An empirical relationship was derived which relates properties of the mobil
e phase modifier to the chiral selectivity factor for a given analyte/chira
l selector combination. Using carbon dioxide and heptane-based mobile phase
s, the effect of various mobile phase modifiers on Pirkle-type stationary p
hases may be accurately modeled using a two-parameter equation. Similar res
ults are obtained using cellulosic stationary phases with carbon dioxide-ba
sed mobile phases. Modeling separations performed using heptane-based mobil
e phases with cellulosic stationary phases were not successful. The predict
ive ability of this modeling approach was demonstrated using novel modifier
s and chiral analytes. (C) 1999 Dupont Pharmaceuticals Co. Published by Els
evier Science B.V. All rights reserved.