References

ACP

Atmospheric Chemistry and Physics

ACP

1680-7324

Copernicus GmbH

Göttingen, Germany

10.5194/acp-11-3227-2011

Atmospheric degradation of 3-methylfuran: kinetic and products study

Tapia

¹ Villanueva

¹ ² Salgado

M. S.

³ Cabañas

³ Martínez

³ Martín

Instituto de Tecnologías Química y Medioambiental (ITQUIMA), Laboratorio de Contaminación Atmosférica, Universidad de Castilla La Mancha, Avda Camilo José Cela s/n, 13071, Ciudad Real, Spain

Parque Científico y Tecnológico de Albacete, Paseo de la Innovación 1, 02006 Albacete, Spain

Departamento de Química Física, Facultad de Ciencias Químicas, Universidad de Castilla La Mancha, Avda Camilo José Cela s/n, 13071 Ciudad Real, Spain

05 04 2011

11 7 3227 3241

This is an open-access article ditributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.

This article is available from http://www.atmos-chem-phys.net/11/3227/2011/acp-11-3227-2011.html

The full text article is available as a PDF file from http://www.atmos-chem-phys.net/11/3227/2011/acp-11-3227-2011.pdf

A study of the kinetics and products obtained from the reactions of 3-methylfuran with the main atmospheric oxidants has been performed. The rate coefficients for the gas-phase reaction of 3-methylfuran with OH and NO3 radicals have been determined at room temperature and atmospheric pressure (air and N2 as bath gases), using a relative method with different experimental techniques. The rate coefficients obtained for these reactions were (in units cm3 molecule−1 s−1) kOH = (1.13 ± 0.22) × 10−10 and kNO3 = (1.26 ± 0.18) × 10−11. Products from the reaction of 3-methylfuran with OH, NO3 and Cl atoms in the absence and in the presence of NO have also been determined. The main reaction products obtained were chlorinated methylfuranones and hydroxy-methylfuranones in the reaction of 3-methylfuran with Cl atoms, 2-methylbutenedial, 3-methyl-2,5-furanodione and hydroxy-methylfuranones in the reaction of 3-methylfuran with OH and NO3 radicals and also nitrated compounds in the reaction with NO3 radicals. The results indicate that, in all cases, the main reaction path is the addition to the double bond of the aromatic ring followed by ring opening in the case of OH and NO3 radicals. The formation of 3-furaldehyde and hydroxy-methylfuranones (in the reactions of 3-methylfuran with Cl atoms and NO3 radicals) confirmed the H-atom abstraction from the methyl group and from the aromatic ring, respectively. This study represents the first product determination for Cl atoms and NO3 radicals in reactions with 3-methylfuran. The reaction mechanisms and atmospheric implications of the reactions under consideration are also discussed.

References 1

% vor jede Referenz Alvarado, A., Atkinson, R., and Arey, J.: Kinetics of the gas-phase reactions of NO3 radicals and O3 with 3-methylfuran and the OH radical yield from the O3 reaction, Int. J. Chem. Kinet., 28(12), 905–909, 1996.

Andreae, M. O. and Merlet, P.: Emission of trace gases and aerosols from biomass burning, Global Biogeochem. Cy., 15(4), 955–966, 2001.

Aschmann, S. M. and Atkinson, R.: Rate constants for the gas-phase reactions of alkanes with Cl atoms at 296 $\pm $ 2 K, Int. J. Chem. Kinet., 27(6), 613–622, 1995.

Atkinson, R.: Kinetics and mechanisms of the gas-phase reactions of the NO3 radical with organic compounds, J. Phys. Chem. Ref. Data, 20, 459–507, 1991.

Atkinson, R.: Gas-Phase Tropospheric Chemistry of Volatile Organic Compounds: Alkanes and Alkenes, J. Phys. Chem. Ref. Data, 26, 215–290, 1997.

Atkinson, R., Aschmann, S. M., Carter, W. P. L., Winer, A. M., and Pitts, J. N. Jr.: Kinetics of the reactions of OH radicals with n-alkanes at 299 $\pm $ 2 K, Int. J. Chem. Kinet., 14, 781–788, 1982.

