Chiral chromatography separates enantiomers using a chiral environment, usually a chiral stationary phase. The two enantiomers form transient diastereomeric interactions with that environment and can therefore have different retention.
An ordinary achiral separation often cannot distinguish enantiomers because their bulk properties are identical in an achiral environment. A successful chiral chromatogram can measure an enantiomer ratio, provided the peaks are resolved and detector responses are interpreted correctly. Peak order alone does not establish absolute configuration without an external assignment.

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