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Journal of Physical Chemistry A, Vol.104, No.22, 5396-5400, 2000
Infinite-dilution partial molar properties of naphthalene and biphenyl in carbon dioxide from supercritical fluid chromatography: Composition effects in the stationary phase
The temperature and pressure effects on retention of naphthalene and biphenyl in supercritical fluid chromatography are investigated within 35-70 degrees C and 75-150 bar. The retention factors are used to derive the infinite-dilution partial molar volumes of the two solutes in supercritical carbon dioxide, and the infinite-dilution molar enthalpies of transfer of the two solutes from the stationary phase to supercritical CO2. The partial molar volumes are converted to quantities characterizing short-range interactions between CO2 and the aromatic hydrocarbon. The resultant partial molar properties are corrected for the pressure- and temperature-dependent dissolution of CO2 in the stationary polymer (poly(dimethylsiloxane)). The corrections for composition changes in the stationary phase include a composition derivative of the solute chemical potential that can only be obtained from a suitable theoretical model. Therefore, it is difficult to give a conclusive account of the performance of the corrections as these reflect the features of the model employed; here, the Scatchard-Hildebrand-Flory-Huggins theory or the Panayiotou-Vera lattice-fluid model are used for the purpose. However, comparison of the resultant partial molar volumes of naphthalene with literature data from high-precision, vibrating-tube densitometry indicates that the composition corrections improve the agreement between chromatographic and densitometric results.