Capillary gas chromatographic separation of organic bases using a pH-adjusted basic water stationary phase

- Use of basic pH water as a stationary phase for organic bases in capillary GC.
- Improved elution and peak shape derived as a function of phase pH.
- Good retention for a wide variety of organic bases in this format.
- Analyte selectivity can be altered with pH.
- Organic bases can be analyzed underivitized and at low mass levels.

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 20 ng. By comparison, analyses on a conventional non-polar capillary GC column yield more peak tailing and only analyte masses of 1 μg 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.