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4.5.3 Partial Molar Volumes When solutes are introduced into such a fluid, substantial solvent density enhancements (clustering) or depletion (cavitation) are often observed around solute molecules. Debenedetti and co-workers identified 3 solute behaviours: repulsive, weakly attractive, and attractive, as follows (Debenedetti and Mohamed, 1989; Petsche and Debenedetti, 1991). 1. Repulsive solutes are those for which the repulsive part of the solute-solvent potential dominates the solute-solvent interactions. In this case, the solute and solvent molecules repel each other and, consequently, the average solvent density around a solute is less than the bulk density. Thus, addition of solute increases the volume of the solution and gives positive partial molar volumes (PMV). Weakly attractive solutes are those for which the solute-solvent potential interaction is dominantly attractive but are less so than the solvent-solvent potential interaction. So, the addition of solute still increases the volume of the solution and gives positive partial molar volumes. Attractive behaviour results when the dominant solvent-solute interaction is more attractive than the solvent-solvent interaction, so that the solute-solvent correlations exceed the solvent-solvent correlations. In this case, addition of solute decreases the volume of the solution and gives negative partial molar volumes. 2. 3. The observed partial molar volumes provided the main impetus for a whole new realm of investigations seeking to better understand the intermolecular interactions between the solute and the other species in SCF solutions. For example the partial molar volume of naphthalene at infinite dilution in a mixture of naphthalene and supercritical carbon dioxide is -2300cm3/mol at P=76 bar and 63PDF Image | MOLECULAR SIMULATION STUDIES IN THE SUPERCRITICAL REGION
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