Compact, Automated, Inexpensive, and Field-Deployable Vacuum-Outlet Gas Chromatograph for Trace-Concentration Gas-Phase Organic Compounds

• Published in: Analytical chemistry (Washington) 2019-01, Vol.91 (2), p.1318-1327
• Main Authors: Skog, Kate M, Xiong, Fulizi, Kawashima, Hitoshi, Doyle, Evan, Soto, Ricardo, Gentner, Drew R
• Format: Article
• Language: English
• Subjects: Adsorptivity; Carrier gases; Chemistry; Chromatography; Compressed gas; Cost analysis; Detectors; Elution; Ethylbenzene; Gas chromatography; Gases; Helium; Isomers; Molecular diffusion; Molecular structure; Optimization; Organic chemicals; Organic compounds; p-Xylene; Phase transitions; Photoionization; Plates (structural members); Purity; Quantitative analysis; Stability analysis; Systems stability; Temperature; Tolerances; Vacuum; VOCs; Volatile organic compounds; Volatility; Water vapor; Xylene
• ISSN: 0003-2700; 1520-6882
• DOI: 10.1021/acs.analchem.8b03095

The identification and quantification of gas-phase organic compounds, such as volatile organic compounds (VOCs), frequently use gas chromatography (GC), which typically requires high-purity compressed gases. We have developed a new instrument for trace-concentration measurements of VOCs and intermediate-volatility compounds of up to 14 carbon atoms in a fully automated (computer-free), independent, low-cost, compact GC-based system for the quantitative analysis of complex mixtures without the need for compressed, high-purity gases or expensive detectors. Through adsorptive analyte preconcentration, vacuum GC, photoionization detectors, and need-based water-vapor control, we enable sensitive and selective measurements with picogram-level limits of detection (i.e., under 15 ppt in a 4 L sample for most compounds). We validate performance against a commercial pressurized GC, including resolving challenging isomers of similar volatility, such as ethylbenzene and m/p-xylene. We employ vacuum GC across the whole column with filtered air as a carrier gas, producing long-term system stability and performance over a wide range of analytes. Through theory and experiments, we present variations in analyte diffusivities in the mobile phase, analyte elution temperatures, optimal linear velocities, and separation-plate heights with vacuum GC in air at different pressures, and we optimize our instrument to exploit these differences. At 2–6 psia, the molecular diffusion coefficients are 6.4–2.1 times larger and the elution temperatures are 39–92 °C lower than with pressurized GC with helium (at 30 psig) depending on the molecular structure, and we find a wide range of optimal linear velocities (up to 60 cm s−1) that are faster with broader tolerances than with pressurized-N2 GC.