FT-IR product study of the gas-phase Br-initiated oxidation of trans-2-butene under atmospheric conditions between 246 and 298 K

A. Bierbach; I. Barnes; And K. H. Becker

doi:10.3402/tellusb.v49i5.16009

FT-IR product study of the gas-phase Br-initiated oxidation of trans-2-butene under atmospheric conditions between 246 and 298 K

Tellus B: Chemical and Physical Meteorology

Volume 49 (1997): Issue 5

By: A. Bierbach, I. Barnes and And K. H. Becker

Open Access

|Jan 1997

Abstract

The products of the Br-atom initiated oxidation of trans-2-butene have been studied in a largevolume reaction chamber between 246 and 298 K using in situ FT-IR for the analysis. 3-Bromobutan-2-one, acetaldehyde and acetylbromide were the major products of this oxidation process. Additional products included formaldehyde and hydrogen bromide and evidence was found for the formation of 3-bromobutan-2-hydroperoxide. Decreasing the temperature from 298 K down to 246 K resulted in an increase in the yield of 3-bromobutan-2-one and a decrease in the yields of acetaldehyde, acetylbromide, formaldehyde and hydrogen bromide. Addition of NO to the reaction system resulted in nearly a doubling of the yields of 3-bromobutan-2-one, acetaldehyde and formaldehyde. The reaction mechanism is discussed and possible consequences of the results for the involvement of bromine/alkene chemistry in the springtime depletion of ozone in the Arctic are considered.

