Characterization of phosphonium ionic liquids through a linear solvation energy relationship and their use as GLC stationary phases

In recent years, room temperature ionic liquids (RTILs) have proven to be of great interest to analytical chemists. One important development is the use of RTILs as highly thermally stable GLC stationary phases. To date, nearly all of the RTIL stationary phases have been nitrogen-based (ammonium, pyrrolidinium, imidazolium, etc.). In this work, eight new monocationic and three new dicationic phosphonium-based RTILs are used as gas–liquid chromatography (GLC) stationary phases. Inverse gas chromatography (GC) analyses are used to study the solvation properties of the phosphonium RTILs through a linear solvation energy model. This model describes the multiple solvation interactions that the phosphonium RTILs can undergo and is useful in understanding their properties. In addition, the phosphonium-based stationary phases are used to separate complex analyte mixtures by GLC. Results show that the small differences in the solvent properties of the phosphonium ILs compared with ammonium-based ILs will allow for different and unique separation selectivities. Also, the phosphonium-based stationary phases tend to be more thermally stable than nitrogen-based ILs, which is an advantage in many GC applications.