The influence of different solute−micelle interactions on
micellar solubilization is studied by using linear
solvation
energy relationship (LSER) modeling. The LSER results
for six anionic micellar systems demonstrate that the
migration behavior of neutral species in micellar electrokinetic chromatography (MEKC) is mainly determined by
their molar volume and their hydrogen bond acceptor
ability. Their polarity and hydrogen bond donor
ability
are shown to be of minor importance with these anionic
surfactants. Large differences in selectivity were
observed
for sodium dodecyl sulfate (SDS) and mixed SDS/Brij 35
micellar systems, primarily due to different hydrogen
bonding characteristics. It is demonstrated that
retention
indexes can be applied for quantitative characterization
of pseudostationary phases in MEKC in a way similar to
the use of the Rohrschneider−McReynolds scale in GC.
This method facilitates classification of
pseudostationary
phases according to several solvatochromic quantities
with a limited number of experiments. Using this approach, six anionic and two cationic micellar systems were
classified according to their hydrogen bond donor and
hydrogen bond acceptor strengths, respectively, giving
results comparable to those obtained with the LSER
models. The relationship between retention indexes
and
n-octanol−water partition coefficients is treated
theoretically and is applied for the prediction of retention
indexes
in a mixed SDS/Brij 35 micellar system.