Thermodynamic characterization of interactions between environmental contaminants and room temperature ionic liquids...

Understanding the thermodynamic interactions between an analyte and the sample phase is of paramount importance when choosing a co-solvent in headspace analysis. A sample phase - gas phase equilibrium partition coefficient (Kp) is used fundamentally to describe the distribution of the analyte between the two phases. Kp determinations by headspace gas chromatography (HS-GC) were acquired by two methods: vapor phase calibration (VPC) and phase ratio variation (PRV). Here, we demonstrated a pressurized - loop headspace system in conjunction with gas chromatography vacuum ultraviolet detection (HS-GC-VUV) to directly calculate the concentration of analytes in the gas phase from room temperature ionic liquids (RTILs) sample phases, using pseudo-absolute quantification (PAQ). PAQ, an attribute of VUV detection, allowed for quick determination of Kp and other thermodynamic properties, such as enthalpy (ΔH) and entropy (ΔS) of the system through the use of van't Hoff plots in the temperature range of 70-110 °C. The Kp determinations by PAQ were comparable to those obtained using the VPC method with percent difference ranging from ≤ 1-33%. Kp determinations were made for analytes (cyclohexane, benzene, octane, toluene, chlorobenzene, ethylbenzene, m-,p-, and o-xylene) at the varying temperatures (70-110 °C) using different RTILs (1-ethyl-3-methylimidazolium ethylsulfate ([EMIM][ESO₄]), 1-ethyl-3-methylimidazolium diethylphosphate ([EMIM][DEP]), and tris(2-hydroxyethyl)methylammonium methylsulfate ([MTEOA][MeOSO₃])) and (1-ethyl-3-methylimidazolium bis(trisfluoromethanesulfonyl)imide ([EMIM] [NTF₂])). The results from the van't Hoff analysis revealed that [EMIM] cation-based RTILs exhibit strong solute-solvent interactions with analytes that have π- electrons.