An attempt to apply a subtraction model for characterization of non-polar stationary phase in supercritical fluid chromatography

Abstract

This study verified the feasibility of using a subtraction model to characterize the non-polar stationary phases (including C4, C8, and phenyl-type) in supercritical fluid chromatography (SFC). The model with 6 terms was expressed as log α = η'H + θ'P + β'A + α'B + κ'C + σ'S, where a term θ'P indicating dipole or induced dipole interaction was intentionally supplemented. Ethylbenzene and SunFire C8 were respectively defined as the reference solute and column. A 7-step modeling procedure was proposed: in the first 6 steps, except σ'S, by the use of a bidirectional fitting method, other parameters were calculated based on the equation: log α = log (ki/kref) ≈ η'H + θ'P + β'A + α'B + κ'C; and in the 7th step, residual analysis was employed to describe the σ'S term according to the equation: σ'S = log αexp. - log αpre. Furthermore, six columns that were not involved in modeling process and 12 compounds with unknown retention were used for methodology validation. It showed good predictions of log k, as demonstrated by adjusted determination coefficient (R2adj) from 0.9927 to 0.9998 (column) and from 0.9940 to 0.9999 (compound), respectively. The subtraction model emphasized the contribution of dipole or induced dipole interaction to the retention in SFC, and it obtained the σ'S term through residual analysis. Moreover, it made reasonable physical-chemical sense as the linear solvation energy relationship (LSER) model did, with the distinct advantages of better fitting and more accurate prediction. This study provided some new insights into the characterization of non-polar stationary phases in SFC.