A series of coumarin-based solutes, consisting of warfarin, coumachlor, coumafuryl, coumatetralyl, and 4-hydroxycoumarin, are utilized to elucidate the thermodynamic and kinetic aspects of chiral separations. These solutes are separated on a b-cyclodextrin stationary phase with a polar-organic mobile phase. Preliminary results demonstrate that the equilibration time is extremely long when the mobile phase consists of acetonitrile, methanol, or mixtures thereof. However, the equilibration time is substantially reduced when acetic acid or triethylamine modifiers are added. Linear isotherms are obtained when acid modifier is present, but nonlinear isotherms are obtained when no modifier or only amine modifier is present. The concentration of each component of the mobile phase is varied individually to observe the effects on the thermodynamic and kinetic behavior, including the retention factor, chiral selectivity, and kinetic mass transfer rate. In general, an increase in methanol or triethylamine concentration decreases retention, but an increase in acetic acid concentration slightly increases retention. However, it is noteworthy that triethylamine enhances chiral selectivity, whereas acetic acid diminishes it. Acetic acid has the opposite effect when amine is not present, indicating that the acid and amine interact with each other. With regard to the kinetic behavior, the mass transfer rate constant of the coumarin solutes generally decreases as the retention factor increases. However, the second enantiomer often has a surprisingly faster mass transfer rate than the first enantiomer, even though it is more retained. This difference indicates that different kinetic contributions arise at the chiral and achiral selective sites.