It has been found that the interconversion of enantiomers on a chromatographic column during the separation process can be studied by the first-order kinetic equations derived both for reversible and irreversible reactions in a stationary system if the extent of interconversion is not too high. The equation derived for irreversible reactions gives, however, results also for higher degrees of enantiomerization while that derived for reversible interconversion failed. The irreversible equation was used to determine the enantiomerization barrier of N-(p-methoxybenzyl)-l,3,2-benzodithiazol-l-oxide enantiomers by supercritical fluid chromatography. The racemate of N-(p-methoxybenzyl)-l,3,2-benzodithiazol-l-oxide was separated by supercritical fluid chromatography on the (R,R)-Whelk-Ol column with supercritical carbon dioxide containing 20% methanol as a mobile phase. Peak areas of enantiomers prior to and after the separation used for the calculation of the enantiomerization barrier were determined by computer-assisted peak deconvolution of peak clusters registered on chromatograms using commercial software. Chirality 14:334–339, 2002. © 2002 Wiley-Liss, Inc.