Kinetics of the Gas-Phase Reactions of OH Radicals, NO3 Radicals and O3 with Three C7-Carbonyls Formed From The Atmospheric Reactions of Myrcene, Ocimene and Terpinolene

Journal of Atmospheric Chemistry - Tập 48 - Trang 241-260 - 2004
Jillian Baker1,2, Janet Arey1,3, Roger Atkinson1,3,4
1Air Pollution Research Center, University of California, Riverside, U.S.A
2Interdepartmental Program in Environmental Sciences, University of California, Riverside, U.S.A
3Department of Environmental Sciences, University of California, Riverside, U.S.A
4Department of Chemistry, University of California, Riverside, U.S.A.

Tóm tắt

Rate constants for the gas-phase reactions of OH radicals, NO3 radicals and O3 with the C7-carbonyl compounds 4-methylenehex-5-enal [CH2=CHC(=CH2)CH2CH2CHO], (3Z)- and (3E)-4-methylhexa-3,5-dienal [CH2=CHC(CH3)=CHCH2CHO] and 4-methylcyclohex-3-en-1-one, which are products of the atmospheric degradations of myrcene, Z- and E-ocimene and terpinolene, respectively, have been measured at 296 ± 2 K and atmospheric pressure of air using relative rate methods. The rate constants obtained (in cm3 molecule−1 s−1 units) were: for 4-methylenehex-5-enal, (1.55 ± 0.15) × 10−10, (4.75 ± 0.35) × 10−13 and (1.46 ± 0.12) × 10−17 for the OH radical, NO3 radical and O3 reactions, respectively; for (3Z)-4-methylhexa-3,5-dienal: (1.61 ± 0.35) × 10−10, (2.17 ± 0.30) × 10−12, and (4.13 ± 0.81) × 10−17 for the OH radical, NO3 radical and O3 reactions, respectively; for (3E)-4-methylhexa-3,5-dienal: (2.52 ± 0.65) × 10−10, (1.75 ± 0.27) × 10−12, and (5.36 ± 0.28) × 10−17 for the OH radical, NO3 radical and O3 reactions, respectively; and for 4-methylcyclohex-3-en-1-one: (1.10 ± 0.19) × 10−10, (1.81 ± 0.35) × 10−12, and (6.98 ± 0.40) × 10−17 for the OH radical, NO3 radical and O3 reactions, respectively. These carbonyl compounds are all reactive in the troposphere, with daytime reaction with the OH radical and nighttime reaction with the NO3 radical being predicted to dominate as loss processes and with estimated lifetimes of about an hour or less.

