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Reaction and Transport Process of Charged Species in Supercritical Fluids

Research Project

Project/Area Number 10044097
Research Category

Grant-in-Aid for Scientific Research (B).

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)

Co-Investigator(Kenkyū-buntansha) ITOH Kengo  University of Tokyo Graduate School, Assistant, 大学院・総合文化研究科, 助手 (40221080)
WISHART Jame  ブルックヘブン国立研究所化学部, 研究員
HOLROYD Rich  ブルックヘブン国立研究所化学部, 主任研究員
Project Period (FY) 1998 – 1999
Project Status Completed (Fiscal Year 1999)
Budget Amount *help
¥6,800,000 (Direct Cost: ¥6,800,000)
Fiscal Year 1999: ¥3,000,000 (Direct Cost: ¥3,000,000)
Fiscal Year 1998: ¥3,800,000 (Direct Cost: ¥3,800,000)
KeywordsSupercritical fluids / Electron mobility / Electron attachment reaction / Attachment / detachment equilibria / Reaction volume change / Electrostriction / ion mobility / Cluster size / 電子付着・脱離平衝定数 / 反応体積
Research Abstract

Electron mobility μ in supercritical fluids
μ-values were measured in upercritical ethane as a function of temperature and pressure over the range 33-47℃ and 40-120 bar. At all temperatures measured, μ decreases exponentially with increasing pressure, but passes through a minimum in the pressure region where x goes through a maximum. Since excess electrons are quasifree in the region of μ minima (μ=50-100 cmィイD12ィエD1/Vs), it is obvious that the scattering of electrons by the maxima in the deformation potential due to density fluctuations are the cause for the minima. Measurement of μ in SC Xe was initiated.
Rate of electron attachment and attachment/detachment equilibria
Electron attachment rate to COィイD22ィエD2 pyrimidine, pyrazine, styrene and NO, was measured in supercritical ethane. By using 10 psec pulse from the laser-electron-accelerator, both attachment and detachment rate were measured for COィイD22ィエD2, pyrimidine and pyrazine. Styrene even at high concentrations are unreactive towa … More rds electrons. For NO, however, only attachment was observed even with 10 psec pulse. Attachment-detachment equilibrium constants KィイD2eqィエD2 were determined for COィイD22ィエD2, pyrimidine and pyrazine as a function of temperature and pressure. The Gibbs energy change △GィイD2rィエD2 and the reaction volume change △VィイD2rィエD2 were estimated from KィイD2eqィエD2. The comparison of △VィイD2rィエD2 with a compressible continum model led to the conclusion that these volume changes were essentially due to the electrostriction of media by negative ions. The model also shows that the trend in △ィイD2rィエD2 with respect to pressure or additives are largely accounted for by the magnitude of polarization energy due to irons.
Ion mobility in supercritical fluids
The mobility of positive ions in ethane and of both positive and negative ions in COィイD22ィエD2 were measured. Cluster radii were estimated by means of (1) Stokes' equation and by (2) a compressible continuum model. Radii go through a maximum at the pressure where compressibility reached its peak. For ethane, both methods give largest values 15-16 nm at 33℃ and ρ/ρィイD2cィエD2-0.8. In COィイD22ィエD2 the radius for the slower ion was 12 nm at 33℃ and ρ/ρィイD2cィエD2=0.8. Preliminary measurements of positive ion mobility μ in Sc Xe indicated that μ is lower that in SC ethane and the cluster radius at the maximum is ca. 1.2nm(293K). Less

Report

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

    (18 results)

All Other

All Publications (18 results)

  • [Publications] M. Nishikawa, R.A.Holroyd, K. Itoh: "Electron attachment to NO in Supercritical Ethane"Journal of Physical Chemistry B. 102. 4189-4192 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] M. Nishikawa, K. Itoh, R.A.Holroyd: "Electron attachment to CO_2 in Supercritical Ethane"Journal of Physical Chemistry A. 103. 550-556 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] R.A.Holroyd, M. Nishikawa, K. Itoh: "Thermodynamics of Electron Attachment of Pyrimidine and Styrene in Supercritical Ethane"Journal of Physical Chemistry B. 103. 9205-9210 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] R.A.Holroyd, M. Nishikawa, K. Itoh: "Charged Species in Supercritical Fluids - Properties and Reactions -"Proc. Int. Symp. Prospects for Appl. Rad. Toward 21st Century. (印刷中). (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] R.A.Holroyd, M. Nishikawa, K. Itoh: "Behavior of Charged Species in Nonpolar Supercritical Fluids-Electron Attachment and Ionic Transport"Proceedings of 5th International Symposium on Supercritical Fluids. (印刷中). (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] M.Nishikawa, R.A.Holroyd, K.Itoh: "Electron attachment to NO in supercritical ethane"J.Phys.Chem.B. 102/21. 4189-4192 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] M.Nishikawa, K.Itoh, R.A.Holroyd: "Electron attachment to COィイD22ィエD2 in Supercritical ethane"J.Phys.Chem.A.. 103/4. 550-557 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] R.A.Holroyd, M.Nishikawa, K.Itoh: "Thermodynamics of clectron attachment to pyrimidine and styrene in supercritical ehtane"J.Phys.Chme.B. 103/43. 9205-9210 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] M.Nishikawa, K.Itoh, R.A.Holroyd: "Behavior of excess electrons in supercritical fluids"Proc.13th Int.Conf.on Diel.Liquids. 9-12 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] R.A.Holroyd, M.Nishikawa, K.Itoh: "Charged species in supercritical fluids"Proc.Int.Symp.Appl.Radiat.21st Century. to appear. (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] R.A.Holroyd, M.Nishikawa, K.Itoh: "Behavior of charged species in Nonpolar supercritical fluids"Proc. 5th Int.Symp.Supercrit Fluids. to appear. (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] M.Nishikawa,K.Itoh,R.A.Holroyd: "Electron Attachement to CO_2 in Suoercritical Ethane"Journal of Physical Chemistry A. 103・4. 550-556 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] R.A.Holroyd,M.Nishikawa,K.Itoh: "Thermodynamics of Electron Attachment to Pyrimidine and Styrene in Supercritical Ethane"ournal of Physical Chemistry B. 103・43. 9205-9210 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] M.Nishikawa,K.Itoh,R.A.Holroyd: "Behavior of Excess Electron in Supercritical Fluids-Electron Attachment-"Proceedings of 13th International Conference Dielectric Liquids. 9-12 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] R.A.Holroyd,M.Nishikawa,K.Itoh: "Charged Species in Supercritical Fluids-Properties and Reactions-"Proceedings of Int.Symposium for Appl. Of Radiation towards 21st Century. 予定 (2000)

    • Related Report
      1999 Annual Research Report
  • [Publications] R.A.Holroyd,M.Nishikawa,K.Itoh: "Behavior of Charged Species in Nonpolar Supercritical Fluids-Electron Attachment and Ionic Transport"Proceedings of 5th International Symposium on Supercritical Fluids. 予定. (2000)

    • Related Report
      1999 Annual Research Report
  • [Publications] Masaru Nishikawa: "Electron attachment to NO in supercritical ethane" Journal of Physical ChemistryB. 102・21. 4189-4192 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] Masaru Nishikawa: "Electron attachment to CO_2 in supercritical ethane" Journal of Physical ChemistryB. (Accepted).

    • Related Report
      1998 Annual Research Report

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

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