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Fast charge transport processes in dielectric liquids under high pressure

Research Project

Project/Area Number 06044048
Research Category

Grant-in-Aid for international Scientific Research

Allocation TypeSingle-year Grants
SectionJoint Research
Research InstitutionKanagawa Institute of Technology

Principal Investigator

NISHIKAWA Masaru  Professor, Kanagawa Insatitute of Technology, 工学部, 教授 (10012329)

Co-Investigator(Kenkyū-buntansha) SCHILLER Robert  Professor, Central Research Institute for Physics Hungarian Academy of Sciences, 化学部, 教授
HOLROYD Rich  ブルックヘブン国立研究所, 化学部, 主任研究員
ITOH Kengo  Assistant, University of Tokyo, 教養学部, 助手 (40221080)
HOLROYD Richard A.  Senior Chemist, Brookhaven National Laboratory
Project Period (FY) 1994 – 1995
Project Status Completed (Fiscal Year 1995)
Budget Amount *help
¥9,800,000 (Direct Cost: ¥9,800,000)
Fiscal Year 1995: ¥5,400,000 (Direct Cost: ¥5,400,000)
Fiscal Year 1994: ¥4,400,000 (Direct Cost: ¥4,400,000)
KeywordsElectron mobility / Electron transport process / Partial molar volume / Dielectric liquid / Liquid hydrocarbon / Nonpolar liquid / Charge transfer / Electron capture reaction / Excess electron / 電荷移動
Research Abstract

The behavior of excess electrons in dielectric liquids was studied both experimentally and theoretically. Experiments include mobility an d reaction rate measurements as a function of pressure (1-3,000 bar) and temperature (0-120゚C). Mobility values were measured in : 1.mixtures of 2,2-dimethylbutane (DMB) and n-hexane, 2.m-and o-xylene, 3.hexamethyldisoloxane (HMDS) and bistrimethylsiylmethane (BTMSM), 4.tri-, tetramethylethylene and 1-pentene. 5.Electron attachment and detachment rates, and equilibrium constants with CO_2 were measured in HMDS and BTMSM.6.The pressure dependence of conducting state energy V_0 in several dielectric liquids were analyzed by means of thermodynamics. Results and Discussion 1.Above 75% DMB electrons are essentially quasifree, and below 75% localization becomes predominant. 2.Pressure dependence of mu in xylenes (0.01-0.2cm^2/Vs) is of hitherto unknown type, namely it goes through a maximum at an intermediate pressure which shifts toward higher values with … More temperature. 3.Although HMDS is an ether-like compound, electrons are not solvated throughout the pressure range (mu*20). mu are still higher (*60) in BTMSM.These higher values are attributed to the highly symmetrical molecular shape. 4.1-pentene is a typical low mu liquid olefin (0.01-0.2). Whereas tri and tetramethylethylene are intermediate mu-liquids (2-5 and 8-12, respectively). 1 through 4, the partial molar volumes of electrons Ve were estimated from the pressuredependence of mu for respective liquids in terms of a 2-state model. 5.From the electron attachment/detachment equilibrium constants with CO_2 in HMDS and BTMSM,the ground-state energy for electrons in these liquids were estimated by means of the Born-Haber cycle. 6.Thermodynamic treatment of V_0 values revealed that Ve of the quasifree electrons are positive (40 for tetramethylsilane-200cm^3/mole for n-pentane).
Conclusion The most important finding of this study is that the behavior of electrons in dielectric liquids are governed by the partial molar volume of electrons in the respective liquids : When the compressibility chi is large, Ve is negative and electron localization (into cavities) becomes predominant, while for liquids with smaller chi, electrons tend to stay quasifree. The importantce of chi is due to the fact that the electrostriction volume and hence Ve are determined by the magnitude of chi. Less

Report

(2 results)
  • 1995 Final Research Report Summary
  • 1994 Annual Research Report
  • Research Products

    (20 results)

All Other

All Publications (20 results)

