Polarity of supercritical fluids

Polarity of Supercritical Fluids. In order to successfully perform any chromatographic separation, the analytes must be sufficiently soluble in the mobile phase. Efforts to ensure solubility have often been based on matching the polarity of the sample components and the mobile phase. For pure fluids, Giddings has reported a polarity classification based on the solubility parameter (18). In contrast to essentially constant values for incompressible fluids (liquids), the solubility parameter (mobile phase strength) of a supercritical fluid varies with its density. 

Liquid modifiers that are commonly used to increase the effective polarity of supercritical fluids such as carbon dioxide frequently have inherent chemical instabilities that must be considered when designing an analysis, or in the interpretation of results.1-3 In many cases, such solvents are obtainable with stabilizers added to control the instability or to slow the reaction. Reactive solvents that do not have stabilizers must be used quickly or be given proper treatment. In either case, it is important to understand that the solvents (as they may be used in an analysis) are not necessarily pure materials. The reader is cautioned that many of the other fluids listed earlier in this section are thermally unstable this table only treats chemical instabilities that are considerable at typical laboratory ambient temperature. 

A variety of modifiers have been used to enhance the polarity of supercritical fluid carbon dioxide, including several of the lower-molecular-mass alcohols, propylene carbonate, 2-methoxyelhanol, methylene chloride, and certain organic acids. The most common modifier is methanol. Figure 29-11 demonstrates the improved efficiency achieved by the presence of a small amount of methanol in the extraction of various materials from soil samples. 

One approach to enhancing the range of selective aohiMiJ phases available for SFC is to use binary mixtures of supercritical fluid and a polar solvent. In this way the availahl ... 

A disadvantage of supercritical fluids for extraction is that most common fluids used for extraction (carbon dioxide, nitrous oxide, sulfur hexafluoride, etc.) are weak solvents, limiting the polarity and molecular weight range of analytes that can be efficiently extracted. Also, for trace analysis the availability of fluids of adeguate ptirity may be a problem. 

Figure 6. A simple model for the aggregation of supercritical fluid molecules around a polar solute molecule.

The popularity of this extraction method ebbs and flows as the years go by. SFE is typically used to extract nonpolar to moderately polar analytes from solid samples, especially in the environmental, food safety, and polymer sciences. The sample is placed in a special vessel and a supercritical gas such as CO2 is passed through the sample. The extracted analyte is then collected in solvent or on a sorbent. The advantages of this technique include better diffusivity and low viscosity of supercritical fluids, which allow more selective extractions. One recent application of SFE is the extraction of pesticide residues from honey [27]. In this research, liquid-liquid extraction with hexane/acetone was termed the conventional method. Honey was lyophilized and then mixed with acetone and acetonitrile in the SFE cell. Parameters such as temperature, pressure, and extraction time were optimized. The researchers found that SFE resulted in better precision (less than 6% RSD), less solvent consumption, less sample handling, and a faster extraction than the liquid-liquid method [27]. 

The second approach was taken by practicing liquid chromatographers. They routinely dealt with thermally labile, highly polar molecules and frequently sacrificed resolution, and speed in their separations because of the aqueous mobile phases that were required. With the enhanced diffusion and decreased viscosity of supercritical fluids over liquids, chromatographic run-time and resolution could be improved when supercritical fluids were used. But solubility in pure carbon dioxide mobile phases, which has the solvating powers from hexane to methylene chloride under normal density ranges, was a problem for these polar molecules. To compensate for this, experimentalists started working with mixed mobile phases. These mixed phases were based on... 

As its name suggests, supercritical fluid extraction (SEE) relies on the solubilizing properties of supercritical fluids. The lower viscosities and higher diffusion rates of supercritical fluids, when compared with those of liquids, make them ideal for the extraction of diffusion-controlled matrices, such as plant tissues. Advantages of the method are lower solvent consumption, controllable selectivity, and less thermal or chemical degradation than methods such as Soxhlet extraction. Numerous applications in the extraction of natural products have been reported, with supercritical carbon dioxide being the most widely used extraction solvent. However, to allow for the extraction of polar compounds such as flavonoids, polar solvents (like methanol) have to be added as modifiers. There is consequently a substantial reduction in selectivity. This explains why there are relatively few applications to polyphenols in the literature. Even with pressures of up to 689 bar and 20% modifier (usually methanol) in the extraction fluid, yields of polyphenolic compounds remain low, as shown for marigold Calendula officinalis, Asteraceae) and chamomile Matricaria recutita, Asteraceae). " ... 

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). 

