Supercritical fluids solubility

Dyeing. Supercritical fluid can be used to provide a water and solvent-free method of textile dyeing. Fluoro-modified dyestuffs have been developed in order to provide improved light-fastness etc. and are readily available. It might be interesting to research die supercritical fluid solubility of these products.23-27... 

Fluorinated Ligands as Supercritical Fluid-Soluble Complexants... 

Solubility Parameters of the Most Common Fluids for Supercritical Fluid Extraction and Chromatography Solubility Parameters of Supercritical Fluids Solubility Parameters of Liquid Solvents Instability of Modifiers Used with Supercritical Fluids... 

All this just to get the ethane for his supercritical fluid solubility studies. 

The snow and frost described are almost assuredly of different morphology, particle size, and size distribution than the starting material Hannay and Hogarth studied salts such as cobalt chloride and potassium iodide. Incidentally, the reference to the precipitation of the solid is not an Isolated report of nucleation from a supercritical fluid. For example, many other references to snow, fog, fumes, and crystals formed during depressurization of a solution of a solute in a supercritical fluid have been made by researchers studying supercritical fluid solubility phenomena. 

As we see again, the principles and applications of supercritical fluid solubility phenomena were quite well understood at the time of the filing of this patent, March 1936. 

This chapter describes a recent and controversial period of supercritical fluid history, 1977-1987. An outline of the information to be covered in this chapter is given in Table I. The history of supercritical fluid solubility phenomena was summarized in an earlier paper (1). That paper reviewed the first literature report on the subject by Hannay and Hogarth in 1879 (2), the work of many researchers who investigated the phase behavior of various materials dissolved in supercritical fluids (3-5), and some process/product applications of supercritical fluid extraction (6-8). A quite detailed historical development, covering in depth the first score years after 1879, has been published elsewhere (9). 

Supercritical extraction LorV Supercritical solvent MSA Supercritical fluid Solubility... 

The WAG process has been used extensively in the field, particularly in supercritical CO2 injection, with considerable success (22,157,158). However, a method to further reduce the viscosity of injected gas or supercritical fluid is desired. One means of increasing the viscosity of CO2 is through the use of supercritical C02-soluble polymers and other additives (159). The use of surfactants to form low mobihty foams or supercritical CO2 dispersions within the formation has received more attention (160—162). Foam has also been used to reduce mobihty of hydrocarbon gases and nitrogen. The behavior of foam in porous media has been the subject of extensive study (4). X-ray computerized tomographic analysis of core floods indicate that addition of 500 ppm of an alcohol ethoxyglycerylsulfonate increased volumetric sweep efficiency substantially over that obtained in a WAG process (156). 

In terms of the solubilities of solutes in a supercritical phase, the following generalizations can be made. Solute solubiUties in supercritical fluids approach and sometimes exceed those of Hquid solvents as the SCF density increases. SolubiUties typically increase as the pressure is increased. Increasing the temperature can cause increases, decreases, or no change in solute solubiUties, depending on the temperature effect on solvent density and/or the solute vapor pressure. Also, at constant SCF density, a temperature increase increases the solute solubiUty (16). 

Adsorption and Desorption Adsorbents may be used to recover solutes from supercritical fluid extracts for example, activated carbon and polymeric sorbents may be used to recover caffeine from CO9. This approach may be used to improve the selectivity of a supercritical fluid extraction process. SCF extraction may be used to regenerate adsorbents such as activated carbon and to remove contaminants from soil. In many cases the chemisorption is sufficiently strong that regeneration with CO9 is limited, even if the pure solute is quite soluble in CO9. In some cases a cosolvent can be added to the SCF to displace the sorbate from the sorbent. Another approach is to use water at elevated or even supercritical temperatures to facilitate desorption. Many of the principles for desorption are also relevant to extraction of substances from other substrates such as natural products and polymers. 

The usual means of identifying and quantifying the level of these additives in polymer samples is performed by dissolution of the polymer in a solvent, followed by precipitation of the material. The additives in turn remain in the Supernatant liquid. The different solubilites of the additives, high reactivity, low stability, low concentrations and possible co-precipitation with the polymer may pose problems and lead to inconclusive results. Another sample pretreatment method is the use of Soxhlet extraction and reconcentration before analysis, although this method is very time consuming, and is still limited by solubility dependence. Other approaches include the use of supercritical fluids to extract the additives from the polymer and Subsequent analysis of the extracts by microcolumn LC (2). 

The coupling of supercritical fluid extraction (SEE) with gas chromatography (SEE-GC) provides an excellent example of the application of multidimensional chromatography principles to a sample preparation method. In SEE, the analytical matrix is packed into an extraction vessel and a supercritical fluid, usually carbon dioxide, is passed through it. The analyte matrix may be viewed as the stationary phase, while the supercritical fluid can be viewed as the mobile phase. In order to obtain an effective extraction, the solubility of the analyte in the supercritical fluid mobile phase must be considered, along with its affinity to the matrix stationary phase. The effluent from the extraction is then collected and transferred to a gas chromatograph. In his comprehensive text, Taylor provides an excellent description of the principles and applications of SEE (44), while Pawliszyn presents a description of the supercritical fluid as the mobile phase in his development of a kinetic model for the extraction process (45). 

A third motivation for studying gas solubilities in ILs is the potential to use compressed gases or supercritical fluids to separate species from an IL mixture. As an example, we have shown that it is possible to recover a wide variety of solutes from ILs by supercritical CO2 extraction [9]. An advantage of this technology is that the solutes can be removed quantitatively without any cross-contamination of the CO2 with the IL. Such separations should be possible with a wide variety of other compressed gases, such as C2LL6, C2LL4, and SF. Clearly, the phase behavior of the gas in question with the IL is important for this application. 

The solubilities, discussed above, of the various gases in the ionic liquids have important implications for applications of IFs. The impact of gas solubilities on reactions, gas separations and the use of compressed gases or supercritical fluids to separate solutes from IFs are discussed below. 

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) have densities similar to those of liquids and a solvent power higher than that of gases, so that compounds which are insoluble in a fluid in ambient conditions become soluble in fluids under supercritical conditions [75]. 

Following this, elastomers can be swollen by some high-pressure gases (especially CO2) as the densities of these gases approach liquid-like levels, at appropriate temperatures they become supercritical fluids which possess a solubility parameter magnitudes that, however, are highly dependent on temperature and pressure... 

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]. 

The supercritical fluid and liquid solubilities reported in Figs. 9-12 suggest that diamondoids will preferentially partition themselves into the high-pressure, high-temperature, and rather low-boiling fraction of any mixture including crude oil. 

Surfactants and Colloids in Supercritical Fluids Because very few nonvolatile molecules are soluble in CO2, many types of hydrophilic or lipophilic species may be dispersed in the form of polymer latexes (e.g., polystyrene), microemulsions, macroemulsions, and inorganic suspensions of metals and metal oxides (Shah et al., op. cit.). The environmentally benign, nontoxic, and nonflammable fluids water and CO2 are the two most abundant and inexpensive solvents on earth. Fluorocarbon and hydrocarbon-based surfactants have been used to form reverse micelles, water-in-C02... 

Regression correlation coefficient Regression coefficient of determination Rolling circle amplification Water solubility Sodium dodecyl sulfate Supercritical fluid extraction Standard operating procedure Solid-phase extraction Surface plasmon resonance Thymine... 

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