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Near the critical point atT TC , the solvent fluid molecules themselves are apt to form clusters of extremely large size. The effect of pressure on the rate of chemical reactions was originally revealed in solutions under pressure (Asano and Lenoble, 1978; Tiltscher and Hofmann, 1987; Vaneldik and Klärner, 2002). These researches were initiated much earlier than researches in supercritical solvents. Elementary chemical reactions are generally classified according to whether or not the reacting complex must surmount a potential energy barrier in the course of reaction. Reactions for which this is true are called activated processes, while those for which it is not are called diffusion controlled processes. The features of supercritical fluids originate mainly from the intermolecular interactions can affect both of the processes. It is obvious that the study on intermolecular interactions in SCF is very important to their applications. Figure 4-4: Different character of clusters formed in different temperature ranges. Near the critical temperature, the solvent molecules tend to form a large cluster even without a solute molecule. At higher temperatures, the solute molecule with strong attractive interaction is necessary to trigger the clustering of solvent molecules (Reprinted from Baker’s work (Baiker, 1999). 51PDF Image | MOLECULAR SIMULATION STUDIES IN THE SUPERCRITICAL REGION
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