Reaction and Transport Process of Charged Species in Supercritical Fluids

超临界流体中的电子流动性μ-在超临界以太中的价值被测量为超临界以太的温度和压力在33-47℃和40-120巴范围内的函数。在所有的温度都被测量了， μ decreases表示有增加的压力，但通过在压力区域的最低限度通过x通过最大限度。由于excess electrons are quasifree in the region of μ minima （μ=50-100 cm μ D12 μ D1/Vs），这是显而易见的，因为在最大化的潜力due to density fluctuations are the cause for the minima。对SC Xe的μ的测量是启动的，电子附着和附着/分离等于电子附着的速率到CO-D22-D2-吡咯烷、吡咯烷、苯乙烯和NO，并在超临界以太网中测量的。通过使用激光-电子-加速器、附件和分离速率的10秒脉冲来测量CO-I-D2、吡咯烷和吡咯烷。Styrene甚至在高浓度下都不活跃 ... More rds electrons。如果没有，则只有附件被观察到，即使是10秒脉冲。附件-分离equilibrium constants Kyi D2 eq D2 were determined for CO D22、pyrimidine和pyrazine作为温度和压力的一个功能。The Gibbs energy change_ The comparison of Oracle D2 r Oracle D2 with a compressible continum model led to the conclusion that these volume changes were essentially due to the electroManagement tion of me\by negative ions。模型also shows that the trend in__簇半径估计是由（1）斯托克斯' equation和（2）一个复杂连续模型的平均值估计的。Radii在压力下通过一个最大限度的复杂性达到了顶峰。For ethane， both methods give largest values 15-16 nm at 33℃ and？/？イD2c？エD2-0.8。D22 the radius for the slower ion was 12 nm at 33 nm at/D2c D2=0.8。在SC ethane和簇半径上的最大值是ca。1.2纳米（293 K）Less（低）

Electron mobility μ in supercritical fluidsμ-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 equilibriaElectron 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 fluidsThe 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