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reaction rate with temperature but there is no similar equation to predict the reaction rate with pressure in SCFs. Solvent properties of SCF are very sensitive to temperature and pressure in the compressible region of the phase diagram in the vicinity of their critical point. This failure reflects the fact that our current theories of solvation and its effect on chemical reaction dynamics do not extrapolate well close to the solvent regime, where novel reactivity has been observed. It is important to keep in mind that the effect of SCF solvents on solubilities, transport properties and the kinetics of the elementary reactions may differ substantially from that expected for non-SCF solvents. An understanding of these effects is needed for the design and optimisation of reaction processes at supercritical conditions (SC). Gaining an understanding of supercritical solvent effects on reaction kinetics from experiment alone is very difficult because of the problems associated with observing the supercritical phase, the reaction rate in such non-ideal environments and characterising their effect on rate constant separately. However, molecular simulation is an appropriate tool for such investigations because these problems do not arise, and system parameters can be precisely controlled and manipulated. Using molecular simulation techniques for that purpose overcomes major problems associated with experimental studies at SC and gives us the opportunity to study microscopic properties such as solution microstructure and their connection to macroscopic properties. Indeed, we believe the main reason for the lack of quantitative prediction of reactivity at SC is the lack of molecular simulation studies connecting microscopic quantities, which are difficult to measure or hard to predict accurately, to macroscopic properties. Potential ways for affecting reactivity at SC is local density augmentation and preferential solvation resulting from the differential stabilization of reactants, products and activated complexes according to the strength 2PDF Image | MOLECULAR SIMULATION STUDIES IN THE SUPERCRITICAL REGION
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