Supercritical fluids cosolvents

Optimizing solvents and solvent mixtures can be done empirically or through modeling. An example of the latter involves a single Sanchez-Lacombe lattice fluid equation of state, used to model both phases for a polymer-supercritical fluid-cosolvent system. This method works well over a wide pressure range both volumetric and phase equilibrium properties for a cross-linked poly(dimethyl siloxane) phase in contact with CO2 modified by a number of cosolvents (West et al., 1998). 

The reaction mixture contains a dilute solution of benzophenone solute, a few mole percent isopropanol and the remainder supercritical carbon dioxide solvent. This is analogous to a solute dissolved in a supercritical fluid/cosolvent mixture. These types of systems are important because in many applications researchers have found that the addition of a small amount of cosolvent (such as acetone or an alcohol) of volatility intermediate between that of the solute and the SCF can greatly enhance the solubility of the solute (Van Alsten, 1986). 

A simple equation for the solubility of a solid in a supercritical fluid cosolvent with a gas or another supercritical fluid. 

A Simple Equation for the Solubility of a Solid in a Supercritical Fluid Cosolvent with a Gas or Another Supercritical Fluid... 

Ruckenstein, E. Shulgin, 1. A simple equation for the solubility of a solid in a supercritical fluid cosolvent with a gas or another supercritical fluid. Ind. Eng. Chem. Res. 2003, 42, 1106-1110. 

Molecular spectroscopy methods have also been applied to the study of the entrainer effect in supercritical fluid-cosolvent mixtures. Again, the molecular probes employed for absorption and fluorescence measurements include the Kamlet-Taft u polarity/polarizability scale probes (13,14), pyrene (15,16), and TICT molecules (17). 

Many other probes have been used to study supercritical fluid-cosolvent mixtures, including the charge transfer complexes Fe°(l,10-phenanthroline)3 " and Fe (2,4-pentadionate)3 (for C02-methanol mixtures) (154), Nile red dye (for Freon-13, Freon-23, and CO2 with the cosolvents methanol, THF, acetonitrile, and dichloromethane) (155), benzophenone (for ethane with the cosolvents... 

As expected, pyrene has also been used to characterize supercritical fluid-cosolvent mixtures. For example, Zagrobelny and Bright used the Py polarity scale and pyrene excimer formation to study supercritical C02-methanol and C02-acetonitrile mixtures (160). Their results suggest the clustering of cosolvent molecules around pyrene. Similarly, Brennecke and coworkers measured Py values in CO2, CHF3, and CO2-CHF3 mixtures (43). 

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. 

Li S and Hartland S. 1992. Influence of cosolvents on solubility and selectivity in extraction of xanthines and cocoa butter from cocoa beans with supercritical carbon CO2. J Supercrit Fluids 5 7-12. 

A subsequent picosecond electronic absorption spectroscopic study of TPE excited with 266- or 355-nm, 30-ps laser pulses in cyclohexane found what was reported previously. However, in addition to the nonpolar solvent cyclohexane, more polar solvents such as THF, methylene chloride, acetonitrile, and methanol were employed. Importantly, the lifetime of S lp becomes shorter as the polarity is increased this was taken to be evidence of the zwitterionic, polar nature of TPE S lp and the stabilization of S lp relative to what is considered to be a nonpolar Sop, namely, the transition state structure for the thermal cis-trans isomerization. Although perhaps counterinmitive to the role of a solvent in the stabilization of a polar species, the decrease in the S lp lifetime with an increase in solvent polarity is understood in terms of internal conversion from to So, which should increase in rate as the S -So energy gap decreases with increasing solvent polarity. Along with the solvent-dependent hfetime of S lp, it was noted that the TPE 5ip absorption band near 425 nm is located where the two subchromophores— the diphenylmethyl cation and the diphenylmethyl anion—of a zwitterionic 5ip should be expected to absorb hght. A picosecond transient absorption study on TPE in supercritical fluids with cosolvents provided additional evidence for charge separation in 5ip. 

