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MOLECULAR SIMULATION STUDIES IN THE SUPERCRITICAL REGION

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MOLECULAR SIMULATION STUDIES IN THE SUPERCRITICAL REGION ( molecular-simulation-studies-insupercritical-region )

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The theory of critical phenomena says that T becomes infinite along the critical isotherm as the system moves close to the critical pressure Figure 8-9: Experimental Isothermal compressibility of CO2 and some mixtures as a function of pressure at temperature T=308.15 K. Data (Zhang et al., 2002a). The maximum value of isothermal compressibility is observed at 8 MPa. In an open system, the isothermal compressibility as we mentioned can be described by the equation 121   (g (r)1)drG Nex vvv vvv vv 0 The Nex is the average excess number of carbon dioxide molecules found around vv another molecule of carbon dioxide (g(r) in terms of solvent, subscribt v denotes the solvent), as compared to the number of molecules which would be found in an uncorrelated (random) system. The isothermal compressibility for an ideal gas system 1  N ex is 0  1/ P . Hence, the isothermal compressibility of a real system is   TTP vv According to the behaviour of isothermal compressibility near the critical point, we can deduce that Nex obtains its maximum value near the critical point. If we express the fluctuation of CO2 molecules around a central CO2 molecule in a fixed volume vv KT(Mpa-1)

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