| Project/Area Number |
06044048
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| Research Category |
Grant-in-Aid for international Scientific Research
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| Allocation Type | Single-year Grants |
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| Section | Joint Research |
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| Research Institution | Kanagawa Institute of Technology |
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Principal Investigator |
NISHIKAWA Masaru Professor, Kanagawa Insatitute of Technology, 工学部, 教授 (10012329)
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| 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
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| Project Period (FY) |
1994 – 1995
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| Project Status |
Completed (Fiscal Year 1995)
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| 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)
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| Keywords | Electron mobility / Electron transport process / Partial molar volume / Dielectric liquid / Liquid hydrocarbon / Nonpolar liquid / Charge transfer / Electron capture reaction / Excess electron / 電荷移動 |
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| 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
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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
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