References

Abbatt , J. P. D . 1994 . Heterogeneous reaction of HOBr with HBr and HCl on ice surfaces at 228 K . Geophys. Res. Lett . 21 , 665 – 668 .
Search in Google Scholar Back to article
Albritton , D. L. and Watson , R. T . 1993. Methyl bromide and the ozone layer: A summary of current under-standing. In: Methyl bromide: its atmospheric science, technology and economics. Montreal Protocol Assess-ment Supplement, (ed. R. T. Watson , D. L. Albritton , S. O. Anderson , and S. Lee-Bapty ) UNEP, Nairobi , Kenya , 3 - 18 .
Search in Google Scholar Back to article
Asplund , G. and Grimvall , A . 1991 . Organohalogens in nature . Environ. Sci. Technol . 25 , 1346 – 1350 .
Search in Google Scholar Back to article
Atkinson , R . 1994 . Gas-phase tropospheric chemistry of organic compounds . J. Phys. Chem. Ref. Data, Mono-graph 2 , 1 – 216 .
Search in Google Scholar Back to article
Atkinson , R . 1995. Gas phase tropospheric chemistry of organic compounds. In: Issues in environmental science and technology 4. Volatile organic compounds in the atmosphere, (ed. R. E. Hester and R. M. Harrison ) The Royal Society of Chemistry , London, UK , 65 - 89 .
Search in Google Scholar Back to article
Atkinson , R. , Baulch , D. L. , Cox , R. A. , Hampson , Jr. , R. F. , Kerr, J. A. and Troe , J. 1992. Evaluated kinetic and photochemical data for atmospheric chemistry, supplement IV. J. Phys. Chem. Ref. Data 21, 1125 - 1568 .
Search in Google Scholar Back to article
Barnes , I. , Bastian , V. , Becker , K. H. , Overath , R. and Tong , Z . 1989 . Rate constants for the reactions of Br atoms with a series of alkanes, alkenes, and alkynes in the presence of 02 . Int. J. Chem. Kinet . 21 , 499 – 517 .
Search in Google Scholar Back to article
Barnes, I. Becker, K. H. and Starcke , J. 1991. Fourier-transform IR spectroscopic observation of gaseous nitrosyl iodine, nitryl iodine, and iodine nitrate. J. Phys. Chem. 95, 9736 - 9740 .
Search in Google Scholar Back to article
Barrie , L. A. , Bottenheim , J. W. , Schnell , R. C. , Crutzen , P. J. and Rasmussen R. A . 1988 . Ozone destruction and photochemical reactions at polar sunrise in the lower arctic atmosphere . Nature 334 , 138 – 141 .
Search in Google Scholar Back to article
Barrie , L. A. , Den Hartog , G. , Bottenheim , J. W. and Landsberger , S . 1989 . Anthropogenic aerosols and gases in the lower troposphere at Alert Canada in April 1986 . J. Atmos. Chem . 9 , 101 – 127 .
Search in Google Scholar Back to article
Barrie , L. A. , Staebler , R. , Toom , D. , Georgi , B. , den Hartog , G. , Landsberger , S. and Wu , D . 1994a . Arctic aerosol size-segregated chemical observations in rela-tion to ozone depletion during polar sunrise experi-ment 1992 . J. Geophys. Res . 99 , 25439 – 25451 .
Search in Google Scholar Back to article
Barrie , L. A. , Li , S. M. , Toom , D. , Landsberger , S. and Sturges , W. T . 1994b . Lower tropospheric measure-ments of halogens, nitrates, and sulphur oxides during polar sunrise experiment 1992 . J. Geophys. Res . 99 , 25453 – 25467 .
Search in Google Scholar Back to article
Becker , K. H. , Barnes , I. , Bastian , V. and Zabel , F . 1990. Reaktionskinetisches Verhalten von Organohalogen-verbindungen unter tropospharischen Bedingungen. Abschlufibericht des Forschungsvorhabens 104 02 720. Umweltbundesamt, FRG.
Search in Google Scholar Back to article
Berg , W. W. , Heidt , L. E. , Pollock , W. , Sperry , P. D. and Cicerone , R. J . 1984 . Brominated organic species in the arctic atmosphere . Geophys. Res. Lett . 11 , 429 – 432 .
Search in Google Scholar Back to article
Bierbach , A. , Barnes , I. and Becker , K. H . 1996 . Rate coefficients for the gas-phase reactions of bromine rad-icals with series of alkenes, dienes and aromatic hydro-carbons at 298 + 2 K . Int. J. Chem. Kinet . 28 , 565 – 577 .
Search in Google Scholar Back to article
