The analytical separation of enantiomers by capillary gas chromatograp
hy on chiral stationary phases (CSPs) is reviewed. Inherent principles
and methodological advances are described. Three principal CSPs tailo
red for hydrogen bonding, coordination and inclusion are currently emp
loyed. Cyclodextrin derivatives have proved to be the most versatile a
nd universal CSPs in gas chromatography. Anchoring the CSPs to a polys
iloxane backbone leads to Chirasil-type stationary phases with improve
d temperature stability, efficiency and lifetimes. Immobilization of C
hirasil-type stationary phases allows enantiomer separations also in c
apillary supercritical fluid chromatography and capillary electrochrom
atography. Thermodynamic parameters of enantioselectivity in gas chrom
atography, kinetic studies of enantiomerization and methods of enantio
mer labelling are discussed.