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Primary Product Distributions from the Reaction of OH with m-, p-Xylene, 1,2,4- and 1,3,5-Trimethylbenzene

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Abstract

A study was conducted to examine the OH-initiated degradation products of the four title compounds in the presence of sub-part-per-million levels of NOx. The oxidation was conducted in a dynamic reactor to minimize the conversion of the aromatic compounds. The experiments were designed to represent reaction pathways that occur in the atmosphere at ambient NO2 concentrations. A wide range of ring-retaining and ring-cleavage products having widely varying yields were measured during the study. For m-xylene, the major primary products observed (with molar yields) were methyl glyoxal (0.40), 4-oxo-2-pentenal (0.12), glyoxal (0.079), and m-tolualdehyde (0.049). For p-xylene, the major primary products were p-tolualdehyde (0.103), 2,5-dimethylphenol (0.13), cis-3-hexene-2,5-dione (0.176), trans-3-hexene-2,5-dione (0.045), 2-methyl-butenedial (0.071), glyoxal (0.394), and methylglyoxal (0.217). Several other reaction products were measured at yields less than 3%. The primary products for OH + 1,2,4-trimethylbenzene were found as follows: methylglyoxal (0.44), glyoxal (0.066), cis-3-hexene-2,5-dione (0.13), trans-3-hexene-2,5-dione (0.031), biacetyl (0.114), 3-methyl-3-hexene-2,5-dione (0.079), and 2-methyl-butenedial (0.045). Six other (ring retaining) products were measured at yields less than 3%. The primary products for OH + 1,3,5-trimethylbenzene were methylglyoxal (0.90), 3-methyl-5-methylidene-5(2H)-furanone (0.1), 3,5-dimethyl-3(2H)-2-furanone (0.1), 3,5-dimethyl-5(2H)-2-furanone biacetyl (0.08), and 2-methyl-4-oxo-2- pentenal (0.05). Three other products were detected at molar yields less than 5%. In some cases, the yields for the ring fragmentation products could only be based on calibrations from surrogate compounds. Yields for several of the unsaturated dicarbonyl compounds have not been reported previously while yields for methylglyoxal, glyoxal, and biacetyl are largely consistent with previous reports. Some of the primary furanone products are the identical to those reported as secondary products in aromatic systems.

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References

  • Andino, J. M., Smith, J. N., Flagan, R. C., Goddard, W. A. III, and Seinfeld, J. H., 1996: Mechanism of atmospheric photooxidation of aromatics: A theoretical study, J. Phys. Chem. 100, 10967–10980.

    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 

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

    Google Scholar 

  • Atkinson, R., Aschmann, S. M., and Arey, J., 1991: Formation of ring retaining products from the OH radical-initiated reactions of o-, m-, and p-xylene, Int. J. Chem. Kinet. 23, 77–97.

    Google Scholar 

  • Bandow, H. and Washida, N., 1985a: Ring-cleavage reactions of aromatic hydrocarbons studied by FT-IR spectroscopy. II. Photooxidation of o-, m-, and p-xylenes in the NOx-air system, Bull. Chem. Soc. Jpn. 58, 2541–2548.

    Google Scholar 

  • Bandow, H. and Washida, N. 1985b: Ring-cleavage reactions of aromatic hydrocarbons studied by FT-IR spectroscopy. III. Photooxidation of 1,2,3-, 1,2,4-, and 1,3,5-trimethylbenzenes in the NOx-air system, Bull. Chem. Soc. Jpn. 58, 2549–2555.

    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 in the NOx-air system, Bull. Chem. Soc. Jpn. 58, 2540–2548.

    Google Scholar 

  • Becker, K. H., Barnes, I., Bierbach, A., Brockmann, K. J., Kirchner, F., Klotz, B., Libuda, H. G., Mayer-Figge, A., Mönninghoff, S., Ruppert, L., Thomas, W., Wiesen, E., Wirtz, K., and Zabel, F., 1997: OH initiated oxidation of VOCs under variable NOx conditions, in G. LeBras (ed.) Transport and Chemical Transformation of Pollutants in the Troposphere, Springer-Verlag, Berlin, pp. 79–97.

    Google Scholar 

  • Besemer, A. C., 1982: Formation of chemical compounds from irradiated mixtures of aromatic hydrocarbons and nitrogen oxides, Atmos. Environ. 16, 1599–1605.

