The products of the OH radical initiated oxidation of dimethyl sulfide (DMS) have been investigated under NOx-free conditions using the photolysis of H2O2 as the OH radical source and FT-IR spectroscopy to monitor reactants and products. The experiments were performed at five different temperatures (260, 270, 280, 290 and 298 K), at three different O2 partial pressure (̃0, 205 and 500 mbar) and at a total pressure of 1,000 mbar diluent gas (N2, synthetic air or N2/O2 mixture). The major sulfur-containing products were dimethyl sulfoxide (DMSO) and sulfur dioxide (SOM2). As minor sulfur-containing products dimethyl sulfone (DMSO2), methyl thiol formate (MTF) and carbonyl sulfide (OCS) have been identified; the formation of trace amounts of methane sulfonic acid (MSA) were also observed. The variation of the product yields with temperature and O2 partial pressure is consistent with the occurrence of both addition and abstraction channels in the OH radical initiated oxidation of DMS. The molar formation yields of DMSO support that a major fraction of the DMS-OH adduct formed in the addition channel reacts with O2 to form DMSO.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
Preview
Unable to display preview. Download preview PDF.
References
Albu, M., Barnes, I., Becker, K.H., Patroescu-Klotz, I., Mocanu, R., and Benter, Th., 2006a, Rate coefficients for the gas-phase reaction of OH radicals with dimethyl sulfide: temperature and O2 partial pressure dependence, Phys. Chem. Chem. Phys. 8, 728 – 736.
Albu, M., Barnes, I., and Mocanu, R., 2006b, Kinetic study of the temperature dependence of the OH initiated oxidation of dimethyl sulfide, in: Proceedings of the NATO Advanced Research Workshop on Environmental Simulation Chambers: Application to Atmospheric Chemical Processes, Zakoppane, Poland, 1 – 4 October 2004, I. Barnes and K.J. Rudzinski, eds., NATO Science Series IV: Earth and Environmental Sciences — Vol. 62, Springer, Dordrecht pp. 223 – 230.
Arsene, C., Barnes, I., and Becker, K.H., 1999, FT-IR product study on the photo-oxidation of dimethyl sulphide: temperature and O2 partial pressure dependence, Phys. Chem. Chem. Phys. 1, 5463 – 5470.
Arsene, C., Barnes, I., Becker, K.H., and Mocanu, R., 2001, FT-IR product study on the photo-oxidation of dimethyl sulphide in the presence of NOx — temperature dependence, Atmos. Environ. 35, 3769 – 3780.
Arsene, C., Barnes, I., Becker, K.H., Schneider, W.F., Wallington, T.J., Mihalopoulos, N., and Patroescu-Klotz, I.V., 2002, Formation of methane sulfinic acid in the gas-phase OH-radical initiated oxidation of dimethyl sulfoxide, Environ. Sci. Technol. 36, 5155 – 5163.
Barnes, I., Becker, K.H., Fink, E.H., Reimer, A., Zabel, F., and Niki, H., 1983, Rate constant and products of the reaction CS2 + OH in the presence of O2, Int. J. Chem. Kinet. 15, 631 – 645.
Barnes, I., Bastian, V., and Becker, K.H., 1988, Kinetics and mechanisms of the reaction of OH radicals with dimethyl sulphide, Int. J. Chem. Kinet. 20 (6), 415 – 431.
Barnes, I., Becker, K.H., and Patroescu, I., 1994, The tropospheric oxidation of dimethyl sulfide: a new source of carbonyl sulphide, Geophys. Res. Lett. 21 (22), 2389 – 2392.
Barnes, I., Becker, K.H., and Patroescu, I., 1996, FTIR product study of the OH initiated oxidation of dimethyl sulphide: observation of carbonyl sulphide and dimethyl sulphoxide, Atmos. Environ. 30 (10/11), 1805 – 1814.
Barnes, I., Hjorth, J., and Mihalopoulos, N., 2006, Dimethyl sulfide and dimethyl sulfoxide and their oxidation in the atmosphere, Chem. Rev. 106 (3), 940 – 975.
Becker, K.H., Nelsen, W., Su, Y., and Wirtz, K., 1990, A new mechanism for the reaction CS2 + OH, Chem. Phys. Lett. 168 (6), 559 – 563.
Berresheim, H., Wine, P.H., and Davis, D.D., 1995, Sulphur in the atmosphere, in: Composition, Chemistry, and Climate of the Atmosphere, H.B. Singh, ed., Van Nostrand Reinhold, New York, pp. 251 – 307.
Charlson, R.J., Lovelock, J.E., Andreae, M.O., and Warren, S.G., 1987, Oceanic phytoplankton, atmospheric sulphur, cloud albedo and climate, Nature 326, 655 – 661.
Hynes, A.J., Wine, P.H., and Semmes, D.H., 1986, Kinetics and mechanism of OH reactions with organic sulphides, J. Phys. Chem. 90, 4148 – 4156.