Atkinson, R., Plum, C. N., Carter, W. P. L., Winer, A. M., and Pitts Jr., J. N.: Rate Constants for the Gas Phase Reactions of NO3 Radicals with a Series of Organics in Air at 298 $\pm $ 1 K, J. Phys. Chem., 88, 1210–1215, 1984.

Atkinson, R., Aschmann, S. A., Tuazon, E. C., Arey, J., and Zielinska, B.: Formation of 3-Methylfuran from the Gas-Phase Reaction of OH Radicals with Isoprene and the Rate Constant for its Reaction with the OH Radical, Int. J. Chem. Kinet., 21, 593–604, 1989.

Barnes, I., Becker, K. H., and Mihalopoulos, N.: An FTIR products study of the photooxidation of dimethyl disulfide, J. Atmos. Chem., 18, 267–289, 1994.

Berndt, T., Böge, O., and Rolle, W.: Products of the gas-phase reactions of NO3 radicals with furan and tetramethylfuran, Environ. Sci. Technol., 31, 1157–1162, 1997.

Bierbach, A., Barnes, I., Becker, K. H., and Wiesen, E.: Atmospheric chemistry of usaturated 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, 1994.

Bierbach, A., Barnes, I., and Becker, K. H.: Product and kinetic study of the OH-initiated gas-phase oxidation of furan, 2-methylfuran and furanaldehydes at 300 K, Atmos. Environ., 29 (19), 2651–2660, 1995.

Cabañas, B., Villanueva, F., Martín, P., Baeza, M. T., Salgado, S., and Jiménez, E.: Study of reaction processes of furan and some furan derivatives initiated by Cl atoms, Atmos. Environ., 39, 1935–1944, 2005.

Cabañas, B., Tapia, A., Villanueva, F., Salgado, S., Monedero, E., and Martín, P.: Kinetic study of 2-furanaldehyde, 3-furanaldehyde and 5-methyl-2-furanaldehyde reactions initiated by Cl atoms, Int. J. Chem. Kinet., 40(10), 670–678, 2008.

Carter, W. P. L.: Development of ozone reactivity scales for volatile organic compounds, J. Air Waste Manage., 44, 881–899, 1994.

Carter, W. P. L.: Development of the SAPRC-07 Chemical Mechanism and Updated Ozone Reactivity Scales. Final report to the California Air Resources, available at: www.cert.ucr.edu/~carter/SAPRC, 2010.

Edney, E. O., Kleindienst, T. E., and Corse, E. W.: Room temperature rate constants for the reaction of OH with selected chlorinated and oxygenated hydrocarbons, Int. J. Chem. Kinet., 18, 1355–1371, 1986.

Finlayson-Pitts, B. J. and Pitts, J. N.: Chemistry of the upper and lower atmosphere: Theory, Experiments and Applications, San Diego, Academic Press, 2000.

Gómez Álvarez, E., Borrás, E., Viidanoja, J., and Hjorth, J.: Unsaturated dicarbonyl products from the OH-initiated Photo-oxidation of furan, 2-methylfuran and 3-methylfuran, Atmos. Environ., 43, 1603–1612, 2009.

Graedel, T. E., Hawkings, D. T., and Claxton, L. D.: Atmospheric chemical compounds: Sources Occurrence, and Bioassay, Academic press, New York, 1986.

Gu, C. L., Rynard C. M., Hendry, D. G., and Mill, T.: Hydroxyl Radical Oxidation of Isoprene, Environ. Sci. Technol., 29, 2467–2469, 1995.

Guenther, A., Karl, T., Harley, P., Wiedinmyer, C., Palmer, P. I., and Geron, C.: Estimates of global terrestrial isoprene emissions using MEGAN (Model of Emissions of Gases and Aerosols from Nature), Atmos. Chem. Phys., 6, 3181–3210, http://dx.doi.org/10.5194/acp-6-3181-2006doi:10.5194/acp-6-3181-2006, 2006.

