Supercritical properties

The value of r can be estimated as that of saturated liquid at the same temperature or related to supercritical properties at temperatures above critical. Critoph [2] found that for the practical purposes of modelling ammonia - carbon adsorption cycles, using experimentally determined porosity data, that the complexity of estimating both r and p at sub and supercritical levels was not justified. The measured porosity data could be fitted to a much simpler version of the equation with no loss of accuracy, as follows ... 

The effects of such precipitation conditions as pressure, temperature, and solute and solvent concentrations are listed in Table 2. These effects are related to the behavior of the maximum attainable supersaturation 5 m, as described by Equation (51) and also to the phase transition at the mcp between the jet mixing and droplet dispersion mechanisms. As follows from our earlier discussions in Sections 2 and 5, the most uniform particles can be produced under conditions very close to the mcp (practically, just above P ), where the supercritical properties are most pronounced, local values of supersaturation are high, and the constants Cgq, Tn, and tq are the smallest. Figure 19a shows that particles produced below the mixture critical pressure are more agglomerated than to the individual and separate crystal particles obtained at high pressure. This is because the nuclei confined within the droplets at P < Pm coalesce and fuse during further growth. In this respect,... 

These results, combining the widely known instability (and dissipative structure ) phenomenon of melt fracture with the new non-equilibrium description of multiphase polymer systems, will hopefully stimulate more experimental and theoretical work devoted to these (frozen) dissipative structures. Up to now, it remains open which property of the melt may be responsible for its suddenly occurring capability to disperse fillers (pigments, carbon-black, etc.) or other incompatible polymers above melt fracture conditions. We can only speculate that the creation of microvoids ( = inner surfaces) in particular and a sudden increase of gas solubilisation capability at and above melt fracture allows the polymer melt to wet the surface of the material to become dispersed. This means that a polymer melt might have completely different (supercritical) properties above melt fracture, than we usually observe. 

However, if the liquid solution contains a noncondensable component, the normalization shown in Equation (13) cannot be applied to that component since a pure, supercritical liquid is a physical impossibility. Sometimes it is convenient to introduce the concept of a pure, hypothetical supercritical liquid and to evaluate its properties by extrapolation provided that the component in question is not excessively above its critical temperature, this concept is useful, as discussed later. We refer to those hypothetical liquids as condensable components whenever they follow the convention of Equation (13). However, for a highly supercritical component (e.g., H2 or N2 at room temperature) the concept of a hypothetical liquid is of little use since the extrapolation of pure-liquid properties in this case is so excessive as to lose physical significance. 

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. 

Typical Properties of Gases, Liquids, and Supercritical Fluids ... 

It is less well known, but certainly no less important, that even with carbon dioxide as a drying agent, the supercritical drying conditions can also affect the properties of a product. Eor example, in the preparation of titania aerogels, temperature, pressure, the use of either Hquid or supercritical CO2, and the drying duration have all been shown to affect the surface area, pore volume, and pore size distributions of both the as-dried and calcined materials (34,35). The specific effect of using either Hquid or supercritical CO2 is shown in Eigure 3 as an iHustration (36). 

Fig. 3. Effect of using either liquid or supercritical carbon dioxide on the textural properties of titania aerogels calcined at the temperatures shown. (—), dried with Hquid carbon dioxide at 6 MPa and 283 K (-------), dried with supercritical carbon dioxide at 30 MPa and 323 K. Reproduced from Ref. 36.

Fig. 4. Comparison of physical properties of silica xerogels and aerogels. Note the similar properties of the aerogels prepared with and without supercritical...

Supercritical Extraction. The use of a supercritical fluid such as carbon dioxide as extractant is growing in industrial importance, particularly in the food-related industries. The advantages of supercritical fluids (qv) as extractants include favorable solubiHty and transport properties, and the abiHty to complete an extraction rapidly at moderate temperature. Whereas most of the supercritical extraction processes are soHd—Hquid extractions, some Hquid—Hquid extractions are of commercial interest also. For example, the removal of ethanol from dilute aqueous solutions using Hquid carbon dioxide... 

Supercritical Fluid Extraction. Supercritical fluid (SCF) extraction is a process in which elevated pressure and temperature conditions are used to make a substance exceed a critical point. Once above this critical point, the gas (CO2 is commonly used) exhibits unique solvating properties. The advantages of SCF extraction in foods are that there is no solvent residue in the extracted products, the process can be performed at low temperature, oxygen is excluded, and there is minimal protein degradation (49). One area in which SCF extraction of Hpids from meats maybe appHed is in the production of low fat dried meat ingredients for further processed items. Its apphcation in fresh meat is less successful because the fresh meat contains relatively high levels of moisture (50). 

Table 2. Comparison of Properties of Gases, Supercritical Fluids, and Liquids...

Physical property Gases Supercritical fluids Liquids... 

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. 

Physical properties of pure supercritical fluids may be found ia many of the standard reference textbooks and journals (10). There are also... 

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). 

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