Transport and Reaction Processes of Charged Species in Dielectric Liquids

介电液体中带电物质的输运和反应过程

• 批准号: 09640699
• 负责人: NISHIKAWA Masaru
• 金额: $ 1.92万
• 依托单位: Kanagawa Institute of Technology
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1997
• 资助国家: 日本
• 起止时间: 1997 至 1999
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-09640699/
• 关键词: Electron mobility; Liquid alkenes; Supercritical fluids; Electron attachment reaction; Attachment-detachment equilibria; Reaction volume change; Electrostriction; Activation volume; 反応速度; C_2F_4; アルケン; 電子捕捉反応; 荷電種; 輸送過程

Electron mobility μ in liquid alkense under high pressureμ-values were measured in liquid 1-pentene, cyclohexene, 2 methyl-2-butene, and 2,3-dimethyl-2-butene in the temperature range 0-80℃ and pressure range 1-3,000 bar. In 1-pentene and 2-methyl-2-butene, μ values (cmィイD12ィエD1/Vs) decrease monotonously with increasing pressure from 0.25 to 0.02 in the former and from 20 to 5 in the latter. In cyclohexene and 2,3-dimethyl-2-butene, μ changes with pressure in a very complicated manner. Especially in the latter compound at 0℃, it increases with pressure from 8 to 12. The difference in μ behavior with respect to pressure increase is due to that in the magnitude of isothermal compressibility x of respect liquid. Namely, in 1-pentene where x is large, the electrostriction of the liquid by the trapped electrons surpasses the cavity volume in which trapped electrons reside, while in cyclohexene where x is small, electron trapping caused volume increase in the liquid by creating cavity.Electr … More on mobility in supercritical ethaneM-values were measured in supercritical 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 it is obvious that excess electrons are quasifree in the region of μ minima (μ=50-100 cmィイD12ィエD1/Vs), these are due to the scattering of electrons by the maximum in the deformation potential due to that in density fluctuations.Rate of electron attachmentElectron attachment rate to NO, COィイD22ィエD2, CィイD22ィエD2FィイD24ィエD2 was measured in supercritical ethane. By using 10 psec pulse from the laser-electron-accelerator(Brookhaven National Lab), both attachment and detachment rate were measured for COィイD22ィエD2. For NO and CィイD22ィエD2FィイD24ィエD2, however, no detachment was observed even with 10 psec pulse. Attachment-detachment equilibrium constant KィイD2eqィエD2 was determined for COィイD22ィエD2 as a function of temperature and pressure. The Gibbs energy change ΔGィイD2rィエD2 and the reaction volume change ΔVィイD2rィエD2 were estimated from KィイD2eqィエD2. The comparison of activation volumes ΔVィイD1*ィエD1 estimated for NO and CィイD22ィエD2FィイD24ィエD2 as well as ΔVィイD2rィエD2 with a compressible continuum model led to the conclusion that these volume changes were essentially due to the electrostriction of media by negative ions. Less

测定了1-戊烯、环己烯、2-甲基-2-丁烯和2,3-二甲基-2-丁烯在温度0 ~ 80℃、压力1 ~ 3000 bar范围内液体烯烃的高压电子迁移率μ值。不能和2-methyl-2-buteneμ值(cmィイD12ィエD1 / Vs)减少单调和越来越大的压力从0.25到0.02在前,后者从20到5。在环己烯和2,3-二甲基-2-丁烯中，μ随压力的变化非常复杂。特别是后一种化合物在0℃时，随着压力从8增加到12。μ对压力的变化是由于液体等温可压缩性的大小x的变化。即，在x较大的1-戊烯中，被困电子对液体的电致伸缩超过了被困电子所在的空腔体积，而在x较小的环己烯中，电子被困通过形成空腔导致液体体积增加。在33-47℃和40-120 bar范围内，测量了超临界乙烷中温度和压力的函数值。在所有测量温度下，μ随压力的增加呈指数下降，但在x达到最大值的压力区，μ经过一个最小值。由于在μ极小值区域（μ=50-100 cm μ μ φ D12 μ μ φ D1/Vs）内多余的电子是准自由的，这是由于密度波动引起的变形势中最大的电子散射造成的。电子速度attachmentElectron附件率不,公司ィイD22摊位ィエD2, CィイD22摊位ィエD2FィイD24ィエD2在超临界乙烷测量。利用来自布鲁克海文国家实验室激光电子加速器的10 psec脉冲，测量了CO的附着率和脱离率。然而，对于NO和C，即使在10秒的脉冲下，也未观察到脱离。以温度和压力为函数，确定了CO φ φ φ φ φ φ φ φ φ φ φ φ φ φ。由K γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ。通过将NO和C的活化体积（ΔV刷刷刷D1*刷刷刷D1）和C刷刷刷D22刷刷刷D2F刷刷刷D24刷刷刷D2以及ΔV刷刷刷D2r刷刷刷D2与可压缩连续体模型进行比较，得出这些体积变化主要是由于负离子对介质的电致伸缩造成的。少

项目成果

M. Nishikawa, K. Itoh, R.A.Holroyd: "Behavior of Excess Electrons in Supercritical Fluids - Electron Attachment -"Proceedings of 13th International Conference on Dielectric Liquids. 9-12 (1999)

M. Nishikawa、K. Itoh、R.A.Holroyd：“超临界流体中多余电子的行为 - 电子附着 -”第 13 届介电液体国际会议论文集。

Masaru.Nishikawa: "Electron attachment to CO_2 in supercritical ethane" Journal of Physical Chemistry B. (Accepted).

Masaru.Nishikawa：“超临界乙烷中 CO_2 的电子附着”《物理化学杂志 B》（已接受）。

R.A.Holroyd,M.Nishikawa,Itoh: "Charged Species Supercritical Fluids-Properties and Rezctions-"proceedings of Int.Symposium on Prospects for Application of Radeation. (発表 予定). (2000)

R.A.Holroyd、M.Nishikawa、Itoh：“带电物质超临界流体 - 性质和反应 -”辐射应用前景国际研讨会论文集（预定的演示文稿）。

M.Nishikawa, K.Itoh, R.A.Holroyd: "Behavior of excess electrons in supercritical fluids"Proc.13th Int.Conf.on Diel.Liquids. 9-12 (1999)

M.Nishikawa、K.Itoh、R.A.Holroyd：“超临界流体中过量电子的行为”Proc.13th Int.Conf.on Diel.Liquids。

K. Itoh, R.A.Holroyd, M. Nishikawa,: "Electron Mobility in Liquid Alkenes under High Pressure"Journal of Physical Chemistry B. 102. 3147-3151 (1998)

K. Itoh、R.A.Holroyd、M. Nishikawa，“高压下液体烯烃中的电子迁移率”物理化学杂志 B. 102. 3147-3151 (1998)