Journal of Atmospheric Chemistry

, Volume 32, Issue 2, pp 205–232 | Cite as

The Reaction of Unsaturated Aliphatic Oxygenates with Ozone

  • Eric Grosjean
  • Daniel GrosjeanEmail author


The reaction of ozone with unsaturated aliphatic oxygenates has been studied at ambient T (287–297 K) and p = 1 atm. of air (RH = 55 ± 10%) with sufficient cyclohexane added to scavenge the hydroxyl radical. Reaction rate constants, in units of 10-18 cm3 molecule-1 s-1, are 10.7 ± 1.4 for methyl trans-3-methoxy acrylate, 63.7 ± 9.9 for 4-hexen-3-one (predominantly the trans isomer), 125 ± 17 for trans-4-methoxy-3-buten-2-one, ≥148 ± 13 for cis-4-heptenal, ≥439 ± 37 for 3- methyl-2-buten-1-ol and ≥585 ± 132 for (cis + trans)-ethyl 1-propenyl ether. The influence of the oxygen-containing substituents on reactivity toward ozone is examined. Unsaturated ethers react with ozone faster than their alkene structural homologues; the reverse is observed for unsaturated esters and unsaturated carbonyls. Major reaction products have been identified by liquid chromatography with ultraviolet detection (LC-UV), particle beam-mass spectrometry (PB- MS) and gas chromatography-mass spectrometry (GC-MS) and are methyl formate and methyl glyoxylate from methyl trans-3-methoxy acrylate, acetaldehyde and 2-oxobutanal from 4-hexen-3-one, propanal and succinic dialdehyde from cis-4-heptenal, hydroxyacetaldehyde and acetone from 3-methyl-2-buten-1-ol, and ethyl formate and acetaldehyde from (cis + trans)-ethyl 1-propenyl ether. PB-MS and GC- MS were also employed to identify new reaction products and to confirm the structure of products tentatively identified in a previous study of the reaction of ozone with five unsaturated oxygenates (Grosjean and Grosjean, 1997a): formic acid and methyl glyoxylate from methyl acrylate, formic acid and formic acetic anhydride from vinyl acetate, 2-oxoethyl acetate and 3-oxopropyl acetate from cis-3-hexenyl acetate, ethyl formate and formic acid from ethyl vinyl ether, and methyl formate from trans-4-methoxy-3- buten-2-one. The nature and formation yields of the reaction products are consistent with (and supportive of) the reaction mechanism: O3 + R1R2C=CR3X → α(R1COR2 + R3C(X)OO) + (1 - α)(R3COX + R1C(R2)OO), where R1, R2 and R3 = H or alkyl, X is the oxygen-containing substituent, R1COR2 and R3COX are the primary products and R1C(R2)OO and R3C(X)OO are the carbonyl oxide biradicals. The variations of the coefficient α, which ranges from 0.25 to 0.61, are discussed in terms of the number and nature of alkyl and oxygen-containing substituents. Subsequent reactions of the alkyl-substituted biradicals R1C(R2)OO and of the biradicals R3C(X)OO that bear the oxygen-containing substituent are discussed. For the biradical CH3CHOO, the ratio ka/kb for the competing pathways of rearrangement to acetic acid (CH3CHOO → CH3C(O)OH, reaction (a) and formation of an unsaturated hydroperoxide (CH3CHOO → CH2=CH(OOH), reaction (b) is <0.25 for ethyl 1-propenyl ether and <0.27 for 4-hexen-3-one. Concentrations measured in co- located samples, one downstream of a water impinger and the other without water impinger, show the uptake in water impingers to be high (from 83.2 to >99.9%) and comparable to that for formaldehyde (98.4%) for formic acetic anhydride and for difunctional oxygenated compounds. Uptake in water impingers was lower (19–78%) for monofunctional aldehydes and ketones.

ozone biogenic hydrocarbons reaction products and mechanisms reaction rate constants unsaturated esters unsaturated ethers unsaturated carbonyls 


