Accurate Measurements of Infinite Dilution Activity Coefficients Using Gas Chromatography with Static-Wall-Coated Open-Tubular Columns

Abstract

Wall-coated open-tubular (WCOT) columns provide higher column efficiency and lower solute interfacial adsorption effect than packed columns. However, previous efforts used to measure the infinite dilution activity coefficient (γ(∞)) via a chromatographic technique have used packed columns, because the low carrier gas flow rate (U) and the small stationary phase amount (n(2)) in WCOT columns raise large errors. By rationally revising the γ(∞)-calculation equation for static-wall-coated open-tubular column, we observed that U and n(2) are not necessarily needed and the resulting error could be reduced, and WCOT column gas chromatography subsequently became a superior method for the accurate γ(∞) determination. In this study, we validate our revised γ(∞)-calculation equation by measuring γ(∞) in an ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate system, in which 55 organic compounds covering a wide range of functional groups were used as probe solutes and their γ(∞) values in the ionic liquid were determined at 40.0, 50.0, and 60.0 °C. Experimental error analysis shows that our revised equation remarkably reduces the error compared to the common γ(∞)-calculation equation. Our data is consistent with previously reported values obtained via other techniques, which further proves the credibility of our revised equation. The accurately determined γ(∞) values can be directly used to calculate the partial molar excess enthalpy, selectivity, and capacity, which will benefit for the rapid screening of solvents (especially ionic liquids) in separation approaches.