Bottenheim , J. W. , Barrie , L. A. , Atlas , E. Heidt , L. E. , Niki , H. , Rasmussen , R. A. , Chen , J. , Catoire , V. and Niki , H. 1995. Mechanistic study of the BrCH₂P radical reaction in 700 Torr air. Chem. Phys. Lett. 245, 519 - 528 .
Search in Google Scholar Back to article
Chen , J. , Young , V. , Catoire , V. and Niki , H . 1996 . FTIR Spectroscopic studies of the mechanisms of the hal-ogen atom initiated oxidation of haloacetaldehydes . J. Phys. Chem . 100 , 6580 – 6586 .
Search in Google Scholar Back to article
Cicerone , R. J. , Heidt , L. E. and Pollock , W. H . 1988 . Measurements of atmospheric methyl-bromide and bromoform . J. Geophys. Res . 93 , 3745 – 3749 .
Search in Google Scholar Back to article
Crowley , J. N. and Moortgat , G. K . 1992 . 2-bro-moethylperoxy and 2-bromo-1-methyl-propylperoxy radicals: Ultraviolet absorption spectra and self-reaction rate constants at 298 K . J. Chem. Soc. Faraday Trans . 88 , 2437 – 2444 .
Search in Google Scholar Back to article
DeMore , W. B. , Sander , S. P. , Golden , D. M. , Hampson , R. F. , Kurylo , M. J. , Howard , C. J. , Ravishankara , A. R. , Kolb , C. E. and Molina , M. J . 1994 . Chemical kinetics and photochemical data for use in stratospheric modeling . JPL Publication 94-26, Jet Propulsion Laboratory , Pasadena , California .
Search in Google Scholar Back to article
Fabian , P. , Borchers , R. and Kourtidis 1994 . Bromine-containing source gases during EASOE . Geophys. Res. Lett . 21 , 1219 – 1222 .
Search in Google Scholar Back to article
Fan , S. M. and Jacob , D. J . 1992 . Surface ozone depletion in arctic spring sustained by bromine reactions on aerosols . Nature 343 , 522 – 524 .
Search in Google Scholar Back to article
Gribble , G. W . 1994a . Natural organohalogens - many more than you think! J . Chem. Education 71 , 907 – 911 .
Search in Google Scholar Back to article
Gribble , G. W . 1994b . The natural production of chlorin-ated compounds . Environ. Sci. Technol . 28 , 310 A–317 A .
Search in Google Scholar Back to article
Hanson , D. R. and Ravishankara , A. R . 1992 . Hetero-genious chemistry of HBr and HF . J. Phys. Chem . 96 , 9441 – 9446 .
Search in Google Scholar Back to article
Hausmann , M. and Platt , U . 1994 . Spectroscopic meas-urement of bromine oxide and ozone in the arctic during polar sunrise experiment 1992 . J. Geophys. Res . 99 , 25399 – 25413 .
Search in Google Scholar Back to article
Hoekstra , E. J. and De Leer , E. W. B . 1995 . Organohalo-gens: the natural alternatives . Chemistry in Britain 127 – 131 .
Search in Google Scholar Back to article
Hov , O. , Penkett , S. A. , Isaksen , I. S. A. and Semb , A . 1984 . Organic gases in the norwegian Acrtic . Geophys. Res. Lett . 11 , 425 – 428 .
Search in Google Scholar Back to article
Iqbal , S. M. and Owen , L. N . 1960. Dithiols. Part XXI. Dithiols from cyclic trithiocarbonates . J. Chem. Soc . , 1030-103 6 .
Search in Google Scholar Back to article
Jobson , B. T. , Niki , H. , Yokouchi , Y. , Bottenheim , J. W. , Hopper , F. and Leaitch , R . 1994 , Measurements of C2-C6 hydrocarbons during the polar sunrise 1992 experiment: Evidence for Cl atom and Br atom chemistry . J. Geophys. Res . 99 , 25355 – 25368 .
Search in Google Scholar Back to article
Kaiser , E. W. and Wallington , T. J . 1995 . CH₃CO reactions with Cl₂ and O₂: more evidence for HCI elimination from the CH₃CHClO radical . J. Phys. Chem . 99 , 8669 – 8672 .
Search in Google Scholar Back to article
Khalil , M. A. K. , Rasmussen , R. A. and Gunawardena , R . 1993 . Atmospheric methyl bromide: Trends and global mass balance . Geophys. Res. Lett . 98 , 2887 – 2896 .
Search in Google Scholar Back to article
Kondo , O. and Bensen , S. W . 1984 . Kinetics and equilib-ria in the system Br + CH₃OOH =HBr +CH₃OO. An upper limit for the heat of formation of the methylper-oxy radical . J. Phys. Chem . 88 , 6675 – 6680 .
Search in Google Scholar Back to article
Laverdet , G. , Le Bras , G. , Mellouki , A. and Poulet , G . 1990 . The BrO + H02 reaction revisited: absolute determination of the rate constant at 298 K. Chem. Phys. Lett. 172, 430 - 434 .
