Characterization of five chemistries and three particle sizes of stationary phases used in supercritical fluid chromatography

•5 different stationary phase chemistries were evaluated with 3 particle sizes.•The systems were compared based on retention measured for over 100 analytes.•Chemometric methods were used to assess the effects of changing particle size.•Method transfer from 5 to 1.7μm particles is possible with weakly compressible fluids. Sub-2-microns particles employed as supporting phases are known to favor column efficiency. Recently a set of columns based on sub-2-microns particles for use with supercritical fluid mobile phases have been introduced by Waters. Five different stationary phase chemistries are available: BEH silica, BEH Ethyl-pyridine, XSelect CSH Fluorophenyl, HSS C18 SB and BEH Shield RP18. This paper describes the characterization of 15 stationary phases, the five different chemistries, and three particle sizes, 1.7 (or 1.8), 3.5 and 5 microns, with the same carbon dioxide–methanol mobile phase and a set of more than a hundred compounds. The interactions established in the 15 different chromatographic systems used in supercritical fluid chromatography (SFC) are assessed with linear solvation energy relationships (LSERs). The results show the good complementarity of the five column chemistries, and their comparative location inside a classification map containing today around 70 different commercial phases. Among the five different chemistries, the HSS C18 SB phase displays a rather unusual behavior in regards of classical C18 phases, as it displays significant hydrogen–bonding interactions. Besides, it appears, as expected, that the BEH Ethyl–pyridine phase has weak interactions with basic compounds. The effect of particle size was studied because smaller particles induce increased inlet and internal pressure. For compressible fluids, this pressure change modifies the fluid density, i.e. the apparent void volume and the eluting strength. These changes could modify the retention and the selectivity of compounds in the case of method transfer, by using different particle sizes, from 5 down to 1.7μm. A hierarchical cluster analysis shows that stationary phase clusters were based on the phase chemistry rather than on the particle size, meaning that method transfer from 5 to 1.7 microns can be achieved in the subcritical domain i.e. by using a weakly compressible fluid.