Equilibrium constant, high pressure chemical effects

Pressure is a fundamental physical property that affects various thermodynamic and kinetic parameters. Pressure dependence studies of a process reveal information about the volume profile of a process in much the same way as temperature dependence studies illuminate the energetics of the process (83). Since chemical transformations in SCF media require relatively high operating pressures, pressure effects on chemical equilibria and rates of reactions must be considered in evaluating SCF reaction processes (83-85). The most pronounced effect of pressure on reactions in the SCF region has been attributed to the thermodynamic pressure effect on the reaction rate constant (86), and control of this pressure dependency has been cited as one means of selecting between parallel reaction pathways (87). This pressure effect can be conveniently evaluated within the thermodynamic framework provided by transition state theory, which has often been applied to reactions in solutions (31,84,88-90). This theory assumes a true chemical equilibrium between the reactants and an activated transition... 

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