R. Silveston et B. Kronberg, ACCURATE MEASUREMENTS OF SOLUBILITY AND THERMODYNAMIC TRANSFER QUANTITIES USING REVERSED-PHASE LIQUID-LIQUID CHROMATOGRAPHY, Journal of chromatography, 659(1), 1994, pp. 43-56
A reversed-phase high-performance liquid chromatographic system, consi
sting of polydimethylsiloxane coated on non-porous glass beads as the
stationary phase and pure water as the mobile phase, was used to measu
re the absolute solubility and the temperature dependence of the solub
ility of a series of alkylbenzenes in water in the temperature range 0
-80 degrees C. The system and the method of analysis provide accurate
values of the molar free energy, enthalpy, entropy acid reasonable val
ues of the heat capacity of transfer of the alkylbenzenes from their o
wn liquids into water. The thermodynamic data were analysed in terms o
f the Flory-Huggins theory giving combinatorial and non-combinatorial,
i.e., interactional, contributions to the free energy of transfer. Al
l the data were found to agree very well with literature values. The s
uccess of the system is attributed to the liquid nature of the station
ary phase, the low surface area-to-volume ratio offered by the support
material chosen and the availability of the absolute Value of the vol
ume of the stationary phase to calculate the phase ratio.