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  1. Atkinson, R. and Carter, W. P. L., 1984: Kinetics and mechanisms of the gas phase reactions of ozone with organic compounds under atmospheric conditions, Chem. Rev. 84, 437–470.Google Scholar
  2. Atkinson, R. and Aschmann, S. M., 1993: OH radical production from the gas phase reactions of O3 with a series of alkenes under atmospheric conditions, Environ. Sci. Technol. 27, 1357–1363.Google Scholar
  3. Atkinson, R., Arey, J., Aschmann, S. M., Corchnoy, S. B., and Shu, Y., 1995: Rate constants for the gas-phase reaction of cis-3-hexen-1-ol, cis-3-hexenyl acetate, trans-2-hexenal and linalool with OH and NO3 radicals and O3 at 296 ± 2 K, and OH radical formation yields from the O3 reactions, Int. J. Chem. Kinet. 27, 941–955.Google Scholar
  4. Bandow, H. and Washida, N., 1985: 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. Japan 58, 2541–2548.Google Scholar
  5. 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
  6. Calogirou, A., Kotzias, D., and Kettrup, A., 1997: Product analysis of the gas phase reaction of β-caryophyllene with ozone, Atmos. Environ. 31, 283–285.Google Scholar
  7. Carter, W. P. L. and Atkinson, R., 1996: Development and evaluation of a detailed mechanism for the atmospheric reactions of isoprene and NOx, Int. J. Chem. Kinet. 28, 497–530.Google Scholar
  8. Dumdei, B. and O'Brien, R. J., 1984: Toluene degradation products in simulated atmospheric conditions, Nature 311, 248–250.Google Scholar
  9. Eichel, C., Krämer, M., Schütz, L., and Wurzler, S., 1996: The water-soluble fraction of atmospheric aerosol particles and its influence on cloud microphysics, J. Geophys. Res. 101, 29399–29510.Google Scholar
  10. 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
  11. Fruekilde, P., Hjorth, J., Jensen, N. R., Kotzias, D., and Larsen, B., 1998: Ozonolysis at vegetation surfaces: a source of acetone, 4-oxopentanal, 6-methyl-5-hepten-2-one and geranyl acetone in the troposphere, Atmos. Environ. 32, 1893–1902.Google Scholar
  12. Fukui, Y. and Doskey, P. V., 1998: Air-surface exchange of non-methane organic compounds at a grassland site: Seasonal variations and stressed emissions, J. Geophys. Res. 103, 13,153–13,168.Google Scholar
  13. Grosjean, D., 1977: Aerosols, Chap. 3 in Ozone and Other Photochemical Oxidants, National Academy of Sciences, Washington, D.C., pp. 45–125.Google Scholar
  14. Grosjean, D., 1990a: Atmospheric chemistry of toxic air contaminants. 1. Reaction rates and atmospheric persistence, J. Air. Waste Manag. Assoc. 40, 1397–1402.Google Scholar
  15. Grosjean, D., 1990b: Atmospheric chemistry of toxic air contaminants. 3. Unsaturated aliphatics: Acrolein, acrylonitrile and maleic anhydride, J. Air Waste Manag. Assoc. 40, 1664–1669.Google Scholar
  16. Grosjean, D., 1995: Atmospheric chemistry of biogenic hydrocarbons: Relevance to the Amazon, Quimica Nova (Brazil) 18, 184–201.Google Scholar
  17. Grosjean, E. and Grosjean, D., 1994: Rate constants for the gas phase reactions of ozone with unsaturated aliphatic alcohols, Int. J. Chem. Kinet. 26, 1185–1191.Google Scholar
  18. Grosjean, E. and Grosjean, D., 1995a: Liquid chromatography analysis of C1–C10 carbonyls, Int. J. Environ. Anal. Chem. 61, 47–64.Google Scholar
  19. Grosjean, E. and Grosjean, D., 1995b: Performance of DNPH-coated cartridges for sampling C1–C9 carbonyls in air, Int. J. Environ. Anal. Chem. 61, 343–360.Google Scholar
  20. Grosjean, D. and Grosjean, E., 1995c: Carbonyl products of the ozone-unsaturated alcohol reaction, J. Geophys. Res. 100, 22815–22820.Google Scholar
