Reaction and Transport Process of Charged Species in Supercritical Fluids

Electron mobility μ in supercritical fluidsμ-values were measured in upercritical ethane as afunction of temperature and pressure over the range 33-47℃and 40-120 bar. At all temperaturesmeasured, μ decreases exponentially with increasing pressure，但是passes through a minimum in the pressure region where x goes through a maximum. Since excesselectrons are quasifree in the region of μ minima (μ=50- 100cm)，it is obvious that the scattering of electrons by the maxima in the deformation potential due todensity fluctuations are the cause for the minima. Measurement of μ in SC Xe was initiated.Rate ofelectron attachment and attachment/detachment equilibriaElectron attachment rate to CO - D22 - D2pyrimidine, pyrazine, styrene and NO，方法在超级critical ethane. By using 10 psec pulse from the lasser -electron-acceleratorboth attachment and detachment rate were measured for CO D22 D2，pyrimidine and pyrazine. Styrene even at high concentrations are unreactive towa…More rds electrons. For NO, however，attachment -detachment equilibrium constants only attachment was observed even with 10 psec pulse. attachment -detachment equilibrium constantski D2eq D2 were determined for CO i D22 D2pyrimidine and pyrazine as a function of temperature and pressure. The Gibbs energy changeG - D2r - D2 and the reaction volume change V - D2r - D2 were estimated from K - D2eq - D2. thecomparison of V - D2r - D2 with a compressible continum model led to the conclusion that these volume模型also改变了传统媒体的内容shows that the trend in△D2r D2 with respect to pressure or additives are largely accounted forby the magnitude of polarization energy due to irons.Ion mobility in supercritical fluidsThemobility of positive ions in ethane and of both positive and negative ions in CO - D22 - D2 weremeasured. Cluster radii were estimated by means of (1) Stokes' equation and by (2) a compressibleRadii go through a maximum at the pressure where compressibility reached its peak.连续模型。for ethane,both methods give largest values 15- 16nm at 33℃and ρ/ρ D2c -0.8. In CO - D22 - D2 the radius forthe slower ion was 12nm at 33℃and ρ/ρ D2c =0.8. Preliminary measurements of positive ionmobility μ in Sc Xe indicated that μ is lower that in Sc ethane and the cluster radius at themaximum is ca. 1.2nm(293k). Less

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