The chromatographic separation of Troger's base enantiomers with ethanol as eluent on microcrystalline triacetate cellulose (CTA) was studied Binary competitive adsorption equilibrium data measured were interpreted using ideal adsorbed solution and real adsorbed solution (RAS) theory. Both models were used to simulate a set of column breakthrough experiments. The competitive behavior of the two enantiomers is quantitatively discussed and the reliability of the two models is assessed The results show that the RAS model can describe with good accuracy the complex competitive adsorption behavior exhibited by the CTA/Troger's base model system. This conclusion is expected to apply to the adsorption of the other enantiomeric mixtures on chiral stationary phases.