Contrasting selectivity between HPLC and SFC using phenyl-type stationary phases: A study on linear polynuclear aromatic hydrocarbons

• SFC was used for the analysis of PAHs.
• Separations on a Cosmosil 5PBB stationary phase were effectively independent of the mobile phase composition.
• RPHPLC separation performance is a poor predictor for RPSFC.

A selectivity study was undertaken using two types of phenyl-type (Synergi polar RP and Cosmosil 5PBB) stationary phases in supercritical fluid chromatography. The mobile phases used in the SFC environment employed CO2 with methanol as the modifier. These columns were tested using linear polynuclear aromatic hydrocarbons as the test solutes. The retention behaviour of these PAHs in SFC was compared to their behaviour in HPLC and there were very distinct differences. On the Synergi-polar stationary phase the PAH selectivity was highly dependent on the methanol modifier concentration, but in comparison on the Cosmosil column, the selectivity between the members of this PAH test group showed almost no change as a function of the methanol concentration, even though the retentivity on the Cosmosil stationary phase was far greater than the Synergi stationary. In fact, the mobile phase played a very passive role in the separations observed on the Cosmosil stationary phase.