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that the supercritical fluids exhibit large diffusion coefficients, which resemble those of gases than those of liquids. The diffusion coefficient in the supercritical region is strongly dependent on temperature and pressure D=D(T, P). The temperature dependence of D in isobaric change can be interpreted through an Arrhenius plot. Transition state theory can be used to interpret the temperature dependence of the diffusion coefficient through the equation (D)p D0 e(E / RT) (equivalent to Arrhenius equation). These activation energies usually depend on pressure and density (Drozdov and Tucker, 2001). In the same way, the pressure dependence on the diffusion coefficient can be interpreted through an equivalent equation. The slope of the diffusivity with pressure gives the activation volume. The activation volume is defined as V RTlnD (8.6) P T const Up to now, we really do not know how or even if, local density inhomogeneities affect molecular diffusion coefficients, which is an important transport property necessary for the prediction of chemical reaction rates and the design of SCF reactors. We present the diffusion coefficient results for the critical isotherm T=1.02Tc. The simulation results are in good agreement with experiments studies. Inspection of Figure 8-11 shows that the diffusion coefficient of CO2 decreases with increasing pressure. Until the pressure reaches the critical pressure, the diffusion coefficient is quite large and resembles the one from gas phase after that, the diffusion coefficient resembles the one from liquid phase. This fact is in a good agreement with the theory of the two supercritical region area divided by a ridge, which the locus of the points where the values of the density fluctuation become maximum in isothermal change (Nakayama et al., 2000; Nishikawa and Morita, 2000). The same can be deducted 125PDF Image | MOLECULAR SIMULATION STUDIES IN THE SUPERCRITICAL REGION
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