In some aspects, supercritical fluids, which represent a state between the gaseous and liquid phases, have properties resembling those of non-polar solvents in being adequate for biotransformations of hydrophobic compounds. Although the use of supercritical fluids is not restricted to hydrolases, the use of this class of enzymes, especially lipases, dominates [3, 4]. Esters represent the main flavour compounds produced by this process [5]. 

In the area of pharmaceuticals, particle formation is currently one of the most popular applications of supercritical fluids. The reasons can be found in the wide variety of particles obtained by the supercritical techniques. Void free particles or very soft particles, composed of polar or non-polar compounds, and with size ranging from 50 nanometr to 50 microns can be produced easily. 

Steady-State Solvatochromism. The majority of the reports on supercritical fluid solvation have used steady-state solvatochromic absorbance measurements (21-28). The original aim of these experiments was to determine the solvating power of supercritical fluids for chromatography and extraction (SFC and SFE) (26,28). To quantify solvent strength, researchers (21-28) adopted the Kamlet-Taft x solvent polarity scale (50-55). This scale best correlates solvatochromic effects on a- x and x- x electronic absorption transitions. 

Environmental applications of SFE appear to be the most widespread in the literature. A typical example is the comparison of extraction efficiency for 2,3,7,8 -tetrachlorodibenzo-p-dioxin (2,3,7,8-TCDD) from sediment samples using supercritical fluid extraction and five individual mobile phases with Soxhlet extraction was made (101). The mobile phases, carbon dioxide, nitrous oxide, pure and modified with 2% methanol as well as sulfur hexafluoride were examined. Pure nitrous oxide, modified carbon dioxide and modified nitrous oxide systems gave the recoveries in the acceptable range of 80 to 100%. Carbon dioxide and sulfur hexafluoride showed recoveries of less than 50% under identical conditions. Classical Soxhlet recoveries by comparison illustrated the poorest precision with average extraction efficiencies of less than 65%. Mobile phase choice, still as yet a major question in the science of supercritical fluid extraction, seems to be dependent upon several factors polarity of the solute of interest, stearic interactions, as well as those between the matrix and the mobile phase. Physical parameters of the solute of interest, as suggested by King, must also be considered. Presently, the science behind the extraction of analytes of interest from complex matrices is not completely understood. 

Since the early days of SFC, there always has been a desire to extend the useful range of the technique to more polar molecules. A similar type of desire exists in SFE. The hope for achieving efficient extractions of polar molecules from polar as well as non-polar substrates can only be realized with the use of more polar primary supercritical fluids or by the use of modifiers. Many of the more primary supercritical fluids that exists namely, ammonia or water, are not effectively usable in the analytical laboratory due to instrumental as well as safety restrictions, therefore, the need to do more research on the use of modifiers in SFE is greatly necessitated. Based upon the limited study that was done within the scope of this chapter, a few conclusions can be drawn. These conclusions are summarized in Figure 16. 

We now turn attention to a completely different kind of supercritical fluid supercritical water (SCW). Supercritical states of water provide environments with special properties where many reactive processes with important technological applications take place. Two key aspects combine to make chemical reactivity under these conditions so peculiar the solvent high compressibility, which allows for large density variations with relatively minor changes in the applied pressure and the drastic reduction of bulk polarity, clearly manifested in the drop of the macroscopic dielectric constant from e 80 at room temperature to approximately 6 at near-critical conditions. From a microscopic perspective, the unique features of supercritical fluids as reaction media are associated with density inhomogeneities present in these systems [1,4],... 

Figure 3 compares values of 6 of supercritical fluids for p = p,jq (where only the chemical nature of the fluid is taken into consideration). From this figure it can be seen that CO2 is a slightly polar fluid, and that at first sight the extraction of solutes strongly linked to a matrix will be difficult. 

In the present study, an instmment has been established for polarized and depolarized Raman scattering measurement of supercritical fluid along its isotherm to realize the investigations stated above. Preliminary results for supercritical CF3H are given to draw a schematic picture of the dynamics. 

The technique may be viewed as an alternative to the addition of cosolvents or modifiers (sometimes termed entraimrs) that are commonly used in supercritical fluid technology to enhance the polarity of the fluid. For cleaning processes, however, these cosolvents may be toxic or detrimental in various ways to the substrate. In addition, these modifiers are usually more difficult to separate downstream from the process due to their high volatility. In contrast, surfactants typically have very low volatility and thus interact to a much lesser degree with the substrate. Furthermore, they often dramatically improve the solubility of polar species, well beyond that of simple modifiers. 

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