Shape selectivity assessment of stationary phases in gas chromatography

Abstract Column selectivity is examined for a series of smectic liquid crystalline columns and is compared with methyl and C18 polysiloxane columns for the separation of polycyclic aromatic hydrocarbon (PAH) isomers. A set of extended and condensed solute probes is described that provides a sensitive indication of variations in column shape selectivity. Examples of shape selectivity differences are presented for smectic liquid crystalline columns and 5% phenyl polysiloxane columns using various PAH isomer sets. Variations in selectivity have been observed among different smectic liquid crystalline columns, and this problem appears more significant than for methyl polysiloxane columns. The selectivity ration for tetraphenylmethane and p‐terphenyl provides a sensitive indication of column shape selectivity, with a change in elution order occurring between ordered (smectic liquid crystalline) columns and non‐ordered (methyl polysiloxane) columns. Shape selectivity differences indicated by this test mixture are apparent for more complex PAH isomer mixtures. Despite stationary phase selectivity variability, smectic liquid crystalline columns offer considerable potential for solving difficult separation problems involving structured solutes.