Abstract
Formal thermodynamic relationships were derived for the specific retention volume of the solute in the solute-carrier gas-stationary liquid ternary system, applicable at higher pressures and with a negligible pressure drop across the column. Special attention has been paid to the effects of the solubility of the carrier gas in the stationary phase and to the non-ideal behaviour of the carrier gas. The relationships derived show that the pressure dependence of the specific retention volume alone can give only approximate information on binary solute-carrier gas systems. If more precise data are to be obtained, it is necessary to know additional parameters (the partial molar volume of solute in the solute-carrier gas-stationary liquid ternary system, activity coefficients of the dissolved carrier gas and their dependence on the composition, and the molar fraction of dissolved carrier gas), which cannot be obtained reliably from chromatographic data.
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