Hjorth, J., Lobse, C., Nielsen, C. J., Skov, H., and Restelli, G.: Products and mechanisms of the gas-phase reactions between NO3 and a series of alkenes, J. Phys. Chem., 94, 7494–7500, 1990.

Jones, B. T. and Ham, J. E.: $\alpha $-Terpineol reactions with the nitrate radical: Rate constant and gas-phase products, Atmos. Environ., 42, 6689–6698, 2008.

Kind, I., Berndt, T., Boge, O., and Rolle, W.: Gas-phase rate constants for the reaction of NO3 radicals with furan and methyl-substituted furans, Chem. Phys. Lett., 256, 679–683, 1996.

Kumar, P. and Pandey, R. K.: An efficient synthesis of 5-hydorxy-2(5H)-furanone, Green Chem., 2(1), 29–32, 2000.

Laothawornkitkul, J., Taylor, J. E., Paul, N. D., and Hewitt, C. N.: Biogenic volatile organic compounds in the Earth system, New Phytol., 183, 27–51, 2009.

Lee, W., Baasandorj, M., Stevens, P. S., and Hites, R. A.: Monitoring OH-Initiated Oxidation Kinetics of Isoprene and Its Products. Products Using Online Mass Spectrometry, J. Phys. Chem. A, 109(21), 4728–4735, 2005.

Logan, J. A.: Tropospheric ozone-seasonal behaviour, trends, and anthropogenic influence, J. Geophys. Res., 90, 463–482, 1985.

Martín, M. P., Tuazon, E. C., Aschmann, S. M., Arey, J., and Atkinson, R.: Formation and atmospheric reactions of 4,5-dihydro-2-methylfuran, J. Phys. Chem. A, 106, 11492–11501, 2002.

Martínez, E., Cabañas, B., Aranda, A., and Martín, P.: Kinetics of the reactions of NO3 radical with selected monoterpenes: a temperature dependence study, Environ. Sci. Technol., 32(23), 3730–3734, 1998.

Montzka, S. A., Trainer, M., Angevine, W. M., and Fehsenfeld, F. C.: Measurements of 3-methyl furan, methyl vinyl ketone, and methacrolein at a rural forested site in the southeastern United States, J. Geophys. Res., 100(D6), 11393–11401, 1995.

Nielsen, O. J., Jorgensen, O., Donlon, M., Sidebottom, H. W., O'Farrell, D. J., and Treacy, J.: Rate constants for the gas-phase reactions of OH radicals with nitroethene, 3-nitropropene and 1-nitrocyclohexene at 298 K and 1 atm, Chem. Phys. Lett., 168, 319–323, 1990.

Picquet-Varrault, B., Doussin, J. F., Durrand-Jolibois, R., Pirali, O., and Carlier, P.: Kinetic and mechanistic study of the atmospheric oxidation by OH radicals of allyl acetate, Environ. Sci. Technol., 36, 4081–4086, 2002.

Pounchert, C. J.: The Aldrich Library of FT-IR spectra, Aldrich Company Inc., Catalog number: z-18400-4, Volume 3, Edition I, 1989.

Prinn, R., Cunnold, D., Simmonds, P., Alyea, F., Boldi, R., Crawford, A., Froser, P., Gutzler, D., Hartley, R., Rosen, R., and Rasmussen, R.: Gloval average concentration and trend for hydroxyl radicals deduced from ALE/GAGE trichloroethane (methylchloroform) data for 1978–1990, J. Geophys. Res., 97, 2445–2461, 1992.

Rollins, A. W., Kiendler-Scharr, A., Fry, J. L., Brauers, T., Brown, S. S., Dorn, H.-P., Dubé, W. P., Fuchs, H., Mensah, A., Mentel, T. F., Rohrer, F., Tillmann, R., Wegener, R., Wooldridge, P. J., and Cohen, R. C.: Isoprene oxidation by nitrate radical: alkyl nitrate and secondary organic aerosol yields, Atmos. Chem. Phys., 9, 6685–6703, http://dx.doi.org/10.5194/acp-9-6685-2009doi:10.5194/acp-9-6685-2009, 2009.

