Journal of Physical Chemistry B, Vol.104, No.11, 2540-2545, 2000
On density microheterogeneities in dilute supercritical solutions
The dilute supercritical mixtures were examined in the framework of the Kirkwood-Buff theory of solutions. Various expressions were employed for the excess number of aggregated molecules of solvent around individual solute molecules to conclude that at infinite dilution the above mentioned excess is zero. This suggested that the density enhancement observed when small amounts of a solute were added to a solvent near the critical point of the latter may not be caused by the aggregation of the solvent molecules around individual solute molecules as usually considered. Further, comparing experimental results, it was shown that the density enhancement caused by the near critical fluctuations in a pure solvent are almost re same, in a wide range of pressures, as those in dilute supercritical mixtures near the critical paint of the solvent.
Keywords:X-RAY-SCATTERING;KIRKWOOD-BUFF INTEGRALS;CARBON-DIOXIDE;PREFERENTIAL SOLVATION;INFINITE DILUTION;PHASE-EQUILIBRIA;FLUIDS;MIXTURES;SPECTROSCOPY;BEHAVIOR