Room-temperature-ionic-liquid coated graphitized carbons for selective preconcentration of polar vapors

Most adsorbent materials used for preconcentrating and thermally desorbing volatile and semi-volatile organic compounds (S/VOCs) in portable or "micro" gas chromatographic (GC/µGC) instruments preferentially capture non-polar or moderately polar compounds relative to more polar compounds. Here, we explore the use of a known trigonal-tripyramidal room-temperature ionic liquid (RTIL) as a surface modifier for the graphitized carbons, Carbopack B (C-B) and Carbopack X (C-X), with the goal of enhancing their capacity and selectivity for polar S/VOCs. Breakthrough tests were performed by challenging tubes packed with ∼2.5 mg of C-B or RTIL-coated C-B (RTIL/C-B) with 13 individual S/VOCs, including several organophosphorus compounds and reference alkyl and aromatic hydrocarbons of comparable vapor pressures, at concentrations ranging from 14 to 130 mg/m³. The 10% breakthrough volume, V_b10, was used as the measure of capacity. For the RTIL/C-B, the V_b10 values of the five organophosphorus vapors tested were consistently ∼2.5 times larger than those for the untreated C-B, and V_b10 values of the four non-polar reference vapors were 11-26 times smaller for the RTIL/C-B than for the untreated C-B. For compounds of similar vapor pressure the capacity ratios for polar vs. non-polar compounds with the RTIL/C-B ranged from 1.8 to 34. Similar results were obtained with C-X and RTIL/C-X on a smaller set of compounds. Tests at 70% relative humidity or with a binary mixture of a polar and non-polar compound had no effect on the capacity of the RTIL/C-B, and there were no changes in V_b10 values after several months of testing that included cycling from 25 to 250 °C. Capacity was strongly correlated with vapor pressure. Attempts to reconcile the selectivity using models based on linear-solvation-energy relationships were only partially successful. Nonetheless, these results indicate that RTIL coating of carbon adsorbents affords a simple, reliable means of rendering them selective for polar S/VOCs.