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point (Nishiumi et al., 1996). The restriction to thermal motion of the solute molecule by formation of clusters near the critical region is considered to be one of the reasons for the anomalous diffusivity. Because the transport and solvating properties of a fluid depend strongly on its density, an ability to tune the solvent density translates into an ability to manipulate the efficiency of separation processes and reaction outcomes. Molecular dynamics simulations have historically provided the most detailed information about diffusion processes in fluids. However, dynamic properties from simulations turn out to be much more sensitive to the selected potential. We have calculated the self diffusion coefficient for pure carbon dioxide at 308.15 K. The self diffusion coefficient was calculated from the Einstein’s relationship: Dlim 1 r(t)r(0)2 (8.5) Figure 8-11 compares the self diffusion coefficients for pure CO2 with experimental data. Experimental and simulation are generally limited in the gaseous region with low pressures in the supercritical region. The first experimental data reported on the measurement of self diffusion coefficient was on 1955 (O'Hern and Martin, 1955) and these are the only ones close to the critical point. With the developments of experimental techniques such as nuclear magnetic resonance and theories, measurements under higher pressures with dense gas and liquid phases are available with improved accuracies (Etesse et al., 1992; Gross et al., 1998; O'Hern and Martin, 1955). There are many simulation works of self-diffusion reported in supercritical phase but except the work from Higashi and Iwai (Higashi et al., 2000; Iwai et al., 1997) none is close to the critical point. Up to date, there is a controversial discussion about if an anomalous behaviour of motion exists near the critical (Drozdov and Tucker, 2001; Drozdov and Tucker, 2002) in a pure solvent. What is well known is i 6t ii 124PDF Image | MOLECULAR SIMULATION STUDIES IN THE SUPERCRITICAL REGION
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