References

ACP

Atmospheric Chemistry and Physics

ACP

Atmos. Chem. Phys.

1680-7324

Copernicus Publications

Göttingen, Germany

10.5194/acp-11-3347-2011

Rate coefficients for the gas-phase reaction of OH with (Z)-3-hexen-1-ol, 1-penten-3-ol, (E)-2-penten-1-ol, and (E)-2-hexen-1-ol between 243 and 404 K

Davis

M. E.

¹ ² ³ Burkholder

J. B.

Earth System Research Laboratory, Chemical Sciences Division, NOAA, 325 Broadway, Boulder Colorado 80305-3328, USA

Cooperative Institute for Research in Environmental Sciences, University of Colorado, Boulder 80309, USA

current address: Michigan State University, East Lansing, MI 48825, USA

08 04 2011

11 7 3347 3358

2011

This work is licensed under the Creative Commons Attribution 3.0 Unported License. To view a copy of this licence, visit https://creativecommons.org/licenses/by/3.0/

This article is available from https://acp.copernicus.org/articles/11/3347/2011/acp-11-3347-2011.html

The full text article is available as a PDF file from https://acp.copernicus.org/articles/11/3347/2011/acp-11-3347-2011.pdf

Rate coefficients, k, for the gas-phase reaction of the OH radical with (Z)-3-hexen-1-ol (Z)-CH3CH2CH = CHCH2CH2OH) (k1), 1-penten-3-ol (CH3CH2CH(OH)CH = CH2) (k2), (E)-2-penten-1-ol ((E)-CH3CH2CH = CHCH2OH) (k3), and (E)-2-hexen-1-ol ((E)-CH3CH2CH2CH = CHCH2OH) (k4), unsaturated alcohols that are emitted into the atmosphere following vegetation wounding, are reported. Rate coefficients were measured under pseudo-first-order conditions in OH over the temperature range 243–404 K at pressures between 20 and 100 Torr (He) using pulsed laser photolysis (PLP) to produce OH radicals and laser induced fluorescence (LIF) to monitor the OH temporal profile. The obtained rate coefficients were independent of pressure with negative temperature dependences that are well described by the Arrhenius expressions k1(T) = (1.3 ± 0.1) × 10−11 exp[(580 ± 10)/T]; k1(297 K) = (1.06 ± 0.12) × 10−10 k2(T) = (6.8 ± 0.7) × 10−12 exp[(690 ± 20)/T]; k2(297 K) = (7.12 ± 0.73) × 10−11 k3(T) = (6.8 ± 0.8) × 10−12 exp[(680 ± 20)/T]; k3(297 K) = (6.76 ± 0.70) × 10−11 k4(T) = (5.4 − 0.6) × 10−12 exp[(690 ± 20)/T]; k4(297 K) = (6.15 ± 0.75) × 10−11 (in units of cm3 molecule−1 s−1). The quoted uncertainties are at the 2σ (95% confidence) level and include estimated systematic errors. The rate coefficients obtained in this study are compared with literature values where possible.

References 1

Alvarado, A., Tuazon, E. C., Aschmann, S. M., Arey, J., and Atkinson, R.: Products and mechanisms of the gas-phase reactions of OH radicals and O3 with 2-methyl-3-buten-2-ol, Atmos. Environ., 33, 2893–2905, 1999.

Arey, J., Winer, A. M., Atkinson, R., Aschmann, S. M., Long, W. D., and Morrison, C. L.: The emission of ($Z)$-3-hexen-1-ol, ($Z)$-3-hexenylacetate and other oxygenated hydrocarbons from agricultural plant-species, Atmos. Environ., 25, 1063–1075, 1991.

Aschmann, S. M., Shu, Y. H., Arey, J., and Atkinson, R.: Products of the gas-phase reactions of cis-3-hexen-1-ol with OH radicals and O3, Atmos. Environ., 31, 3551–3560, 1997.

Atkinson, R., Arey, J., Aschmann, S. M., Corchnoy, S. B., and Shu, Y. H.: Rate constants for the gas-phase reactions of cis-3-hexen-1-ol, cis-3-hexenylacetate, 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, 1995.

Baasandorj, M. and Stevens, P. S.: Experimental and theoretical studies of the kinetics of the reactions of OH and OD with 2-methyl-3-buten-2-ol between 300 and 415 K at low pressure, J. Phys. Chem. A, 111, 640–649, 2007.

Baker, J., Arey, J., and Atkinson, R.: Rate constants for the gas-phase reactions of OH radicals with a series of hydroxyaldehydes at 296 ± 2 K, J. Phys. Chem. A, 108, 7032–7037, 2004.

Davis, M. E., Gilles, M. K., Ravishankara, A. R., and Burkholder, J. B.: Rate coefficients for the reaction of OH with ($E)$-2-pentenal, ($E)$-2-hexenal, and ($E)$-2-heptenal, Phys. Chem. Chem. Phys., 9, 2240–2248, 2007.

Ebel, R. C., Mattheis, J. P., and Buchanan, D. A.: Drought stress of apple-trees alters leaf emissions of volatile compounds, Physiol. Plantarum., 93, 709–712, 1995.

Fisher, A. J., Grimes, H. D., and Fall, R.: The biochemical origin of pentenol emissions from wounded leaves, Phytochemistry, 62, 159–163, 2003.

Grosjean, E. and Grosjean, D.: The gas phase reaction of unsaturated oxygenates with ozone: Carbonyl products and comparison with the alkene-ozone reaction, J. Atmos. Chem., 27, 271–289, 1997.

