Rw. Stringham et Ja. Blackwell, FACTORS THAT CONTROL SUCCESSFUL ENTROPICALLY DRIVEN CHIRAL SEPARATIONS IN SFC AND HPLC, Analytical chemistry, 69(7), 1997, pp. 1414-1420
With temperature increases, selectivity of chiral separations decrease
s until enantiomers coelute at an isoelution temperature. Above this t
emperature, elution order should reverse and selectivity will increase
with temperature, In this region, separation is termed ''entropically
driven'', Entropically driven chiral separations hold the promise of
being able to concurrently increase selectivity and column efficiency
by means of increased temperature, The ability to achieve such separat
ions is hindered by high isoelution temperatures, The isoelution tempe
rature is determined by a balance of enthalpic and entropic contributi
ons, A variety of mobile phase modifiers are evaluated for their abili
ty to moderate these contributions, Results suggest that more use shou
ld be made of nonalcohol modifiers. The major barrier to entropically
driven separations was found to be the nonspecific retention increase
that is characteristic when the critical temperature is traversed, Use
of hexane in place of CO2 shifts the position of the retention increa
se away from the temperature range used in this study, and dramaticall
y successful entropically driven chiral separations are obtained.