Elution supercritical fluids

Shan, S. Ashraf-Khorassani, M. Taylor, L.T. Analysis of triazine and triazole herbicides by gradient-elution supercritical fluid chromatography. J. Chromatogr. 1990, 505, 293-298. 

The most common mobile phase for supercritical fluid chromatography is CO2. Its low critical temperature, 31 °C, and critical pressure, 72.9 atm, are relatively easy to achieve and maintain. Although supercritical CO2 is a good solvent for nonpolar organics, it is less useful for polar solutes. The addition of an organic modifier, such as methanol, improves the mobile phase s elution strength. Other common mobile phases and their critical temperatures and pressures are listed in Table 12.7. 

A method which uses supercritical fluid/solid phase extraction/supercritical fluid chromatography (SE/SPE/SEC) has been developed for the analysis of trace constituents in complex matrices (67). By using this technique, extraction and clean-up are accomplished in one step using unmodified SC CO2. This step is monitored by a photodiode-array detector which allows fractionation. Eigure 10.14 shows a schematic representation of the SE/SPE/SEC set-up. This system allowed selective retention of the sample matrices while eluting and depositing the analytes of interest in the cryogenic trap. Application to the analysis of pesticides from lipid sample matrices have been reported. In this case, the lipids were completely separated from the pesticides. 

An on-line supercritical fluid chromatography-capillary gas chromatography (SFC-GC) technique has been demonstrated for the direct transfer of SFC fractions from a packed column SFC system to a GC system. This technique has been applied in the analysis of industrial samples such as aviation fuel (24). This type of coupled technique is sometimes more advantageous than the traditional LC-GC coupled technique since SFC is compatible with GC, because most supercritical fluids decompress into gases at GC conditions and are not detected by flame-ionization detection. The use of solvent evaporation techniques are not necessary. SFC, in the same way as LC, can be used to preseparate a sample into classes of compounds where the individual components can then be analyzed and quantified by GC. The supercritical fluid sample effluent is decompressed through a restrictor directly into a capillary GC injection port. In addition, this technique allows selective or multi-step heart-cutting of various sample peaks as they elute from the supercritical fluid... 

Another application of SFC-GC was for the isolation of chrysene, a poly aromatic hydrocarbon, from a complex liquid hydrocarbon industrial sample (24). A 5 p.m octadecyl column (200 cm X 4.6 mm i.d.) was used for the preseparation, followed by GC analysis on an SE-54 column (25 m X 0.2 mm i.d., 0.33 p.m film thickness). The direct analysis of whole samples transferred from the supercritical fluid chromatograph and selective and multi-heart-cutting of a particular region as it elutes from the SFC system was demonstrated. The heart-cutting technique allows the possibility of separating a trace component from a complex mixture (Figure 12.21). 

On-going studies to improve analytical methods for hexachloroethane and related compounds include the EPA "Master Analytical Scheme" being developed for organic compounds in water (Michael et al. 1988) and the research in supercritical fluid extraction (Lopez-Avila et al. 1991 Wieboldt et al. 1988). Research continues on improving extraction, concentration, and elution techniques, and detection devices (Eichelberger et al. 

Ho JS, Tang PH, Eichelberger JW, et al. 1993. Determination of organic compounds in water by liquid solid extraction followed by supercritical fluid elution and capillary column gas chromatography/mass spectrometry. Denver, CO American Chemical Society, 313-315. 

Supercritical fluid extraction (EPA 3540, for total recoverable petroleum hydrocarbons EPA 3561 for polynuclear aromatic hydrocarbons) is applicable to the extraction of semivolatile constituents. Supercritical fluid extraction involves heating and pressuring a mobile phase to supercritical conditions (where the solvent has the properties of a gas and a liquid). The supercritical fluid is passed through the soil sample, and the analytes are concentrated on a sorbent or trapped cryogenically. The analytes are eluted with a solvent and analyzed using conventional techniques. Carbon dioxide is the most popular mobile phase. 

Box 25-2 (pages 568-569) describes gradient elution in supercritical fluid chromatography. 

Equipment for supercritical fluid chromatography is similar to that for HPLC with packed columns12 or open tubular columns. Eluent strength is increased in HPLC by gradient elution and in gas chromatography by raising the temperature. In supercritical... 

The separation of all eight cis/trans isomers of methyl 18 3 was similar to, but with better resolution than, the separation obtained with a 50-m CP Sil 88 capillary GC column (46) or by packed capillary supercritical fluid chromatography (47], The FAMEs eluted in four peaks or sets of peaks corresponding to the total number of cis and trans double bonds. These are marked as A (three trans), B (two trans, one cis), C (one trans, two cis), and D (three cis). 

The use of supercritical fluid chromatography for carotene separation has been examined and optimized, especially in regard to temperature, pressure, and organic modifiers in the supercritical fluid (71). With an RP column it was possible to resolve an a-carotene-cis isomer from an all-trans carotene as well as two cis isomers of /3-carotene from an all-trans /3-carotene. As with HPLC, only polymeric C,8 columns were able to resolve the cis isomers of a- and /3-carotene from the all-trans isomers. Supercritical fluid chromatography offers the advantage not only of an efficient separation but also of fast analysis. Indeed, the use of SFC with ODS-based columns for the analysis of carotenoid pigments affords a threefold reduction of analysis time compared to HPLC (72). The elution order of carotenoids and their cis isomers was found to be the same as in RP-HPLC. The selectivity of the system could further be increased by adding modifiers (e.g.,... 

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