  21. 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.Google Scholar
  22. Grosjean, E. and Grosjean, D., 1997a: The gas phase reaction of unsaturated oxygenates with ozone: Carbonyl products and comparison with the alkene-ozone reaction, J. Atmos. Chem. 27, 271–289.Google Scholar
  23. Grosjean, E. and Grosjean, D., 1997b: The gas phase reaction of alkenes with ozone: Formation yields of primary carbonyls and biradicals, Environ. Sci. Technol. 31, 2421–2427.Google Scholar
  24. Grosjean, E. and Grosjean, D., 1998a: The gas phase reaction of alkenes with ozone: Formation yields of carbonyls from biradicals in ozone-alkene-cyclohexane experiments, Atmos. Environ. 32, 3393–3402.Google Scholar
  25. Grosjean, E. and Grosjean, D., 1998b: Rate constants for the gas phase reaction of ozone with unsaturated oxygenates, Int. J. Chem. Kinet. 30, 21–29.Google Scholar
  26. Grosjean, D. and Grosjean, E., 1998c: Reaction of ozone with biogenic unsaturated oxygenates, final Report from DGA, Inc., Ventura, CA, to the Electric Power Research Institute, Palo Alto, CA, Contract WO4578–01, March.Google Scholar
  27. Grosjean, D., Van Cauwenberghe, K., Schmid, J. P., Kelley, P. E., and Pitts, J. N., Jr., 1978: Identification of C3–C10 aliphatic dicarboxylic acids in airborne particulate matter, Environ. Sci. Technol. 12, 313–317.Google Scholar
  28. Grosjean, D., Williams, E. L. II, and Seinfeld, J. H., 1992: Atmospheric oxidation of selected terpenes and related carbonyls: Gas phase carbonyl products, Environ. Sci. Technol. 26, 1526–1523.Google Scholar
  29. Grosjean, D., Williams, E. L. II, Grosjean, E., Andino, J. M., and Seinfeld, J. H., 1993: Atmospheric oxidation of biogenic hydrocarbons: Reaction of ozone with β-pinene, d-limonene and transcaryophyllene, Environ. Sci. Technol. 27, 2754–2758.Google Scholar
  30. Grosjean, D., Williams, E. L. II, Grosjean, E., and Novakov, T., 1994a: Evolved gas analysis of second organic aerosols, Aerosol Sci. Technol. 21, 306–324.Google Scholar
  31. Grosjean, D., Williams, E. L. II, and Grosjean, E., 1994b: Atmospheric chemistry of olefins: A product study of the ozone-alkene reaction with cyclohexane added to scavenge OH, Environ. Sci. Technol. 28, 186–196.Google Scholar
  32. Grosjean, E., Grosjean, D., Fraser, M. P., and Cass, G. R., 1996a: An air quality model evaluation data set for organics. 2. C1–C14 carbonyls in Los Angeles air, Environ. Sci. Technol. 30, 2687–2703.Google Scholar
  33. Grosjean, E., Grosjean, D., and Seinfeld, J. H., 1996b: Gas phase reaction of ozone with trans-2-hexenal, trans-2-hexenyl acetate, ethyl vinyl ketone and 6-methyl-5-hepten-2-one, Int. J. Chem. Kinet. 28, 373–382.Google Scholar
  34. Grosjean, E., Green, P. G., and Grosjean, D., 1998: Analysis of carbonyls as 2,4-dinitrophenylhydrazones by liquid chromatography with detection by diode array ultraviolet spectroscopy and atmospheric pressure negative chemical ionization mass spectrometry (submitted).Google Scholar
  35. Hakola, H., Arey, J., Aschmann, S. M., and Atkinson, R., 1994: Product formation from the gas phase reactions of OH radicals and O3 with a series of monoterpenes, J. Atmos. Chem. 18, 75–102.Google Scholar
  36. Hatakeyama, S., Izumi, K., Fukuyama, T., and Akimoto, H., 1989: Reactions of ozone with α-pinene and β-pinene in air: Yields of gaseous and particulate products, J. Geophys. Res. 94, 13013–13024.Google Scholar
  37. Hoffmann, T., Odum, J. R., Bowman, F., Collins, D., Klockow, D., Flagan, R. C., and Seinfeld, J. H., 1997: Formation of organic aerosols from the oxidation of biogenic hydrocarbons, J. Atmos. Chem. 26, 189–222.Google Scholar
