Supercritical fluids critical phenomena

Compare the behavior of the ethylene-n-propanol system to a type I system, CO2-hexane, shown in Figure 13. Note that in both cases, solubility of the supercritical component in the liquid phase increases rapidly as the pressure increases. This phenomenon can lead to substantial swelling of the liquid phase. The solubility of the heavy component in the lighter phase does not increase rapidly with an increase in pressure until the mixture critical point is approached or an additional phase is formed. The conditions of these occurrences may be substantially removed from the pure supercritical fluid critical conditions. 

Water has an unusually high (374°C) critical temperature owing to its polarity. At supercritical conditions water can dissolve gases such as 02 and nonpolar organic compounds as well as salts. This phenomenon is of interest for oxidation of toxic wastewater (see Waste treatments, hazardous waste). Many of the other more commonly used supercritical fluids are listed in Table 1, which is useful as an initial screening for a potential supercritical solvent. The ultimate choice for a specific application, however, is likely to depend on additional factors such as safety, flammability, phase behavior, solubility, and expense. 

There is one more unique feature of supercritical fluid solvents that will be a recurring theme in this chapter. Several studies have demonstrated that near the critical point, the density of the solvent about a solute is enhanced relative to the bulk density (solvent/solute clustering). As such, the mobility of the solute may be impeded to an extent greater than expected on the basis of the bulk viscosity. This phenomenon may also affect reactivity for reactions that are diffusion-controlled or for which cage effects are important, particularly near the critical point (vide infra). 

Precipitation from supercritical fluids is of interest not only in relation to the production of uniform particles. The thermodynamics of dilute mixtures in the vicinity of the solvent s critical point (more specifically, the phenomenon known as retrograde solubility, whereby solubility decreases with temperature near the solvent s critical point) has been cleverly exploited by Chlmowitz and coworkers (12-13) and later by Johnston et al. (14). These researchers implemented an elegant process based on retrograde solubility for the separation of physical solid mixtures which gives rise to high purity materials. 

As is by now evident to the reader, the phenomenon of solubility in supercritical fluids is not new. Since 1879 (or 1861, if we include the high-pressure, near-critical liquid carbon dioxide studies of Gore), solubility, phase, and spectroscopic studies have been performed on a large number of solute-SCF mixtures. They were made for their inherent scientific and technical interest and value. And they received a resurgence of interest with the work of Diepen, Scheffer, and coworkers in the late 1940s and early 1950s. 

In thermally non-homogeneous supercritical fluids, very intense convective motion can occur [Ij. Moreovei thermal transport measurements report a very fast heat transport although the heat diffusivity is extremely small. In 1985, experiments were performed in a sounding rocket in which the bulk temperature followed the wall temperature with a very short time delay [11]. This implies that instead of a critical slowing down of heat transport, an adiabatic critical speeding up was observed, although this was not interpreted as such at that time. In 1990 the thermo-compressive nature of this phenomenon was explained in a pure thermodynamic approach in which the phenomenon has been called adiabatic effect [12]. Based on a semi-hydrodynamic method [13] and numerically solved Navier-Stokes equations for a Van der Waals fluid [14], the speeding effect is called the piston effecf. The piston effect can be observed in the very close vicinity of the critical point and has some remarkable properties [1, 15] ... 

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