  • [Publications] Holroyd・ Schwartz・ Stradowska・伊藤・二宮・西川: "The e^- + 1,3-butadiene 【double arrow】 1,3butadiene^- Equilibrium in n-Hexane" Journal of Physical Chemistry. 98. 7142-7146 (1994)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Schiller・ Holroyd・西川: "Some thermodynamic considerations on the quasifree state of excess electrons in hydrocarbons" NATO ASl Ser. B, Physics. 326. 121-125 (1994)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Schiller・ Holroyd・西川: "Thermodynamics of electron injection" NATO ASl Ser. B, Physics. 326. 347-352 (1994)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Holroyd・ Stradowska・伊藤 西川: "Volume and entropy changes in electron attachment reactions : butadiene in 2,2-dimethylbutane" Radiat. Phys. Chem.47. 39-42 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] 伊藤・西川・Holroyd: "Electron mopbility in liquid n-hexane/2,2-dimethylbutane mixtures under high pressure" J. Chem. Phys.104. 1545-1548 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] 伊藤・西川・Holroyd: "Electron transport in liquid o- and m- xylene under high pressure" (in preparation).

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] 伊藤・西川・Holroyd: "Electron mobility and energy level in hexamethyldisiloxane and bistrimethyl-methane as a function of pressure and temperature" (in preparation).

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] 伊藤・西川・Holroyd: "Electron mobility in liquid tetra-, tri-methylethylene and 1-pentene under high pressure" (in preparation).

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] R.A.Holroyd, H.A.Schwarz, E.Stradowska, K.Itoh, S.Ninomiya M.Nishikawa: "The e^- + 1,3-butadiene <double arrow> 1,3-butadiene^- equilibrium in n-hexane" Journal of Physical Chemistry. 98. 7142-7146 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] R.Schiller, R.A.Holroyd, M.Nishikawa: "Some thermodynamic considerations on the quasifree state of excess electrons in hydrocarbon" NATO ASI Ser.B.Physics. 326. 121-125 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] R.Schiller, R.A.Holroyd, M.Nishikawa: "Thermodynamics of electron injection" NATO ASI Ser.B.Phsics. 326. 347-352 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] R.A.Holroyd, E.Stradowska, K.Itoh, M.Nishikawa: "Volume and entropy changes in electron attach ment reactions : Butadiene in 2,2-dimethylbutane" Radiation Physics and Chemistry. 47. 39-42 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] K.Itoh, M.Nishikawa, R.A.Holroyd: "Electron mobility in liquid n-hexane/2,2-dimethylbutane mixtures under high pressure" Journal of Chemical Physics. 104. 1545-1548 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] K.Itoh, M.Nishikawa, R.A.Holroyd: "Electron transport in liquid o-and m-xylene under high pressure" in preparation.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] K.Itoh, M.Nishikawa, R.A.Holroyd: "Electron mobility and energy level in hexamethyl-disiloxane and bistrimethylmethane as a function of pressure and temperature" in preparation.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] K.Itoh, M.Nishikawa, R.A.Holroyd: "Electron mobility in liquid tri-, tetramethylethylene and 1-pentene under high pressure" in preparation.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] 伊藤・二宮・西川・Holroyd: "Charge transport at high pressure in toluene-n-pentanemixtures" Journal of Physical Chemistry. 98. 1974-1977 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] Holroyd・Schwartz・Stradowska・伊藤・二宮・西川: "The e^- + 1,3-butadiene【double arrow】1,3-butadiene^- equilibrium in n-hexane" Journal of Physical Chemistry. 98. 7142-7146 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] Schiller・Holroyd・西川: "Some thermodynamic considerations on the quasifree state of excess electrons in hydrocarbons" NATO ASI Ser.B,Physics. 326. 121-125 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] Schiller・Holroyd・西川: "Thermodynamics of electron injection" NATO ASI Ser.B,Physics. 326. 347-351 (1994)

    • Related Report
      1994 Annual Research Report

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Published: 1994-04-01   Modified: 2016-04-21  

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