Current work with supercritical fluids can also illustrate the importance of cosolvents. Cosolvent effects in supercritical fluids can be considerable for systems where the cosolvent interacts strongly with the solute. A correlation suggests that both physical and chemical forces are important in the solvation process in polar cosolvent supercritical CO2 mixtures. The model coupled with the correlation represents a step toward predicting solubilities in cosolvent-modified supercritical fluids using nonthermody-namic data. This method of modeling cosolvent effects allows a more intuitive interpretation of the data than either a purely physical equation of state or ideal chemical theory can provide (Ting et al., 1993). 

The benefits from tuning the solvent system can be tremendous. Again, remarkable opportunities exist for the fruitful exploitation of the special properties of supercritical and near-critical fluids as solvents for chemical reactions. Solution properties may be tuned, with thermodynamic conditions or cosolvents, to modify rates, yields, and selectivities, and supercritical fluids offer greatly enhanced mass transfer for heterogeneous reactions. Also, both supercritical fluids and near-critical water can often replace environmentally undesirable solvents or catalysts, or avoid undesirable byproducts. Furthermore, rational design of solvent systems can also modify reactions to facilitate process separations (Eckert and Chandler, 1998). 

Remarkable tuning of reaction rates has been achieved for the isomerization of several dye molecules in supercritical fluid solvents using both small pressure changes and small additions of cosolvents. Rates of the thermal cis-trans relaxation were measured spectroscopically following irradiation for three dyes in supercritical carbon dioxide and ethane, pure and with several polar and protic cosolvents. These results demonstrate the versatility of supercritical fluid solvents, both to examine reaction mechanisms and as a means to tune rates (DiUow et al., 1998). 

Ethanol, cosolvent for supercritical fluid extraction of cholesterol from beef tallow, 125,126/... 

Fluorescence Investigation of Cosolvent—Solute Interactions in Supercritical Fluid Solutions... 

One of the challenges to the development of supercritical fluid (SCF) processes is understanding the solution thermodynamics on a molecular scale. Fluorescence spectroscopy has been shown to probe the local environment around chromophores. We now extend its use to SCF systems containing a cosolvent. 

In supercritical fluids, the possibility of local composition enhancements of cosolvent about a solute suggests that we should see enhancement of anion fluorescence if the water cosolvent clusters effectively about the 2-naphthol solute. Although in liquids the water concentration must be >30% to see anion emission, the higher diffusivity and density fluctuations in SCFs could allow stabilization of the anion at much lower water concentrations provided that the water molecules provide sufficient structure. Therefore the purpose of these experiments was to investigate 2-naphthol fluorescence in supercritical CO 2 with water cosolvent in the highly compressible region of the mixture to probe the local environment about the solute. 

Proton transfer is sensitive to the local solute environment in liquid solutions as evidenced by the water quenching curves for 2-naphthol and its cyano- derivatives. We have used proton transfer as a mechanism to probe the cosolvent composition around a solute in supercritical fluids to discern any difference between local and bulk concentrations. No proton transfer was observed from either 2-naphthol or 5-cyano-2-naphthol, presumably indicating insufficient structure in the SCF to solvate the proton. Although significant cosolvent effects on the fluorescence emission were observed, these appear to be independent of the thermodynamic variables. 

Investigations of Solute—Cosolvent Interactions in Supercritical Fluid Media... 

Solvation in supercritical fluids depends on the interactions between the solute molecules and die supercritical fluid medium. For example, in pure supercritical fluids, solute solubility depends upon density (1-3). Moreover, because the density of supercritical fluids may be increased significantly by small pressure increases, one may employ pressure to control solubility. Thus, this density-dependent solubility enhancement may be used to effect separations based on differences in solute volatilities (4,5). Enhancements in both solute solubility and separation selectivity have also been realized by addition of cosolvents (sometimes called entrainers or modifiers) (6-9). From these studies, it is thought that the solubility enhancements are due to the increased local density of the solvent mixtures, as well as specific interactions (e.g., hydrogen bonding) between the solute and the cosolvent (10). 

Cosolvent-modifled supercritical fluids are also used routinely in supercritical fluid chromatography (SFC) to modify solute retention times (11-20). In these reports, cosolvents are used to alter the mobile and stationary phase chemistries (16t17t20). However, distinguishing between such effects in a chromatography... 

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