Abstract
Unsaturated alcohols are important components in complex mixtures of oxygenated volatile organic compounds, and play a significant role in atmospheric chemistry. The uptake kinetics of 3-buten-1-ol (BO31), 4-penten-1-ol (PO41) and 3-methyl-3-buten-1-ol (MBO331) into 20 wt%-80 wt% H2SO4 solutions were studied, using a rotated wetted-wall reactor coupled to a differentially pumped single-photon ionization time of flight mass spectrometer (SPI-TOFMS). With increasing acidity, the uptake processes changed from reversible to irreversible (reactive). Reactive uptake was observed in 60 wt%-80 wt%, 50 wt%-80 wt% and 30 wt%-80 wt% H2SO4 solutions for BO31, PO41 and MBO331, respectively. Reactive uptake coefficients were acquired and are reported here for the first time. Reactivity order followed the trend: BO31<PO41<MBO331. An electrophilic addition mechanism of H2SO4 to the C=C double bond was used to explain this trend. Atmospheric implications were discussed, based on the reactive uptake coefficients. This heterogeneous reaction with sulfuric acid aerosols may be a potential degradation pathway of unsaturated alcohols, and should not be neglected.
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References
Jang M, Kamens R M. Atmospheric secondary aerosol formation by heterogeneous reactions of aldehydes in the presence of a sulfuric acid aerosol catalyst. Environ Sci Technol, 2001, 35: 4758–4766
Jang M, Czoschke N M, Lee S, et al. Heterogeneous atmospheric aerosol production by acid-catalyzed particle-phase reactions. Science, 2002, 298: 814–817
Jang M, Lee S, Kamens R M. Organic aerosol growth by acid-catalyzed heterogeneous reactions of octanal in a flow reactor. Atmos Environ, 2003, 37: 2125–2138
Liggio J, Li S M, Mclaren R. Heterogeneous reactions of glyoxal on particulate matter: Identification of acetals and sulfate esters. Environ Sci Technol, 2005, 39: 1532–1541
Goldan P D, Kuster W C, Fehsenfeld F C, et al. The observation of a C5 alcohol emission in a North American pine forest. Geophys Res Lett, 1993, 20: 1039–1042
König G, Brunda M, Puxbai]m H, et al. Relative contribution of oxygenated hydrocarbons to the total biogenic VOC emissions of selected mid-European agricultural and natural plant species. Atmos Environ, 1995, 29: 861–874
Fall R, Karl T, Jordan A, et al. Biogenic C5 VOCs: Release from leaves after freeze-traw wounding and occurrence in air at a high mountain observatory. Atmos Environ, 2001, 35: 3905–3916
Cometto P M, Dalmasso P R, Taccone R A, et al. Rate coefficients for the reaction of OH with a series of unsaturated alcohols between 263 and 371 K. J Phys Chem A, 2008, 112: 4444–4450
Carrasco N, Doussin J F, O’Connor M, et al. Simulation chamber studies of the atmospheric oxidation of 2-methyl-3-buten-2-ol: Reaction with hydroxyl radical and ozone under a variety of conditions. J Atmos Chem, 2007, 56: 33–55
Noda J, Nyman G, Langer S. Kinetics of the gas-phase reaction of some unsaturated alcohols with the nitrate radical. J Phys Chem A, 2002, 106: 945–951
Wang L, Ge M F, Wang W G. Kinetic study of the reaction of chlorine atoms with 3-methyl-3-buten-1-ol. Chinese Sci Bull, 2009, 54: 3808–3812
Nozière B, Voisin D, Longfellow C A, et al. The uptake of methyl vinyl ketone, methacrolein, and 2-methyl-3-butene-2-ol onto sulfuric acid solutions. J Phys Chem A, 2006, 110: 2387–2395
Liu Z, Ge M F, Yin S, et al. Uptake and reaction kinetics of α-pinene or β-pinene with sulfuric acid solutions. Chem Phys Lett, 2010, 491: 146–150
Yin S, Ge M F, Wang W G, et al. Uptake of gas-phase alkylamines by sulfuric acid. Chinese Sci Bull, 2011, 56: 1241–1245
Murphy D M, Fahey D W. Mathematical treatment of the wall loss of a trace species in denuder and catalytic converter tubes. Anal Chem, 1987, 59: 2753–2759
Hanson D R, Burkholder J B, Howard C J, et al. Measurement of hydroxyl and hydroperoxy radical uptake coefficients on water and sulfuric acid surfaces. J Phys Chem, 1992, 96: 4979–4985
Gershenzon Y M, Grigorieva V M, Ivanov A V, et al. O3 and OH sensitivity to heterogeneous sinks of HOx and CH3O2 on aerosol particles. Faraday Discuss, 1995, 100: 83–100
Fuller E N, Schettler P D, Giddings J C. A new method for prediction of binary gas-phase diffusion coefficients. Ind Eng Chem, 1966, 58: 19–27
Howard C J. Kinetic measurements using flow tubes. J Phys Chem, 1979, 83: 3–9
Ganor E. A method for identifying sulfuric acid in single cloud and for droplets. Atmos Environ, 1999, 33: 4235–4242
Hindman E E, Borys R D, Lowenthal D H, et al. Long-term, wintertime aerosol, cloud and precipitation measurements in the Northern Colorado Rocky Mountains, USA. Atmos Res, 2006, 82: 194–202
Ferek R J, Lazrus A L, Haagenson P L, et al. Strong and weak acidity of aerosols collected over the Northeastern United States. Environ Sci Technol, 1983, 17: 315–324
Curtius J, Sierai] B, Arnold F, et al. Measurement of aerosol sulfuric acid. 2. Pronounced layering in the free troposphere during the second Aerosol Characterization Experiment (ACE 2). J Geophys Res Atmos, 2001, 106: 31975–31990
Esteve W, Nozière B. Uptake and reaction kinetics of acetone, 2-butanone, 2,4-pentanedione, and acetaldehyde in sulfuric acid solutions. J Phys Chem A, 2005, 109: 10920–10928
Timonen R S, Leu M T. Interaction of ethyl alcohol vapor with sulfuric acid solutions. J Phys Chem A, 2006, 110: 6660–6666
Levitt N P, Zhao J, Zhang R. Heterogeneous chemistry of butanol and decanol with sulfuric acid: Implications for secondary organic aerosol formation. J Phys Chem A, 2006, 110: 13215–13220
Wang L, Lal V, Khalizov A F, et al. Heterogeneous chemistry of alkylamines with sulfuric acid: Implications for atmospheric formation of alkylaminium sulfate. Environ Sci Technol, 2010, 44: 2461–2465
Godin S, Poole L R. Scientific Assessment of Ozone Depletion. Global Ozone Research and Monitoring Project-Report No. 44. Geneva: World Meteorological Organization, 1998
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Xu, Z., Liu, Z., Ge, M. et al. Uptake kinetics of 3-buten-1-ol, 4-penten-1-ol and 3-methyl-3-buten-1-ol into sulfuric acid solutions. Chin. Sci. Bull. 56, 1352–1356 (2011). https://doi.org/10.1007/s11434-011-4461-8
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DOI: https://doi.org/10.1007/s11434-011-4461-8