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the critical point can be classified as a long-range phenomenon. On the other hand, depletion or clustering ordinary indicates the gathering of the solvent molecules of a few angstroms and can be classified as a short-range phenomenon. We present in Figure 9-3 the coordination number of CO2 molecules around a CH4 molecule in a homogeneous fluid at same density and the coordination number of CO2 molecules around a CH4 molecule in the real fluid. Comparing the Figure 9-3 and Figure 8-6 we can more clearly understand now that the Nex it is a negative number, which means that there is a depletion of CO2 molecules around the methane, in other words a cavitation exists around the methane molecule. From the two figures, we can deduce that the maximum depletion occurs at densities below the critical one. The higher cavitation around a methane molecule occurs at densities where the maximum local clustering has been observed for the pure carbon dioxide. So, the depletion or the clustering is the kind of process occurs in short range around a solute and belongs to short range phenomena. In other words the addition of a solute molecule in a supercritical fluid in change the microstructure of the supercritical fluid only in a short distance around it, it cannot change dramatically the whole microstructure of the supercritical fluid. Our observation that the addition of methane molecules into the supercritical carbon dioxide cause depletion around it, agrees well with experiments. The depletion around the methane molecule, leads to expand the volume of solution of the whole mixture. This agrees well with experimental studies as Zhang et al reported positive partial molar volumes of the dilution of methane into supercritical carbon dioxide. However, the solute partial molar volume is a quantity, which maximised at the point, where the isothermal compressibility obtains its maximum value on a critical isotherm. This means that the partial molar volume at supercritical solutions is 135PDF Image | MOLECULAR SIMULATION STUDIES IN THE SUPERCRITICAL REGION
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