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strong indication of the unusual behaviours at supercritical conditions. The isothermal compressibility (κT) can be obtained from densities of the fluids according to equation (4.9) 1V 1 (4.9) T V P P T T The theory of critical phenomena (Tucker and Maddox, 1998) tells us that, as the critical point of a fluid is approached (T → Tc), the isothermal compressibility diverges (i.e., it becomes infinite). Since this divergence occurs smoothly, there must exist a region of the phase diagram with T > Tc for which the compressibility is large, by which we mean that T > T0 , where κ is the compressibility of an ideal gas (The compressibility of a perfect gas is given asT0 ). As it turns out, this region of large , which is called the‘compressible regime’ extends well beyond the near- critical region of the phase diagram in which all fluids behave universally and the theories of critical phenomena apply (Tucker, 1999). Macroscopically, a large compressibility means that there is very little cost associated with an increase in solvent density, so we can easily compress the fluid. From a molecular point of view, a large compressibility means that there is enough free space, (a big voidage) between molecules, allowing the system to be compressed. In this case, there are two pictures of molecular microstructure that can satisfy this situation. Firstly, if the voidage is uniformly distributed between the molecules, or secondly, if there are high and low density regions. In the first case, a little effort is required to compress and condense the molecules together. In second case, a little cost is required to transfer a molecule from a low-density region to a high-density one. According to Morita (Nishikawa and Morita, 2000) there is a ridge that separates the supercritical region into more liquid-like and more gas-like regions in the supercritical 66PDF Image | MOLECULAR SIMULATION STUDIES IN THE SUPERCRITICAL REGION
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