453–472.

    Google Scholar 

  • Taylor, W. D., Allston, D., Moscato, M. J., Fazekas, G. D., Kozlowski, R., and Takacs, G. D., 1980: Atmospheric photodissociation lifetimes for nitromethane, methyl nitrite, and methyl nitrate, Int. J. Chem. Kinet. 12, 231–240.

    Google Scholar 

  • Tuazon, E. C., MacLeod, H., Atkinson, R., and Carter, W. P. L., 1986: Dicarbonyl yields from the NOX-air photooxidations of a series of aromatic hydrocarbons in air, Environ. Sci. Technol. 20,383–387.

    Google Scholar 

  • Yu, J., Jeffries, H. E., and Le Lacheur, R. M., 1995: Identifying airborne carbonyl compounds in isoprene atmospheric photooxidation products by their PFBHA oximes using gas chromatography/ ion trap mass spectrometry, Environ. Sci. Technol. 29, 1923–1932.

    Google Scholar 

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Smith, D.F., McIver, C.D. & Kleindienst, T.E. Primary Product Distribution from the Reaction of Hydroxyl Radicals with Toluene at ppb NOX Mixing Ratios. Journal of Atmospheric Chemistry 30, 209–228 (1998). https://doi.org/10.1023/A:1005980301720

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