Guenther, A., Geron, C., Pierce, T., Lamb, B., Harley, P., and Fall, R.: Natural emissions of non-methane volatile organic compounds; carbon monoxide, and oxides of nitrogen from North America, Atmos. Environ., 34, 2205–2230, 2000.

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.: A global-model of natural volatile organic-compound emissions, J. Geophys. Res. Atmos., 100, 8873–8892, 1995.

Hatanaka, A. and Harada, T.: Leaf-alcohol formation of cis-3-hexenal, trans-2-hexenal and cis-3-hexenol in macerated thea-sinensis leaves, Phytochemistry, 12, 2341–2346, 1973.

Heiden, A. C., Kobel, K., Langebartels, C., Schuh-Thomas, G., and Wildt, J.: Emissions of oxygenated volatile organic compounds from plants – part I: Emissions from lipoxygenase activity, J. Atmos. Chem., 45, 143–172, 2003.

Imamura, T., Iida, Y., Obi, K., Nagatani, I., Nakagawa, K., Patroescu-Klotz, J., and Hatakeyama, S.: Rate coefficients for the gas-phase reactions of OH radicals with methylbutenols at 298 K, Int. J. Chem. Kinet., 36, 379–385, 2004.

Jiménez, E., Lanza, B., Antiñolo, M., and Albaladejo, J.: Photooxidation of leaf-wound oxygenated compounds, 1-penten-3-ol, ($Z)$-3-hexen-1-ol, and 1-penten-3-one, initiated by OH radicals and sunlight, Environ. Sci. Technol., 43, 1831–1837, 2009.

Karl, T., Fall, R., Jordan, A., and Lindinger, W.: On-line analysis of reactive VOCs from urban lawn mowing, Environ. Sci. Technol., 35, 2926–2931, 2001.

Kirstine, W., Galbally, I., Ye, Y. R., and Hooper, M.: Emissions of volatile organic compounds (primarily oxygenated species) from pasture, J. Geophys. Res. Atmos., 103, 10605–10619, 1998.

Kwok, E. S. C. and Atkinson, R.: Estimation of hydroxyl radical reaction-rate constants for gas-phase organic-compounds using a structure-reactivity relationship – an update, Atmos. Environ., 29, 1685–1695, 1995.

Nakamura, S. and Hatanaka, A.: Green-leaf-derived C6-aroma compounds with potent antibacterial action that act on both gram-negative and gram-positive bacteria, J. Agricult. Food Chem., 50, 7639–7644, 2002.

Noda, J., Hallquist, M., Langer, S., and Ljungstrom, E.: Products from the gas-phase reaction of some unsaturated alcohols with nitrate radicals, Phys. Chem. Chem. Phys., 2, 2555–2564, 2000.

Noda, J., Nyman, G., and Langer, S.: Kinetics of the gas-phase reaction of some unsaturated alcohols with the nitrate radical, J. Phys. Chem. A, 106, 945–951, 2002.

Orlando, J. J., Tyndall, G. S., and Ceazan, N.: Rate coefficients and product yields from reaction of OH with 1-penten-3-ol, ($Z)$-2-penten-1-ol, and allyl alcohol (2-propen-1-ol), J. Phys. Chem. A, 105, 3564–3569, 2001.

Papagni, C., Arey, J., and Atkinson, R.: Rate constants for the gas-phase reactions of OH radicals with a series of unsaturated alcohols, Int. J. Chem. Kinet., 33, 142–147, 2001.

Pfrang, C., Martin, R. S., Canosa-Mas, C. E., and Wayne, R. P.: Gas-phase reactions of NO3 and N2O5 with ($Z)$-hex-4-en-1-ol, ($Z)$-hex-3-en-1-ol ("leaf alcohol"), ($E)$-hex-3-en-1-ol, ($Z)$-hex-2-en-1-ol and ($E)$-hex-2-en-1-ol, Phys. Chem. Chem. Phys., 8, 354–363, 2006.

Pfrang, C., Romero, M. T. B., Cabanas, B., Canosa-Mas, C. E., Villanueva, F., and Wayne, R. P.: Night-time tropospheric chemistry of the unsaturated alcohols ($Z)$-pent-2-en-1-ol and pent-1-en-3-ol: Kinetic studies of reactions of NO3 and N2O5 with stress-induced plant emissions, Atmos. Environ., 41, 1652–1662, 2007.

Rudich, Y., Talukdar, R., Burkholder, J. B., and Ravishankara, A. R.: Reaction of methylbutenol with hydroxyl radical – Mechanism and atmospheric implications, J. Phys. Chem., 99, 12188–12194, 1995.

Sander, S. P., Golden, D. M., Kurylo, M. J., Huie, R. E., Orkin, V. L., Moortgat, G. K., Ravishankara, A. R., Kolb, C. E., Molina, M. J., Finlayson-Pitts, B. J., and Wine, P. H.: Chemical Kinetics and Photochemical Data for Use in Atmospheric Studies, Evaluation Number 15, JPL Publication 06–2, Jet Propulsion Laboratory, California Institute of Technology, 2006.

Upadhyaya, H. P., Kumar, A., Naik, P. D., Sapre, A. V., and Mittal, J. P.: Kinetics of OH radical reaction with allyl alcohol (H2C = CHCH2OH) and propargyl alcohol (HC${\equiv}$CCH2OH) studied by LIF, Chem. Phys. Lett., 349, 279–285, 2001.

Vaghjiani, G. L. and Ravishankara, A. R.: Kinetics and mechanism of OH Reaction with CH3OOH, J. Phys. Chem., 93, 1948–1959, 1989.