  38. Kirstine, W., Galbally, I., Ye, Y., Hopper, M., 1998: Emissions of volatile organic compounds (primarily oxygenated species) from pasture, J. Geophys. Res. 103, 10605–10619.Google Scholar
  39. Koenig, G., Brunda, M., Puxbaum, H., Hewitt, C. N., Duckman, S. C., and Rudolph, J., 1995: Relative contribution of oxygenated hydrocarbons to the total biogenic VOC emissions of selected mid-European agricultural and natural plant species, Atmos. Environ. 29, 861–874.Google Scholar
  40. LaPalme, R., Borschberg, H.-J., Soucy, P., and Deslongchamps, P., 1979: Thermal decomposition of ozonides. A complementary method to the Baeyer-Villiger oxidation of hindered ketones, Canadian J. Chem. 57, 3272–3277.Google Scholar
  41. Matsumoto, K., Tanaka, H., Nagao, I., and Ishizaka, Y., 1997: Contribution of particulate sulfate and organic carbon to cloud condensation nuclei in the marine atmosphere, Geophys. Res. Lett. 24, 655–658.Google Scholar
  42. Novakov, T. and Penner, J. E., 1993: Large contribution of organic aerosols to cloud-condensation nuclei concentrations, Nature 365, 823–826.Google Scholar
  43. Novakov, T., Hegg, D. A., and Hobbs, P. V., 1997: Airborne measurements of carbonaceous aerosols on the east coast of the United States, J. Geophys. Res. 102, 30023–30030.Google Scholar
  44. Pilinis, C., Pandis, S., and Seinfeld, J. H., 1995: Sensitivity of direct climate forcing by atmospheric aerosols to aerosol size and composition, J. Geophys. Res. 100, 18739–18754.Google Scholar
  45. Puxbaum, H., 1997: Biogenic emissions of alcohols, esters, ethers and higher aldehydes, Chap. 7 in G. Helas, J. Slanina and R. Steinbrecher (eds), Biogenic Volatile Organic Compounds in the Atmosphere, SPB Academic Publishing, Amsterdam, pp. 79–100.Google Scholar
  46. Saxena, P., Hildemann, L. M., McMurry, P. H., and Seinfeld, J. H., 1995: Organics alter hygroscopic behavior of atmospheric particles, J. Geophys. Res. 100, 18755–18770.Google Scholar
  47. Saxena, P. and Hildemann, L. M., 1996: Water-soluble organics in atmospheric particles: A critical review of the literature and application of thermodynamics to identify candidate compounds, J. Atmos. Chem. 24, 57–109.Google Scholar
  48. Saxena, P. and Hidemann, L. M., 1997: Water absorption by organics: Survey of laboratory evidence and evaluation of UNIFAC for estimating water activity, Environ. Sci. Technol. 31, 3318–3324.Google Scholar
  49. Schueltze, D. and Rasmussen, R. A., 1978: The molecular composition of secondary aerosol particles formed from terpenes, J. Air Pollut. Control Assoc. 28, 236–240.Google Scholar
  50. Tuazon, E. C. and Atkinson, R. A., 1990: A product study of the gas phase reaction of isoprene with the OH radical in the presence of NOx, Int. J. Chem. Kinet. 22, 1221–1236.Google Scholar
  51. U.S. EPA, 1996: Air Quality Criteria for Particulate Matter, Report EPA/600/P-95/001, Office of Research and Development, U.S. Environmental Protection Agency, Washington, D.C.Google Scholar
  52. Weschler, C. J., Hodgson, A. T., and Wooley, J. D., 1992: Indoor chemistry: Ozone, volatile organic compounds, and carpets, Environ. Sci. Technol. 26, 2371–2377.Google Scholar
  53. Williams, D. C., O'Rji, L. N., and Stone, D. A., 1993: Kinetics of the reactions of OH radicals with selected acetates and other esters under simulated atmospheric conditions, Int. J. Chem. Kinet. 25, 539–548.Google Scholar
  54. 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

Copyright information

© Kluwer Academic Publishers 1999

Authors and Affiliations

  1. 1.DGA, Inc.VenturaU.S.A

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