Search in Google Scholar Back to article
Leaitch W. R. , Barrie , L. A. , Bottenheim , J. W. , Li , S. M. , Shepson , P. B. , Muthuramu , K. and Yokouchi , Y . 1994 . Airborne observations related to ozone deple-tion at polar sunrise . J. Geophys. Res . 99 , 25499 – 25517 .
Search in Google Scholar Back to article
Li , S. M. , Yokouchi , Y. , Barrie , L. A. , Muthuramu , K. , Shepson , P. B. , Bottenheim , J. W. , Sturges , W. T. and Landsberger , S . 1994 . Organic and inorganic bromine compounds and their composition in the artic tropo-sphere during polar sunrise . J. Geophys. Res . 99 , 25415 – 25428 .
Search in Google Scholar Back to article
Lightfoot , P. D. , Cox , R. A. , Crowley , J. N. , Destriau , M. , Hayman , G. D. , Jenkin , M. E. , Moortgat , G. K. and Zabel , F . 1992 . Organic peroxy radicals: kinetics, spectroscopy and tropospheric chemistry . Atmospheric Environ . 26A , 1805 – 1964 .
Search in Google Scholar Back to article
Lobert , J. M. , Butler , J. H. , Montzka , S. A. , Geller , L. S. , Myers , R. C. and Elkins , J. W . 1995 . A net sink for atmospheric CH₃Br in the East Pacific Ocean . Science 276 , 1002 – 1005 .
Search in Google Scholar Back to article
Manö , S. and Andreae , M. O . 1994. Emission of methyl bromide from biomass burning. In: Physicochemical behaviour of atmospheric pollutants (eds. G. Angeletti and G. Restelli ). Report EUR 15609/1 EN, 431 - 434 .
Search in Google Scholar Back to article
Maricq , M. M. , Szente , J. J. , Kaiser , E. W. and Shi , J . 1994 . Reactions of chlorine atoms with methylper-oxy and ethylperoxy radicals . J. Phys. Chem . 98 , 2083 – 2089 .
Search in Google Scholar Back to article
McCulloch , A . 1992 . Global production and emissions of bromochlorodifluoromethane and bromotrifluor-omethane (Halons 1211 and 1301) . Atmos. Environ . 26A , 1325 – 1329 .
Search in Google Scholar Back to article
McConnell , J. C. , Henderson , G. S. , Barrie , L. A. , Bottenheim , J. W. , Niki , H. , Langford , C. H. and Templeton , E. M. J . 1992 . Photochemical bromine production implicated in arctic boundary-layer ozone depletion . Nature 355 , 150 – 152 .
Search in Google Scholar Back to article
Mickle , R. E. , Bottenheim , J. W. , Leaitch , W. R. and Evans , W. F. J . 1989 . Boundary layer ozone depletion during AGASP-II . Atmos. Environ . 23 , 2443 – 2449 .
Search in Google Scholar Back to article
Niki , H. , Maker , P. D. , Savage , C. M. and Breitenbach , L. P . 1985 . An FTIR spectroscopic study of the reactions Br + CH₃CHO → HBr + CH₃CO and CH₃C(O)OO + NO₂= CH₃C(O)OONO₂ (PAN) . Int. J. Chem. Kinet . 17 , 525 – 534 .
Search in Google Scholar Back to article
Oltmans , S. J. Schnell , R. C. , Sheridan , P , J. , Peterson , R. E. , Li , S. M. , Winchester , J. W. , Tans , P. P. , Sturges , W. T. , Kahl , J. D. and Barrie , L. A . 1989 . Seasonal surface ozone filterable bromine relationship in the high arctic . Atmos. Environ . 23 , 2431 – 2441 .
Search in Google Scholar Back to article
Orlando , J. J. , Tyndall , G. S. and Wallington , T. J . 1996 . Atmospheric oxidation of CH₃Br: chemistry of the CH₂BrO radical . J. Phys. Chem . 100 , 7026 – 7033 .
Search in Google Scholar Back to article
Orlando , J. J. , Tyndall , G. S. , Wallington , T. J. and Dill , M . 1995 . Atmospheric chemistry of CH₂Br₂: rate coefficients for its reaction with Cl atoms and OH and the chemistry of the CHBr₂O radical . Int. J. Chem. Kinetics 28 , 433 – 442 .
Search in Google Scholar Back to article
Penkett , S. A. , Jones , B. M. R. , Rycroft , M. J. and Sim-mons , D. A . 1985 . An interhemispheric comparison of the concentrations of bromine compounds in the atmosphere . Nature 318 , 550 – 553 .
Search in Google Scholar Back to article
Platt , U. and Janssen , C . 1995 . Observation and role of the free radicals NO₃, ClO, BrO and IO in the tropo-sphere . Faraday Discuss . 100 , 175 – 198 .
Search in Google Scholar Back to article