Tài liệu tham khảo

Alvarado, A., Arey, J., and Atkinson, R., 1998: Kinetics of the gas-phase reactions of OH and NO3 radicals and O3 with the monoterpene reaction products pinonaldehyde, caronaldehyde, and sabi-naketone, J. Atmos. Chem. 3 1, 281–297. Atkinson, R., 1991: Kinetics and mechanisms of the gas-phase reactions of the NO3 radical with organic compounds, J. Phys. Chem. Ref. Data 2 0, 459–507. Atkinson, R., 1997: Gas-phase tropospheric chemistry of volatile organic compounds. 1. Alkanes and alkenes, J. Phys. Chem. Ref. Data 2 6, 215–290. Atkinson, R., 2000: Atmospheric chemistry of VOCs and NOx,Atmos. Environ. 3 4, 2063–2101. Atkinson, R. and Arey, J., 1998: Atmospheric chemistry of biogenic compounds, Acc. Chem. Res. 3 1, 574–583. Atkinson, R. and Arey, J., 2003: Gas-phase tropospheric chemistry of biogenic volatile organic com-pounds: A review, Atmos. Environ. 3 7(Suppl. 2), S197–S219. Atkinson, R. and Aschmann, S. M., 1993: Atmospheric chemistry of the monoterpene reaction prod-ucts nopinone, camphenilone, and 4-acetyl-1-methylcyclohexene, J. Atmos. Chem. 1 6, 337–348. Atkinson, R., Aschmann, S. M., and Arey, J., 1990: Rate constants for the gas-phase reactions of OH and NO3 radicals and O3 with sabinene and camphene at 296 ±2 K,Atmos. Environ. 24 A, 2647–2654. Atkinson, R., Aschmann, S. M., Arey, J., and Shorees, B., 1992: Formation of OH radicals in the gas-phase reactions of O3 with a series of terpenes, J. Geophys. Res. 9 7, 6065–6073. Atkinson, R., Carter, W. P. L., Winer, A. M., and Pitts, J. N., Jr., 1981: An experimental protocol for the determination of OH radical rate constants with organics using methyl nitrite photolysis as an OH radical source, J. Air Pollut. Control Assoc. 3 1, 1090–1092. Atkinson, R., Plum, C. N., Carter, W. P. L., Winer, A. M., and Pitts, J. N., Jr., 1984: Rate constants for the gas-phase reactions of nitrate radicals with a series of organics in air at 298 ±1 K,J. Phys. Chem. 8 8, 1210–1215. Bertele, E. and Schudel, P., 1967: Synthese von á-and â-sinensal, Helv. Chim. Acta 5 0, 2445–2456. Calogirou, A., Jensen, N. R., Nielsen, C. J., Kotzias, D., and Hjorth, J., 1999: Gas-phase reactions of nopinone, 3-isopropenyl-6-oxo-heptanal, and 5-methyl-5-vinyltetrahydrofuran-2-ol with OH, NO3, and ozone, Environ. Sci. Technol. 3 3, 453–460. Calvert, J. G., Atkinson, R., Kerr, J. A., Madronich, S., Moortgat, G. K., Wallington, T. J., and Yarwood, G., 2000: The Mechanisms of Atmospheric Oxidation of the Alkene s, Oxford University Press, New York, NY. Fall, R., 1999: Biogenic emissions of volatile organic compounds from higher plants, in (ed.) C. N. Hewitt, Reactive Hydrocarbons in the Atmospher e, Academic Press, San Diego, CA. Fuentes, J. D., Lerdau, M., Atkinson, R., Baldocchi, D., Bottenheim, J. W., Ciccioli, P., Lamb, B., Geron, C., Gu, L., Guenther, A., Sharkey, T. D., and Stockwell, W., 2000: Biogenic hydrocarbons in the atmospheric boundary layer: A review, Bull. Am. Meteor. Soc. 8 1, 1537–1575. Glasius, M., Calogirou, A., Jensen, N. R., Hjorth, J., and Nielsen, C. J., 1997: Kinetic study of gas-phase reactions of pinonaldehyde and structurally related compounds, Int. J. Chem. Kinet. 2 9, 527–533. Guenther, A., Geron, C., Pierce, T., Lamb, B., Harley, P., and Fall, R., 2000: Natural emissions of non-methane volatile organic compounds, carbon monoxide, and oxides of nitrogen from North America, Atmos. Environ. 3 4, 2205–2230. Guenther, A., Hewitt, C. N., Erickson, D., Fall, R., Geron, C., Graedel, T., Harley, P., Klinger, L., Lerdau, M., McKay, W. A., Pierce, T., Scholes, B., Steinbrecher, R., Tallamraju, R., Taylor, J., and Zimmerman, P., 1995: A global model of natural volatile organic compound emissions, J. Geophys. Res. 10 0, 8873–8892. 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. 1 8, 75–102. Hallquist, M., Wängberg, I., and Ljungström, E., 1997: Atmospheric fate of carbonyl oxidation products originating from á-pinene and 3-carene: Determination of rate of reaction with OH and NO3 radicals, UV absorption cross sections, and vapor pressures, Environ. Sci. Technol. 3 1, 3166–3172. IUPAC, 2003: Evaluated kinetic data, http://www.iupac-kinetic.ch.cam.ac.uk/ Kramp, F. and Paulson, S. E., 1998: On the uncertainties in the rate coefficients for OH reactions with hydrocarbons, and the rate coefficients of the 1,3,5-trimethylbenzene and m-xylene reactions with OH radicals in the gas phase, J. Phys. Chem. A 10 2, 2685–2690. Kwok, E. S. C. and Atkinson, R., 1995: Estimation of hydroxyl radical reaction rate constants for gas-phase organic compounds using a structure-reactivity relationship: An update, Atmos. Environ. 2 9, 1685–1695. Logan, J., 1985: Tropospheric ozone: Seasonal behavior, trends, and anthropogenic influence, J. Geophys. Res. 9 0, 10463–10482. Nozière, B., Spittler, M., Ruppert, L., Barnes, I., Becker, K. H., Pons, M., and Wirtz, K., 1999: Kinetics of the reactions of pinonaldehyde with OH radicals and with Cl atoms, Int. J. Chem. Kinet. 3 1, 291–301. Prinn, R. G., Huang, J., Weiss, R. F., Cunnold, D. M., Fraser, P. J., Simmonds, P. G., McCulloch, A., Harth, C., Salameh, P., O'Doherty, S., Wang, R. H. J., Porter, L., and Miller, B. R., 2001: Evidence for substantial variations of atmospheric hydroxyl radicals in the past two decades, Science 29 2, 1882–1888. Reissell, A., Aschmann, S. M., Atkinson, R., and Arey, J., 2002: Products of the OH radical-and O3-initiated reactions of myrcene and ocimene, J. Geophys. Res. 107 (D12), 10.1029/2001JD001234, ACH3-1 to 3-6. Reissell, A., Harry, C., Aschmann, S. M., Atkinson, R., and Arey, J., 1999: Formation of acetone from the OH radical-and O3-initiated reactions of a series of monoterpenes, J. Geophys. Res. 10 4, 13869–13879.