Supercritical fluids, properties density

A supercritical fluid is formed whenever a substance is heated above its critical temperature. The critical temperature of a substance is the temperature above which a distinct liquid phase cannot exist, regardless of pressure. The vapor pressure of a substance at its critical temperature is itscriticalpressure. At temperatures and pressures above its critical teniperaiure and pressure (its critical point), a substance is called a supercritical fluid. Supercritical fluids have densities, viscosities, and other properties that are intermediate between those of the substance in its gaseous and liquid states. Table 29-1 compares some properties of supercritical fluids to those of typical gases and liquids. I hesc properties are important in gas. liquid, and supercritical fluid chromatography and extractions. 

The properties of fluids under supercritical conditions are considered ideal for extracting substances from exhausted activated carbons. Two supercritical fluids are of particular interest, carbon dioxide and water. Carbon dioxide has a low critical temperature of 304 K and a moderate critical pressure of 73 bar, while water has a critical temperature of 647 K and a critical pressure of 220 bar. The character of water at supercritical conditions changes from one that supports only ionic species at ambient conditions to one that dissolves paraffins, aromatics, gases and salts [65]. These supercritical fluids exhibit densities similar to those of liquids (high solvent strengths) and diffusion coefficients similar to those of gases (excellent transport characteristics), enabling them to effectively dissolve and/or desorb contaminants from the carbon surface and to easily enter/exit even the smallest pores and carry away any... 

Table 10 compares. some important physicochemical properties of a liquid (HPLC). a gas (GC). and a supercritical fluid. The density— and thus the solvation characteristics of the supercritical fluid — are very similar to those of a liquid. 

Water becomes less dense due to thermal expansion with increase in temperature. The density of water is 1.0 g/cm at room temperature, which changes to 0.7 g/cm at 306 C. At critical point, the densities of the two phases become identical and they become a single fluid, which is called supercritical fluid. The density of water at this point is 0.3 g/cm In the supercritical region, most of the properties of water vary widely. The most important of these is the heat capacity at constant pressure, which approach infinity at the critical point. Also, the dielectric constant of dense, supercritical water ranges from 5 to 20 on variation of applied pressure. 

Several research groups have used pyrene as a fluorescent probe in the study of supercritical fluid properties (2,3,40-48). In particular, the density dependence of the Py scale has been examined systematically in a number of supercritical fluids such as CO2 (2,3,40-43,45,46), ethylene (40,41,47), fluoro-form (3,40,41,43,47), and C02-fluoroform mixtures (43). The Py values obtained in various supercritical fluids correlate well with the polarity or polarizability parameters of the fluids (3,40,41,43,47). For example, Brennecke et al. (40) found that the Py values obtained in fluoroform were consistently larger than those obtained in CO2, which were, in turn, consistently larger than those found in ethylene over the entire density region examined. In addition, the Py values obtained in the liquid-like region (reduced density 1.8) indicate that the local polarity of fluoroform is comparable to that of liquid methanol, CO2 with xylenes, and ethane with simple aliphatic hydrocabons (15,16). 

As it has appeared in recent years that many hmdamental aspects of elementary chemical reactions in solution can be understood on the basis of the dependence of reaction rate coefficients on solvent density [2, 3, 4 and 5], increasing attention is paid to reaction kinetics in the gas-to-liquid transition range and supercritical fluids under varying pressure. In this way, the essential differences between the regime of binary collisions in the low-pressure gas phase and tliat of a dense enviromnent with typical many-body interactions become apparent. An extremely useful approach in this respect is the investigation of rate coefficients, reaction yields and concentration-time profiles of some typical model reactions over as wide a pressure range as possible, which pemiits the continuous and well controlled variation of the physical properties of the solvent. Among these the most important are density, polarity and viscosity in a contimiiim description or collision frequency. 

A paiticularly attiactive and useful feature of supeicritical fluids is that these materials can have properties somewhere between those of a gas and a hquid (Table 2). A supercritical fluid has more hquid-hke densities, and subsequent solvation strengths, while possessiag transport properties, ie, viscosities and diffusivities, that are more like gases. Thus, an SCF may diffuse iato a matrix more quickly than a Hquid solvent, yet still possess a Hquid-like solvent strength for extracting a component from the matrix. 

Reactions. Supercritical fluids are attractive as media for chemical reactions. Solvent properties such as solvent strength, viscosity, diffusivity, and dielectric constant may be adjusted over the continuum of gas-like to Hquid-like densities by varying pressure and temperature. Subsequently, these changes can be used to affect reaction conditions. A review encompassing the majority of studies and apphcations of reactions in supercritical fluids is available (96). 

Thermodynamic Properties The variation in solvent strength of a supercritical fluid From gaslike to hquidlike values may oe described qualitatively in terms of the density, p, or the solubihty parameter, 6 (square root of the cohesive energy density). It is shown For gaseous, hquid, and SCF CO9 as a function of pressure in Fig. 22-17 according to the rigorous thermodynamic definition ... 

Transport Properties Although the densities of supercritical fluids approach those of conventional hquids, their transport properties are closer to those of gases, as shown for a typical SCF such as CO9 in Table 22-12. For example, the viscosity is several orders of magnitude lower than at liquidlike conditions. The self-diffusion coefficient ranges between 10" and 10" em /s, and binaiy-diffusiou coefficients are similar [Liong, Wells, and Foster, J. Supercritical Fluids 4, 91 (1991) Catchpole and King, Ind. Eng. Chem. Research, 33,... 

TABLE 22-12 Density and Transport Properties of a GaS/ Supercritical Fluid/ and a Liquid... 

Ionic liquids have been described as designer solvents [11]. Properties such as solubility, density, refractive index, and viscosity can be adjusted to suit requirements simply by making changes to the structure of either the anion, or the cation, or both [12, 13]. This degree of control can be of substantial benefit when carrying out solvent extractions or product separations, as the relative solubilities of the ionic and extraction phases can be adjusted to assist with the separation [14]. Also, separation of the products can be achieved by other means such as, distillation (usually under vacuum), steam distillation, and supercritical fluid extraction (CO2). 

Supercritical fluids (SCFs) are compounds that exist at a temperature and pressure that are above their corresponding critical values [70,71]. They exhibit the properties of both gases and Hquids. With gases, they share the properties of low surface tension, low viscosity, and high diffusivity. Their main Hquid-like feature is the density, which results in enhanced solubility of solutes compared with the solubility of gases. Furthermore, the solubility of solutes can be manipulated by changes in pressure and temperature near the critical point [72]. 

In general, the properties of supercritical fluids make them interesting media in which to conduct chemical reactions. A supercritical fluid can be defined as a substance or mixture at conditions which exceed the critical temperature (Tc) and critical pressure (Pc). One of the primary advantages of employing a supercritical fluid as the continuous phase lies in the ability to manipulate the solvent strength (dielectric constant) simply by varying the temperature and pressure of the system. Additionally, supercritical fluids have properties which are intermediate between those of a liquid and those of a gas. As an illustration, a supercritical fluid can have liquid-like density and simultaneously possess gas-like viscosity. For more information, the reader is referred to several books which have been published on supercritical fluid science and technology [1-4],... 

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