Extension of the system constants database for open-tubular columns: System maps at low and intermediate temperatures for four new columns

The solvation parameter model is used to characterize the separation properties of four open-tubular columns for gas chromatography at low and intermediate column temperatures covering the range 60–240 °C. Solute descriptors for compounds suitable for characterizing columns over the intermediate temperature range are optimized using an iterative procedure. These compounds, and those previously recommended for the lower temperature range, are used to provide system constant maps for Rxi-5Sil MS, Rxi-17, Rtx-TNT and Rtx-TNT2 columns suitable for merging with a system constants database with entries for more than 50 columns. The Rxi-5Sil MS column is shown to have separation properties similar to the silphenylene–dimethylsiloxane copolymer stationary phase (DB-5ms) but these two columns are not selectivity equivalent. The Rxi-17 column has similar separation properties to the Rxi-50 column but is not selectivity equivalent to it. Rxi-17 is a poly(dimethyldiphenylsiloxane) stationary phase containing 50% diphenylsiloxane monomer and Rxi-50 a poly(methylphenylsiloxane) stationary phase with the same nominal composition but a different monomer structure. The difference in monomer structure results in only small changes in selectivity, and for all but the most demanding separations, the columns are interchangeable. The application-specific column (energetic materials) Rtx-TNT is shown to be selectivity equivalent to columns coated with the poly(dimethyldiphenylsiloxane) stationary phases containing 5% diphenylsiloxane monomer. The Rtx-TNT2 column is selectivity equivalent to the proprietary Rtx-OPPesticides column. Rtx-OPPesticides is a low bleed stationary phase, possibly based on silarylene–siloxane chemistry, with a composition designed to mimic the separation properties of the poly(dimethylmethyltrifluoropropylsiloxane) stationary phases containing 35% methyltrifluoropropylsiloxane monomer. Selectivity equivalence of columns is determined by the statistical agreement in system constants at 20 °C intervals over the full temperature range from 60 to 240 °C, and by the construction of correlation plots for the retention factors of varied compounds for the same temperature intervals.