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Reactivity of charged species and cluster in supercritical fluids -Fast time-resolved spectroscopy and conductivity study-

Research Project

Project/Area Number 15550019
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Physical chemistry
Research InstitutionKanagawa Institute of Technology

Principal Investigator

NISHIKAWA Masaru  Kanagawa Institute of Technology, Faculty of Engineering, Professor, 工学部, 教授 (10012329)

Project Period (FY) 2003 – 2004
Project Status Completed (Fiscal Year 2004)
Budget Amount *help
¥3,800,000 (Direct Cost: ¥3,800,000)
Fiscal Year 2004: ¥1,800,000 (Direct Cost: ¥1,800,000)
Fiscal Year 2003: ¥2,000,000 (Direct Cost: ¥2,000,000)
Keywordssupercritical fluid / xenon / krypton / electron attachment reaction / electron mobility / charge transfer reaction / 超臨界 / 酸素 / 電子捕捉反応速度 / 電子移動反応速度 / ヘキサフルオロベンゼン / ピラジン / 二酸化炭素
Research Abstract

The most salient feature of supercritical fluids is the divergent increase of compressibility near the critical point, which is the governing factor of the behavior of charged species.
1. Excess electrons in supercritical Xe and Kr are quasi-free and their mobility below the respective critical density can be accurately predicted by the deformation potential theory in terms of acoustical phonon scattering utilizing adiabatic compressibility
2. The excimer (Xe_2^*) is produced by the recombination of Xe_2^+ with electrons. Xe_2^* can be quenched rapidly by molecular additives like ethane.
3. Reaction rates of electron attachment to solutes increase sharply near the critical point due to stabilization of resultant ions by cluster formation. The rate constant for attachment to C_6F_6 reaches 1×10^<15>m^<-1>s^<-1>, however, that with oxygen is only about 2×10^<11> m^<-1>s^<-1>. The activation volume for the former reaction can be described by the continuum compressible model.
4. Charge transfer reaction from C_6F_6^- ion to benzoquinone is diffusion-controlled and reaches a maximum 1.8×10^<11> m^<-1>s^<-1> at the density of isothermal compressibility peak.

Report

(3 results)
  • 2004 Annual Research Report   Final Research Report Summary
  • 2003 Annual Research Report
  • Research Products

    (9 results)

All 2005 2003 Other

All Journal Article (8 results) Publications (1 results)

  • [Journal Article] Properties and reactions of charged species in nonpolar supercritical fluids2005

    • Author(s)
      R.Holroyd, M.Nishikawa, K.Itoh
    • Journal Title

      J.Phys.Chem.B 109

      Pages: 2478-2486

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Rates and energy of reactions of charged species in supercritical xenon2005

    • Author(s)
      R.Holroyd, M.Nishikawa, K.Itoh
    • Journal Title

      Radiat.Phys.Chem. 73(印刷中)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Properties and reactions of charged species in nonpolar supercritical fluids2005

    • Author(s)
      R.Holroyd, M.Nishikawa, K.Itoh
    • Journal Title

      J.Phys.Chem.B 109(7)

      Pages: 2478-2486

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Rates and energy of reactions of charged species in supercritical xenon2005

    • Author(s)
      R.Holroyd, M.Nishikawa, K.Itoh
    • Journal Title

      Radiat.Phys.Chem. (accepted)

      Pages: 73-73

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Properties and Reactions of Charged Species in Nonpolar fluids2005

    • Author(s)
      R.Holroyd, M.Nishikawa, K.Itoh
    • Journal Title

      Journal of Physical Chemistry B 109・7

      Pages: 2478-2486

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Rates and Energy of Reactions of Charged Species in supercritical Xenon2005

    • Author(s)
      R.Holroyd, M.Nishikawam, K.Itoh
    • Journal Title

      Radiation Physics and Chemistry (Accepted)

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Reactions of charged species in supercritical xenon as studied by pulse radiolysis2003

    • Author(s)
      R.Holroyd, J.F.Wishart, M.Nishikawa, K.Itoh
    • Journal Title

      J.Phys.Chem.B 107

      Pages: 7281-7287

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Reactions of charged species in supercritical xenon as studied by pulse radiolysis2003

    • Author(s)
      R.Holroyd, J.F.Wishart, M.Nishikawa, K Itoh
    • Journal Title

      J.Phys.Chem.B 107(30)

      Pages: 7281-7287

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Publications] 西川 勝他: "Reactions of charged species in supercritical xenon as studied by pulse radiolysis"J.Phys.Chem.B. 107. 7281-7287 (2003)

    • Related Report
      2003 Annual Research Report

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Published: 2003-04-01   Modified: 2016-04-21  

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