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The formation of cavitations around repulsive solutes is an interesting process but to the best of our knowledge, there is no industrial application using this feature. We believe this kind of solvent can used as co-solvents in order to expand the common features (clustering) of supercritical fluids. All the supercritical solutions in technological applications are cases of attractive clustering mixtures e.g., decaffeination of coffee and other examples of supercritical fluid extraction, supercritical chromatography, sorbent regeneration by supercritical fluids. These mixtures are characterised by large negative solute partial molar volumes near the solvent critical point. The mixture of water and supercritical carbon dioxide belongs to that category. We will examine that system in the next section. 9.3 INFINITE DILUTION OF WATER IN SUPERCRITICAL CARBON DIOXIDE The research group of (Zhang et al., 2002a) reported negative partial molar volumes of water and carbon dioxide at infinite dilution. We followed exactly the same approach as in the case of methane with carbon dioxide, in order to examine the microstructure of the solution. We present the coordination number of CO2 around a water molecule in Figure 9-4. There is an enhancement of local density around the water molecule. The degree of density enhancement is stronger than those of a CO2 molecule. According to experimental studies (Song et al., 2000) the larger degree of clustering appears at densities below the critical one. Figure 9-4 shows the maximum clustering occurs at densities around 300 kg/m3. Our simulation results are in line with experimental observations and we can verify that the maximum degree of clustering occurs at densities around (2/3)c for an attractive solute. 137PDF Image | MOLECULAR SIMULATION STUDIES IN THE SUPERCRITICAL REGION
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