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Kinetic isotope effects (KIEs) in the free radical reactions-application to the atmospheric chemistry

Research Project

Project/Area Number 10640505
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Physical chemistry
Research InstitutionKYOTO UNIVERSITY (2000)
National Institute for Environmental Studies (1998-1999)

Principal Investigator

WASHIDA Nobuaki  Professor, Department of Chemistry Graduate School of Science, Kyoto University, 大学院・理学研究科, 教授 (70101045)

Co-Investigator(Kenkyū-buntansha) 猪俣 敏  国立環境研究所, 大気圏環境部, 研究員 (80270586)
古林 仁  環境庁, 国立環境研究所・大気圏環境部, 研究員 (00270588)
Project Period (FY) 1998 – 2000
Project Status Completed (Fiscal Year 2000)
Budget Amount *help
¥2,700,000 (Direct Cost: ¥2,700,000)
Fiscal Year 2000: ¥600,000 (Direct Cost: ¥600,000)
Fiscal Year 1999: ¥1,000,000 (Direct Cost: ¥1,000,000)
Fiscal Year 1998: ¥1,100,000 (Direct Cost: ¥1,100,000)
Keywordsrate constant / isotope / isotope effect / photoionization / mass spectrometer / atomospheric chemistry / methyl radical / laser-induced fluorescence / 同位体蓄積
Research Abstract

Stable isotope analysis of atmospheric trace gases can be very useful in improving our understanding of their sources, sinks, and transport. The rationale is that various sources have characteristic isotopic ratios and that sink processes are accompanied by isotope fractionation. The last few years have witnessed great concern about changes in the chemical composition of the Earth's atmosphere, and a significant amount of research has been devoted to this questions. One of the principal subjects of the recent studies is methane. Methane is an important greenhouse gas whose relative concentrations in the stratosphere and troposphere is affected by reaction with the radicals OH, O (^1D), and Cl. A very useful indicator of the sources and sinks of methane in the environment is provided by measurements of the ^<12>C/^<13>C ratios, and interpretation of these data requires an understanding of the kinetic isotope effects (KIEs) of several processes that lead to fractionation. Kinetic isotope effects (KIEs) are rats of ratios of rate constants for pains of isotopically different molecules. They are widely used as tools for elucidating reaction mechanism and have been investigated both experimentally and theoretically. In this project a new method to determine the KIEs value of free radical reactions has been developed by using the high sensitive photoionization mass spectrometer. The KIEs values for reactions of methyl radicals (^<12>CH_3, ^<12>CH_3, CD_3) with atomic or molecular oxygen were determined.

Report

(4 results)
  • 2000 Annual Research Report   Final Research Report Summary
  • 1999 Annual Research Report
  • 1998 Annual Research Report
  • Research Products

    (34 results)

All Other

All Publications (34 results)

  • [Publications] R.Zils: "Direct Observation of the Equilibrium between Cycohexenyl Radicals, O2, and Cyclohexenylperoxy Radicals."Chemical Physics. 231. 303-313 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] N.Washida: "Laser-Induced Fluorescence of Methyl Substituted Vinoxy Radicals and Reactions of Oxygen Atoms with Olefins."Journal of Physical Chemistry. A・102. 7924-7930 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] S.Inomata: "Rate Constant for the Reaction of NH_2 and HNO with Atomic Oxygen, O(^3P), at Temperature between 242 and 473K."Journal of Physical Chemistry A. A・103. 5023-5031 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] S.Inomata: "Laser-Induced Fluorescence of the CD_2CFO Radical."Journal of Chemical Physics. 111. 6356-6362 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] T.Oguchi: "Kinetic Study on Reaction of 1-and 2-Methylvinoxy Readicals with O_2."Journal of Physical Chemistry. A・105. 378-382 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] R.Zils: "Determination of the Equilibrium Constant and Thermodynamic Parameters for the Reaction of Pentadienyl radicals with O_2."Journal of Physical Chemistry. A・105. 1277-1282 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] 鷲田伸明: ""大気圏の光化学-その現状と課題"、季刊化学総説 NO.36,光化学の基礎と先端研究"日本化学会編. 17 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] 鷲田伸明: ""大気の化学"、物質の科学・反応と物性"土屋,平川 編、放送大学教育振興会. 12 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] R.Zils: "Direct Observation of the Equilibrium between Cycohexenyl Radicals, O_2, and Cyclohexenylperoxy Radicals."Chemical Physics. 231. 303-313 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] N.Washida: "Laser-Induced Fluorescence of Methyl Substituted Vinoxy Radicals and Reactions of Oxygen Atoms with Olefins."Journal of Physical Chemistry. A 102. 7924-7930 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] S.Inomata: "Rate Constant for the Reaction of NH_2 and HNO with Atomic Oxygen, O(^3P), at Temperature between 242 and 473K."Journal of Physical Chemistry. A 103. 5023-5031 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] S.Inomata: "Laser-Induced Fluorescence of the CD_2CFO Radical."Journal of Chemical Physics. 111. 6356-6362 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] T.Oguchi: "Kinetic Study on Reaction of 1- and 2- Methylvinoxy Readicals with O_2."Journal of Physical Chemistry. A 105. 378-382 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] R.Zils: "Determination of the Equilibrium Constant and Thermodynamic Parameters for the Reaction of Pentadienyl radicals with O_2."Journal of Physical Chemistry. A 105. 1277-1282 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] R.Zils: "Direct Observation of the Equilibrium between Cycohexenyl Radicals, O2,and Cyclohexenylperoxy Radicals."Chemical Physics. 231. 303-313 (1998)