    Google Scholar 

  • Bierbach, A., Barnes, I., Becker, K. H., and Wiesen, E., 1994: Atmospheric chemistry of unsaturated carbonyls: Butenedial, 4-oxo-2-pentenal, 3-hexene-2,5-dione, maleic anhydride, 3H-furan-2-one, and 5-methyl-3H-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 

  • Darnall, K. R., Atkinson, R., and Pitts, Jr., J. N., 1979: Observation of biacetyl from the reaction of OH radicals with o-xylene: Evidence for ring cleavage, J. Phys. Chem. 83, 1943–1946.

    Google Scholar 

  • Dumdei, B. E., Kenny, 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 mutagenic activity, Environ. Sci. Technol. 22, 1493–1498.

    Google Scholar 

  • Forstner, H. J. L., Flagan, R. C., and Seinfeld, J. H., 1997: Secondary organic aerosol from the photooxidation of aromatic hydrocarbons: Molecular composition, Environ. Sci. Technol. 31, 1345–1358.

    Google Scholar 

  • Gery, M. W., Fox, D. L., Jeffries, H. E., Stockburger, L., 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 

  • Gery, M.W., Fox, D. L., Kamens, R. M., and Stockburger, L., 1987: Investigation of hydroxyl radical reactions with o-xylene and m-xylene in a continuous tank reactor, Environ. Sci. Technol. 21, 339–348.

    Google Scholar 

  • Jorgensen, A. D., Picel, K. C., and Stamoudis, V. C., 1990: Prediction of gas chromatography flame ionization detector response factors from molecular structures, Analyt. Chem. 62, 683–689.

    Google Scholar 

  • Kleindienst, T. E., Smith, D. F., Li, W., Edney, E. O., Driscoll, D. J., Speer, R. E., and Weathers, W. S., 1999: Secondary organic aerosol formation from the oxidation of aromatic hydrocarbons in the presence of dry ammonium sulfate aerosol, Atmos. Environ. 33, 3669–3681.

    Google Scholar 

  • LeLacheur, R. M., Sonnenberg, P. C., 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 

  • Pouchert, C. J. (ed.), 1989: The Aldrich Library of FT-IR Spectra, Edition I, Volume 3, Vapor Phase, Aldrich Chemical Company, Inc.

  • Scanlon, J. T. and Willis, D. E., 1985: Calculation of flame ionization detector relative response factors using the effective carbon number concept, J. Chromat. Sci. 23, 333–340.

    Google Scholar 

  • Shepson, P. B., Edney, E. O, and Corse, E. W., 1984: Ring fragmentation reactions on the photooxidations 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., 1998: Primary product distribution from the reaction of hydroxyl radicals with toluene at ppb NOx mixing ratios, J. Atmos. Chem. 30, 209–228.

    Google Scholar 

  • Tuazon, E. C., Atkinson, R., MacLeod, H., Biermann, H. W., Winer, A. M., Carter, W. P. L., and Pitts, Jr., J. N., 1984: Yields of glyoxal and methylglyoxal from the NOx air photooxidations of toluene, and m-, and p-xylene, Environ. Sci. Technol. 18, 981–987.

    Google Scholar 

  • Tuazon, E. C., Atkinson, R., and Carter, W. P. L., 1985: Atmospheric chemistry of cis-and trans-3-hexene-2,5-dione, Environ. Sci. Technol. 19, 265–269.

    Google Scholar 

  • Tuazon, E. C., MacLeod, H., Atkinson, R., and Carter, W. P. L., 1986: α-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 Sexton, K. G., 1997: Atmospheric photooxidation of alkylbenzenes: I. Carbonyl product analyses, Atmos. Environ. 31, 2261–2280.

    Google Scholar 

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  1. ManTech Environmental Sciences, PO Box 12313, Research Triangle Park, NC, 27709, U.S.A

    D. F. Smith, T. E. Kleindienst & C. D. McIver

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  1. D. F. Smith
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  2. T. E. Kleindienst
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  3. C. D. McIver
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Smith, D.F., Kleindienst, T.E. & McIver, C.D. Primary Product Distributions from the Reaction of OH with m-, p-Xylene, 1,2,4- and 1,3,5-Trimethylbenzene. Journal of Atmospheric Chemistry 34, 339–364 (1999). https://doi.org/10.1023/A:1006277328628

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