Supercritical fluids, properties viscosity

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). 

Conventional nitrocellulose lacquer finishing leads to the emission of large quantities of solvents into the atmosphere. An ingeneous approach to reducing VOC emissions is the use of supercritical carbon dioxide as a component of the solvent mixture (172). The critical temperature and pressure of CO2 are 31.3°C and 7.4 MPa (72.9 atm), respectively. Below that temperature and above that pressure, CO2 is a supercritical fluid. It has been found that under these conditions, the solvency properties of CO2 ate similar to aromatic hydrocarbons (see Supercritical fluids). The coating is shipped in a concentrated form, then metered with supercritical CO2 into a proportioning airless spray gun system in such a ratio as to reduce the viscosity to the level needed for proper atomization. VOC emission reductions of 50% or more are projected. 

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,... 

Supercritical fluid chromatography (SFC) refers to the use of mobile phases at temperatures and pressures above the critical point (supercritical) or just below (sub-critical). SFC shows several features that can be advantageous for its application to large-scale separations [132-135]. One of the most interesting properties of this technique is the low viscosity of the solvents used that, combined with high diffusion coefficients for solutes, leads to a higher efficiency and a shorter analysis time than in HPLC. 

The use of both sub- and supercritical fluids as eluents yields mobile phases with increased diffusivity and decreased viscosity relative to liquid eluents [23]. These properties enhance chromatographic efficiency and improve resolution. Higher efficiency in SFC shifts the optimum flowrate to higher values so that analysis time can be reduced without compromising resolution [12]. The low viscosity of the eluent also reduces the pressure-drop across the chromatographic column and facilitates the... 

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]. 

A supercritical fluid exhibits physical-chemical properties intermediate between those of liquids and gases. Mass transfer is rapid with supercritical fluids. Their dynamic viscosities are nearer to those in normal gaseous states. In the vicinity of the critical point the diffusion coefficient is more than 10 times that of a liquid. Carbon dioxide can be compressed readily to form a liquid. Under typical borehole conditions, carbon dioxide is a supercritical fluid. 

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],... 

Because their solvent properties are very good and their viscosities are very low, supercritical fluids can be used for very efficient extraction of analytes from solid phase samples. The solid phase sample is held in a tube or cartridge and the supercritical fluid made to flow through (minimal pressure required). The fluid with the analyte is then made to flow through a trap solvent. The analyte dissolves in this solvent and the fluid reverts back to the gas phase. 

The first use of supercritical fluid extraction (SFE) as an extraction technique was reported by Zosel [379]. Since then there have been many reports on the use of SFE to extract PCBs, phenols, PAHs, and other organic compounds from particulate matter, soils and sediments [362, 363, 380-389]. The attraction of SFE as an extraction technique is directly related to the unique properties of the supercritical fluid [390]. Supercritical fluids, which have been used, have low viscosities, high diffusion coefficients, and low flammabilities, which are all clearly superior to the organic solvents normally used. Carbon dioxide (C02, [362,363]) is the most common supercritical fluid used for SFE, since it is inexpensive and has a low critical temperature (31.3 °C) and pressure (72.2 bar). Other less commonly used fluids include nitrous oxide (N20), ammonia, fluoro-form, methane, pentane, methanol, ethanol, sulfur hexafluoride (SF6), and dichlorofluoromethane [362, 363, 391]. Most of these fluids are clearly less attractive as solvents in terms of toxicity or as environmentally benign chemicals. Commercial SFE systems are available, but some workers have also made inexpensive modular systems [390]. 

Supercritical fluid chromatography (SFC) is an intermediate chromatographic technique between GC and HPLC. It depends upon the fact that when a fluid becomes supercritical (both the temperature and pressure are at or above its critical point) it develops some of the solvating properties of a liquid whilst retaining the low viscosity of a gas. Hence, mass transfer (essential to efficient chromatography) is more akin to that of GC than HPLC, but many compounds can be chromatographed at temperatures much lower than what would be required by GC, so some thermally labile compounds are amenable to SFC where they would degrade under GC conditions [28]. 

A special area of HP NMR in catalysis involves supercritical fluids, which have drawn substantial attention in both industrial applications and basic research [249, 254, 255]. Reactions in supercritical fluids involve only one phase, thereby circumventing the usual liquid/gas mixing problems that can occur in conventional solvents. Further advantages of these media concern their higher diffusivities and lower viscosities [219]. The most commonly used supercritical phase for metal-catalyzed processes is supercritical CO2 (SCCO2), due to its favorable properties [256-260], i. e., nontoxicity, availability, cost, environmental benefits, low critical temperature and moderate critical pressure, as well as facile separation of reactants, catalysts and products after the reaction. 

An even more useful property of supercritical fluids involves the near temperature-independence of the solvent viscosity and, consequently, of the line-widths of quadrupolar nuclei. In conventional solvents the line-widths of e. g. Co decrease with increasing temperature, due to the strong temperature-dependence of the viscosity of the liquid. These line-width variations often obscure chemical exchange processes. In supercritical fluids, chemical exchange processes are easily identified and measured [249]. As an example. Figure 1.45 shows Co line-widths of Co2(CO)g in SCCO2 for different temperatures. Above 160 °C, the line-broadening due to the dissociation of Co2(CO)g to Co(CO)4 can be easily discerned [249]. 

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