Solvation thermodynamics of xenon in n-alkanes, n-alcohols and water

Experimental thermodynamic data for the solvation of xenon in n-alkanes, water and n-alcohols, from different sources, are analysed by means of a general theory of solvation. The standard solvation Gibbs energy change is given by the sum of the work spent to create a cavity suitable to host xenon and the energy gained to turn on xenon-solvent attractive interactions. The latter contribution is larger in magnitude than the former in both n-alkanes and n-alcohols; the reverse holds in water. This finding is due to the fact that liquid water is characterized by the largest work of cavity creation, because of the smallness of its molecules. Since the two contributions to the solvation Gibbs energy change are both larger in magnitude in n-alcohols with respect to n-alkanes of the same number of heavy atoms, the xenon solubility is not so different between the two classes of solvents. The H-bonds play an indirect role, being important to determine the density of the liquid. It is also shown that there is no clear correlation between the cohesive energy density of the liquid and the solubility of xenon in the liquid itself. The present study confirms that the effective molecular size of solvent molecules is the principal factor in controlling the solvation Gibbs energy changes.