Ruppert, L. and Becker, K. H.: A product study of the OH radical-initiated oxidation of isoprene: formation of C5-unsaturated diols, Atmos. Environ., 34(10), 1529–1542, 2000.

Scalon, T. J. and Willis, D. E.: Calculation of flame ionization detector response factors using effective number concept, J. Chromatogr. Sci., 23, 333–340, 1985.

Skov, H., Hjorth, J., Lohse, C., Jensen, N. R., and Restelli, G.: Products and mechanisms of the reactions of the nitrate radical (NO$_3)$ with isoprene, 1,3-butadiene and 2,3-dimethyl-1,3-butadiene in air, Atmos. Environ., 26A(15), 2771–2783, 1992.

Smith, D. F., Kleindienst, T. E., and McIver, C. D.: Primary product distributions from the reaction of OH with m-,p-xylene, 1,2,3- and 1,3,5-trimethylbenzene, J. Atmos. Chem., 34, 339–364, 1999.

Spicer, C. W., Champman, E. G., Finlayson-Pitts, B. J., Plastidge, R. A., Hubbe, J. M., Fast, J. D., and Berkowitz, C. M.: Observations of molecular chlorine in coastal air, Nature, 394(6691), 353–356, 1998.

Tang, Y. and Zhu, L.: Photolysis of butenedial at 193, 248, 280, 308, 351, 400, and 450 nm, Chem. Phys. Lett., 409, 151–156, 2005.

Tuazon, E. C., Mac Leod, H., Atkinson, R., and Carter, W. P. L.: $\alpha $-Dicarbonyl yields fron the NOx-air photooxidations of a series of aromatic hydrocarbons in air, Environ. Sci. Technol., 20, 383–387, 1986.

Tuazon, E. C., Alvarado, A., Aschmann, S., Atkinson, R., and Arey, J.: Products of the gas-phase reactions of 1,3-butadiene with OH and NO3 radicals, Environ. Sci. Technol., 33, 3586–3595, 1999.

Villanueva, F., Barnes, I., Monedero, E., Salgado, S., Gómez, M. V., and Martín, P.: Primary product distribution from the Cl-atom initiated atmospheric degradation of furan: Environmental implications, Atmos. Environ., 41(38), 8796–8810, 2007.

Villanueva, F., Cabañas, B., Monedero, E., Salgado, S., Bejan, I., and Martín, P.: Atmospheric degradation of alkylfurans with chlorine atoms: product and mechanistic study, Atmos. Environ., 43(17), 2804–2813, 2009.

Wang, L., Arey, J., and Atkinson, R.: Reactions of chlorine atoms with a series of aromatic hydrocarbons, Environ. Sci. Technol., 39, 5302–5310, 2005.

Wängberg, I., Barnes, I., and Becker, K. H.: Product and Mechanistic Study of the Reaction of NO3 Radicals with $\alpha $-Pinene, Environ. Sci. Technol., 31, 2130–2135, 1997.

Wingenter, O. W., Kubo, M. K., Blake, N. J., Smith Jr., T. W., Blake, D. R., and Rowland, F. S.: Hydrocarbon and halocarbon measurements as photochemical and dynamical indicators of atmospheric hydroxyl, atomic chlorine, and vertical mixing obtained during Lagrangian flights, J. Geophys. Res., 101, 4331–4340, 1996.

Zhang, W., Du, B., Mu, L., and Feng, C.: Mechanism for the gas-phase reaction between OH and 3-methylfuran: Mechanism for the gas-phase reaction between OH and 3-methylfuran: A theoretical study, Int. J. Quant. Chem., 108, 1232–1238, 2008.

Zhou, S., Barnes, I., Zhu, T., Bejan, I., and Benter, T.: Kinetic study of the gas-phase reactions of OH and NO3 radicals and O3 with selected vinyl ethers, J. Phys. Chem. A, 110(23), 7386–7392, 2006.