    • Related Report
      2000 Annual Research Report
  • [Publications] N.Washida: "Laser-Induced Fluorescence of Methyl Substituted Vinoxy Radicals and Reactions of Oxygen Atoms with Olefins."Journal of Physical Chemistry. A・102. 7924-7930 (1998)

    • Related Report
      2000 Annual Research Report
  • [Publications] S.Inomata: "Rate Constant for the Reaction of NH_2 and HNO with Atomic Oxygen, O(^3P), at Temperature between 242 and 473K."Journal of Physical Chemistry A. A・103. 5023-5031 (1999)

    • Related Report
      2000 Annual Research Report
  • [Publications] S.Inomata: "Laser-Induced Fluorescence of the CD_2CFO Radical."Journal of Chemical Physics. 111. 6356-6362 (1999)

    • Related Report
      2000 Annual Research Report
  • [Publications] T.Oguchi: "Kinetic Study on Reaction of 1-and 2-Methylvinoxy Readicals with O_2"Journal of Physical Chemistry. A・105. 378-382 (2001)

    • Related Report
      2000 Annual Research Report
  • [Publications] R.Zils: "Determination of the Equilibrium Constant and Thermodynamic Parameters for the Reaction of Pentadienyl radicals with O_2"Journal of Physical Chemistry. A・105. 1277-1282 (2001)

    • Related Report
      2000 Annual Research Report
  • [Publications] 鷲田伸明: ""大気圏の光化学-その現状と課題",季刊化学総説NO.36,光化学の基礎と先端研究"日本化学会 編. 17 (1998)

    • Related Report
      2000 Annual Research Report
  • [Publications] 鷲田伸明: ""大気の化学",物質の科学・反応と物性"土屋,平川 編、放送大学教育振興会. 12 (1999)

    • Related Report
      2000 Annual Research Report
  • [Publications] R.Zils,S.Inomata,Y.Okunuki,N.Washida: "DirectObservation of the Equilibrium between Cycohexenyl Radicals, Oz, and Cyclohexenylperoxy Radicals"Chemical Physics. 231. 303-313 (1998)

    • Related Report
      1999 Annual Research Report
  • [Publications] N.Washida,S.Inomata,M.Furubayashi: "Laser-Induced Fluorescence of Methyl Substituted Vinoxy Radicals and Reactions of Oxygen Atoms with Olefins"Journal of Physical Chemistry. A, 102. 7924-7930 (1998)

    • Related Report
      1999 Annual Research Report
  • [Publications] M.Yamaguchi,M.Furobayashi,S.Inomata,N.Washida: "Analysis of Laser-Induced Fluorescence Spectra of theB^^< 〜>-X ^^< 〜>Transition with Calculated Franck-Condon Factors of CH_2CFO"Chemical Physics Letters. 298. 93-100 (1998)

    • Related Report
      1999 Annual Research Report
  • [Publications] S.Inomata,N.Washida: "Rate Constant for the Reaction of NHz and HNO wite Atomic Oxygen, O(3p), at Temperature between 242 and 473K"Journal of Physical Chemistry. A, 103. 5023-5031 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] S.Inomata,M.Furubayashi,T.Imamura,N.Washida: "Laser-Induced Fluorescence of the CD_2CFO Radical"Journal of Chemical Physics. 111. 6356-6362 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] R.Zils,S.Inomata,A.Miyoshi,N.Washida: "Determination of the Equilibrium Constant and Thermodynamic Parameters for the Reaction of Pentadienyl Radicals with Oz"Journal of Physical Chemistry. A, 103. 00-00 (2000)

    • Related Report
      1999 Annual Research Report
  • [Publications] 鷲田伸明: ""大気圏の光化学―その現状と課題", 季刊化学総説NO.36, 光化学の基礎と先端研究"日本化学会編. 17 (1998)

    • Related Report
      1999 Annual Research Report
  • [Publications] 鷲田伸明: ""大気の化学", 物質の科学・反応と物性"土屋, 平川編, 放送大学教育振興会. 12 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] R.Zils, S.Inomata, Y.Okunuki, N.Washida: "Direct Observation of the Equilibrium between Cycohexenyl Radicals,O_2,and Cyclohexenylperoxy Radicals." Chemical Physics. 231. 303-313 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] N.Washida, S.Inomata, M.Furubayashi: "Laser-Induced Fluorescence of Methyl Substituted Vinoxy Radicals and Reactions of Oxygen Atoms with Olefins." Journal of Physical Chemistry. A,102. 7924-7930 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] M.Yamaguchi, M.Furubayashi, S.Inomata, N.Washida: "Analysis of Laser-Induced Fluorescence Spectra of the B-X Transition with Calculated Franck-Condon Factors of CH_2CFO." Chemical Physics Letters. 298. 93-100 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] S.Inomata, N.Washida: "Rate Constant for the Reaction of NH_2 and HNO with Atomic Oxygen,O(^3P),at Temperature between 242 and 473 K." Journal of Physical Chemistry. A,103. 00-00 (1999)

    • Related Report
      1998 Annual Research Report

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Published: 1998-04-01   Modified: 2016-04-21  

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