A novel chromatographic separation method is introduced which employs water (saturated with CO(2)) as a stationary phase and CO(2) (saturated with water) as a mobile phase. Since water and CO(2) have little miscibility, conditions can be attained that create a stationary phase of water lining the inside of an uncoated stainless steel capillary. Because altering temperature and pressure can change both the density of the mobile phase and the polarity of the stationary phase, these experimental parameters offer good flexibility for optimizing separations and allow for different gradient programmed separation options. Further, since this method is free of organic stationary and mobile phase components, it is environmentally compatible and allows the use of universal flame ionization detection. This system offers very good sample capacity, peak symmetry, and retention time reproducibility (∼1% RSD run-to-run, ∼4% RSD day-to-day). Analytes such as alcohols, carboxylic acids, phenols, and tocopherols are employed to investigate this relatively inexpensive and robust method. As an application, the system is used to quantify ethanol in alcoholic beverages and biofuel and to analyze caffeine levels in drinks. In all cases, quantitative results are obtained with quick throughput times and often little need for sample preparation.

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The coating properties of a novel water stationary phase used in capillary supercritical fluid chromatography were investigated. The findings confirm that increasing the length or internal diameter of the type 316 stainless-steel column used provides a linear increase in the volume of stationary phase present. Under normal operating conditions, results indicate that about 4.9 ± 0.5 μL/m of water phase is deposited uniformly inside of a typical 250 μm internal diameter 316 stainless-steel column, which translates to an area coverage of about 6.3 ± 0.5 nL/mm(2) regardless of dimension. Efforts to increase the stationary phase volume present showed that etching the stainless-steel capillary wall using hydrofluoric acid was very effective for this. For instance, after five etching cycles, this volume doubled inside of both the type 304 and the type 316 stainless-steel columns examined. This in turn doubled analyte retention, while maintaining good peak shape and column efficiency. Overall, 316 stainless-steel columns were more resistant to etching than 304 stainless-steel columns. Results indicate that this approach could be useful to employ as a means of controlling the volume of water stationary phase that can be established inside of the stainless-steel columns used with this supercritical fluid chromatography technique.

The use of a pH-adjusted water stationary phase for analyzing organic bases in capillary gas chromatography (GC) is demonstrated. Through modifying the phase to typical values near pH 11.5, it is found that various organic bases are readily eluted and separated. Conversely, at the normal pH 7 operating level, they are not. Sodium hydroxide is found to be a much more stable base than ammonium hydroxide for altering the pH due to the higher volatility and evaporation of the latter. In the basic condition, such analytes are not ionized and are observed to produce good peak shapes even for injected masses down to about 20ng. By comparison, analyses on a conventional non-polar capillary GC column yield more peak tailing and only analyte masses of 1μg or higher are normally observed. Through carefully altering the pH, it is also found that the selectivity between analytes can be potentially further enhanced if their respective pKa values differ sufficiently. The analysis of different pharmaceutical and petroleum samples containing organic bases is demonstrated. Results indicate that this approach can potentially offer unique and beneficial selectivity in such analyses.

A multiple flame photometric detector (mFPD) based on many flames operated in series is introduced for the detection of sulfur and phosphorus compounds. The method employs attributes of a previously developed micro counter-current flame technique to readily establish any number of very small compact flames inside a narrow quartz tube. Results show for the first time that a five flame mFPD mode can improve hydrocarbon quenching resistance nearly 20-fold relative to a single flame (i.e., conventional FPD) mode, and nearly 10-fold relative to a two flame (i.e., dual FPD) mode. Under these conditions, the five flame mFPD mode is shown to maintain about 60% of its original analyte chemiluminescence even in the presence of over 100 mL/min of methane flow into the detector. In contrast to a conventional dual FPD device, the five flame mFPD mode also provides analyte sensitivity that is similar to a conventional FPD. Of note, the mFPD yields minimum detectable limits for sulfur and phosphorus of 4 x 10(-11) g S/s and 3 x 10(-12) g P/s respectively. Analyte selectivity over hydrocarbons, signal reproducibility, and response equimolarity are also improved in the mFPD, making it a potentially useful detector for applications in gas chromatography.