Published:Journal of Chromatographic Science,
ISSN 0021-9665Volume
39, Number 10, October 2001, pp. 215-222
Solute–Solvent Interactions From Gas Chromatographic Activity
Coefficients and the Solvation Parameter Model for Nitrogen-Containing Stationary
Phases
José M. Santiuste
Instituto de Química Física “Rocasolano”, CSIC, Department
of Structure and Molecular Dynamics, C. Serrano, 119, 28006-Madrid, Spain
Infinite dilution gas–liquid chromatographic activity
coefficients (g) and excess thermodynamic molar partial magnitudes [Gibbs energy
(GE), enthalpy (HE), and entropy (SE)] for 37 solutes of varied polarity on
four stationary phases with –NH groups are obtained from partition coefficients
taken from literature. Relationships between GE and SE with the 37 solutes’ structure
in terms of the molecular connectivity index (1cv) are investigated. Correlations
of solute–solvent interactions calculated in light of the solvation parameter
model for selected solutes and stationary phases are tested. The effect of
the solute’s structure, expressed as the molecular connectivity index,
on the nonpolar (cavity formation and dispersion interaction) [c+l. log L(16)]
and the effect of the dipole moment and of the activity coefficient on the
dipolarity–polarizability interaction (spH2) are studied. The correlation
between the nonpolar interaction with the athermal activity coefficient on
the nonpolymeric stationary phases is also attempted. In addition, the influence
of the stationary phase polarity on the solute–stationary phase interactions
for a series of solutes is studied.
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