The effect of temperature on selectivity in capillary SFC

Abstract

Abstract Retention indices (RI) for a variety of probe compounds were determined on 50‐μm i. d. columns coated with eight different stationary phases under density programmed SFC conditions at isothermal temperatures of 80 and 150°C. RI values were strongly dependent on temperature for polar probes on the polar phases containing high levels of cyanopropyl or polyethylene glycol (PEG) functionality. A lower apparent polarity was observed for polar columns at higher temperatures. Moderate RI differences were apparent with the same probes on columns with polarizable stationary phases of high phenyl or biphenyl content. Nonpolar alkyl substituted stationary phases showed only a slight temperature dependence on RI for all test compounds. Alkanes of lower molecular weight eluted at lower densities on all columns when the temperature was raised because of the contribution of volatility to elution in SFC. This same effect was observed for the higher alkanes on both nonpolar and PEG columns, but they eluted at similar densities on cyanopropyl columns and at higher densities on columns with polarizable phases when the temperature was raised. Temperature controlled selectivity tuning is a useful tool in optimizing separations in SFC.