Kukui, A., Borissenko, D., Laverdet, G., and LeBras, G., 2003, Gas-phase reactions of OH radicals with dimethyl sulfoxide and methane sulfinic acid using turbulent flow reactor and chemical ionization mass spectrometry, J. Phys. Chem. A 107 (30), 5732 – 5742.
Librando, V., Tringali, G., Hjorth, J., and Coluccia, S., 2004, OH-initiated oxidation of DMS/DMSO: reaction products at high NOx levels, Environ. Poll. 127, 403 – 410.
Niki, H., Maker, P.D., Savage, C.M., and Breitenbach, L.P., 1983a, An FTIR study of the mechanism for the reaction HO + CH3SCH3, Int. J. Chem. Kinet. 15, 647 – 654.
Niki, H., Maker, P.D., Savage, C.M., and Breitenbach, L.P., 1983b, Spectroscopic and photochemical properties of CH3SNO, J. Phys. Chem. 87 (1), 7 – 9.
Patroescu, I.V., Barnes, I., and Becker, K.H., 1996, FTIR kinetic and mechanistic study of the atmospheric chemistry of methyl thiolformate, J. Phys. Chem. 100 (43), 17,207 – 17,217.
Patroescu, I.V., Barnes, I., Becker, K.H., and Mihalopoulos, N., 1999, FT-IR product study of the OH-initiated oxidation of DMS in the presence of NOx, Atmos. Environ. 33, 25 – 35.
Sørensen, S., Falbe-Hansen, H., Mangoni, M., Hjorth, J., and Jensen, N.R., 1996, Observation of DMSO and CH3S(O)OH from the gas phase reaction between DMS and OH, J. Atmos. Chem. 24, 299 – 315.
Tuazon, E.C., MacLeod, H., Atkinson, R., and Carter, W.P.L., 1986, α -Dicarbonyl yields from the NOx-air photooxidations of a series of aromatic hydrocarbons in air, Environ. Sci. Technol. 20, 383 – 387, 1986
Turnipseed, A.A., Barone, S.B., and Ravishankara, A.R., 1996, Reaction of OH with dimethyl sulphide. 2. Products and mechanisms, J. Phys. Chem. 100 (35), 14,703 – 14,713.
Urbanski, S.P. and Wine, P.H., 1999, Chemistry of gas phase organic sulfur-centred radicals, in: S-Centred Radicals, Z.B. Alfassi, ed., Wiley, New Jersey, pp. 97 – 140.
Urbanski, S.P., Stickel, R.E., Zhao, Z., and Wine, P.H., 1997, Mechanistic and kinetic study of formaldehyde production in the atmospheric oxidation of dimethyl sulfide, J. Chem. Soc., Faraday Trans. 93 (16), 2813 – 2819.
Urbanski, S.P., Stickel, R.E., and Wine, P.H., 1998, Mechanistic and kinetic study of the gas-phase reaction of hydroxyl radical with dimethyl sulfoxide, J. Phys. Chem. A 102 (51), 10,522 – 10,529.
Williams, M.B., Campuzano-Jost, P., Bauer, D., and Hynes, A.J., 2001, Kinetic and mechanistic studies of the OH-initiated oxidation of dimethylsulfide at low temperature — a reevaluation of the rate coefficient and branching ratio, Chem. Phys. Lett. 344, 61 – 67.
Williams, M.B., Campuzano-Jost, P., Cossairt, B.M., Hynes, A.J., and Pounds, A.J., 2007, Experimental and theoretical studies of the reaction of the OH radical with alkyl sulfides: 1. direct observations of the formation of the OH-DMS adduct-pressure dependence of the forward rate of addition and development of a predictive expression at low temperature, J. Phys. Chem. A 111, 89 – 104.
Yin, F., Grosjean, D., and Seinfeld, J.H., 1990a, Photooxidation of dimethyl sulfide and dimethyl disulfide. I: Mechanism development, J. Atmos. Chem. 11 (4), 309 – 364.
Yin, F., Grosjean, D., Flagan, R.C., and Seinfeld, J.H., 1990b, Photooxidation of dimethyl sulfide and dimethyl disulfide. II: Mechanism evaluation, J. Atmos. Chem. 11 (4), 365 – 399.
Author information
Authors and Affiliations
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 2008 Springer Science + Business Media B.V
About this paper
Cite this paper
Albu, M., Barnes, I., Becker, K.H., Patroescu-Klotz, I., Benter, T., Mocanu, R. (2008). Ft-Ir Product Study On The Oh Radical Initiated Oxidation Of Dimethyl Sulfide: Temperature And O2 Partial Pressure Dependence. In: Barnes, I., Kharytonov, M.M. (eds) Simulation and Assessment of Chemical Processes in a Multiphase Environment. NATO Science for Peace and Security Series C: Environmental Security. Springer, Dordrecht. https://doi.org/10.1007/978-1-4020-8846-9_41
Download citation
DOI: https://doi.org/10.1007/978-1-4020-8846-9_41
Publisher Name: Springer, Dordrecht
Print ISBN: 978-1-4020-8845-2
Online ISBN: 978-1-4020-8846-9
eBook Packages: Earth and Environmental ScienceEarth and Environmental Science (R0)