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At present, however, the properties of SCFs and their effects on solute reaction are not well understood, and the way is open for computation to provide the underlying insight necessary for efficient development of SCF technologies. When T exceeds Tc, there can be no phase transition between the vapour and liquid phases. Instead, as the pressure is increased the fluid density is changed continuously from gas-like to liquid-like densities. Consequently, density-dependent solvent properties, such as the dielectric constant and the viscosity, will also vary continuously. Pressure thus provides direct control of the fluid’s solvating properties. This tunability is more effective when large changes in density accompany small changes in pressure, i.e., when the isothermal compressibility is large. Coincidentally, the compressibility of a fluid diverges as its critical point is approached, and there exists a region of the phase diagram surrounding the critical point (with the restriction that T>Tc) within which the fluid’s compressibility is anomalously large (Figure 4-5). Evidentially, it is in this compressible regime that pressure-controlled tunability of the solvent properties is maximised, and it is thus of primary interest to understand solute reactivity in this solvent regime. 4.5.1 Effect of density on Equilibrium Constant The effect of pressure (P) on reaction equilibrium constant (Kc), which is the ratio of forward and reverse rate constantskf kr , is expressed in terms of the reaction volume Vrxn : Kc Vrxn P RT T i (4.2) T 61 For a general reaction αΑ + βΒ ... kf γΓ + δΔ ... krPDF Image | MOLECULAR SIMULATION STUDIES IN THE SUPERCRITICAL REGION
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