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2.1 INTRODUCTION The main advantage in application of high pressure to gas phase reactions is seen by the increase of concentrations of the reactants due to compression. Thus, the reaction rates increase as well as the equilibrium conversions, since pressure affects directly the equilibrium (Gao et al., 2003; Peck et al., 1989). With knowledge of the P, V, T-behaviour of the system one can calculate this pressure effect, which is defined as ‘thermodynamic pressure effect’. On the other hand, it is less known that the rate constant coefficient of a reaction also depends on pressure. This pressure effect is called ‘kinetic pressure effect’ (Brennecke and Chateauneuf, 1999; Viana and Reis, 1996). However, the kinetic approach to elucidate the mechanism of a chemical reaction involves the measurement of reaction rates and rate constants as a function of many chemical and physical variables. Much emphasis is usually placed on the activation parameters obtained from the temperature dependence of the reaction. The accuracy of the suggested reaction mechanism is likely to increase with increasing number of variables covered during such investigations (Tiltscher and Hofmann, 1987). This is one of the reasons why pressure has been included as a kinetic (or thermodynamic) variable in an increasing number of studies over the past decades (Jenner, 2002; Tiltscher and Hofmann, 1987). Such additional information may assist not only in the elucidation of the intrinsic reaction mechanism, but it may also reveal new fundamental aspects of the studied systems, and thus add to the understanding of underlying principles of reaction kinetics. Pressure is a fundamental physical property that influences the values of different thermodynamic and kinetic parameters. In the same way as temperature dependence studies tell us something about the energetics of 8PDF Image | MOLECULAR SIMULATION STUDIES IN THE SUPERCRITICAL REGION
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