A statistical thermodynamic theory of chiral solute retention and separation using chiral stationary phase high-performance liquid chromatography (CSP-HPLC) is formulated and applied in the limit of infinite dilution of solute to models of chemically bonded CSPs consisting of either chiral tetrahedral moieties or chiral molecular cavities intended to simulate a cyclodextrin CSP. Explicit expressions are derived for the corresponding separation factors and the likelihood of enantiomeric separation is investigated as a function of the multitude of possible interactions and retention modes for the enantiomers and CSPs considered. The separation factor reduces to a simple Boltzmann factor whenever a dominant retention mode, usually involving strong hydrogen bonding, prevails for both enantiomers. In mixed mobile phases, inversion of enantiomer elution order as a function of composition is a predicted possibility with a cyclodextrin CSP. Enantiomeric separation by diffusion through aqueous solution interphases of cyclodextrin is also investigated. © 1988, American Chemical Society. All rights reserved.
R. E. Boehm et al., "Theoretical Considerations Concerning The Separation Of Enantiomeric Solutes By Liquid Chromatography," Analytical Chemistry, vol. 60, no. 6, pp. 522 - 528, American Chemical Society, Mar 1988.
The definitive version is available at https://doi.org/10.1021/ac00157a006
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01 Mar 1988