Rasmussen , R. A. and Khalil , M. A. K . 1984 . Gaseous bromine in the arctic and arctic haze . Geophys. Res. Lett . 11 , 433 – 436 .
Search in Google Scholar Back to article
Reeves , C. E. and Penkett , S. A . 1993 . An estimate of the anthropogenic contribution to atmospheric methyl bromide . Geophys. Res. Lett . 20 , 1563 – 1566 .
Search in Google Scholar Back to article
Roberts , J. M . 1990 . Review article: the atmospheric chemistry of organic nitrates . Atmos. Environ . 24 , 243 – 287 .
Search in Google Scholar Back to article
Seakins , P. W. , Pilling , M. , Niiranen , J. T. , Gutman , D. and Krasnoperov , L. N . 1992 . Kinetics and thermo-chemistry of R + HBr = RH + Br reactions. Determina-tions of the heat of formation of C₂H₅, i-C₃H₇, sec-C₄H₉, and t-C₄H₉ . J. Phys. Chem . 96 , 9847 – 9855 .
Search in Google Scholar Back to article
Shepson , P. B . 1990 . Depletion of lower tropospheric ozone during arctic spring: The polar sunrise experi-ment 1988 . J. Geophys. Res . 95 , 18555 – 18568 .
Search in Google Scholar Back to article
Shi , J. , Wallington , T. J. and Kaiser , E. W . 1993 . FTIR product study of the Cl-initiated oxidation of C₂H₅Cl: reactions of the alkoxy radical CH₃CHClO . J. Phys. Chem . 97 , 6184 – 6192 .
Search in Google Scholar Back to article
Singh , H. B. and Kanakidou , M . 1993 . An investigation of the atmospheric sources and sinks of methylbromide . Geophys. Res. Lett . 20 , 133 – 136 .
Search in Google Scholar Back to article
Solberg , S. , Hermansen , O , Joranger , E. , Schmidtbauer , N. , Stordal , F. and Hov , O . 1994. NILU Report OR 27/94. ISBN 82-425-0575-6.
Search in Google Scholar Back to article
Tokarczyk , R. and Moore , R. M . 1994 . Production of volatile organohalogens by phytoplankton cultures . Geophys. Res. Lett . 21 , 285 – 288 .
Search in Google Scholar Back to article
Villenave , E. and Lesclaux , R . 1995 . The UV absorption spectra of CH₂Br and CH₂BrO₂ and the reaction kin-etics of CH₂BrO₂ with itself and with H02 at 298 K . Chem. Phys. Letters 236 , 376 – 384 .
Search in Google Scholar Back to article
Wallington , T. J ., Dagaut and Kurylo, M. J. 1992. Ultra-violet absorption cross sections and reaction kinetics and mechanisms for peroxy radicals in the gas phase. Chem. Rev. 92, 667-710.
Search in Google Scholar Back to article
Wallington , T. J. , Orlando , J. J. and Tyndall , G. S . 1995 . Atmospheric chemistry of chloroalkanes: Intramolecu-lar elimination of HCl from chloromethoxy radicals over the temperature range 264-336 K . J. Phys. Chem . 99 , 9437 – 9442 .
Search in Google Scholar Back to article
Wallington , T. J. , Skewes , L. , Siegl , W. O. and Japar , S. M . 1989 . A relative rate study of the reaction of brom-ine atoms with a variety of organic compounds at 295 K . Int. J. Chem. Kinet . 21 , 1069 – 1076 .
Search in Google Scholar Back to article
Yarwood , G. , Peng , N. and Niki , H . 1992 . FTIR spectro-scopic study of the Cl- and Br-atom initiated oxidation of ethene . Int. J. Chem. Kinet . 24 , 369 – 383 .
Search in Google Scholar Back to article
Yokouchi , Y. , Akimoto , H. , Barrie , L. A. , Bottenheim , J. W. , Anlauf , K. and Jobson , B. T . 1994 . Serial gas chromatographic/mass spectromentric measurements of some volatile organic compounds in the arctic atmosphere during the 1992 polar sunrise experiment . J. Geophys. Res . 99 , 25379 – 25389 .
Search in Google Scholar Back to article

Articles in this issue

DOI: https://doi.org/10.3402/tellusb.v49i5.16009 | Journal eISSN: 1600-0889

Journal RSS Feed

Language: English

Page range: 566 - 582

Submitted on: Nov 27, 1996

Accepted on: Jul 15, 1997

Published on: Jan 1, 1997

Published by: Stockholm University Press

In partnership with: Paradigm Publishing Services

© 1997 A. Bierbach, I. Barnes, And K. H. Becker, published by Stockholm University Press
This work is licensed under the Creative Commons Attribution 4.0 License.

Volume 49 (1997): Issue 5