Thermodynamic properties at high pressure

Thermodynamic properties at high pressures are of great interest for instance to Earth scientists who wish to understand the behaviour of the Earth s mantle, where pressures reach 100 GPa. To carry out energy minimizations in the static limit at non-zero pressures we minimize the enthalpy H = U + pV with respect to all the variables that define the structure, where p is the applied pressure and V the volume. When p is zero we regain eq. (11.7). 

After in the foregoing chapter thermodynamic properties at high pressure were considered, in this chapter other fundamental problems, namely the influence of pressure on the kinetic of chemical reactions and on transport properties, is discussed. For this purpose first the molecular theory of the reaction rate constant is considered. The key parameter is the activation volume Av which describes the influence of the pressure on the rate constant. The evaluation of Av from measurement of reaction rates is therefor outlined in detail together with theoretical prediction. Typical value of the activation volume of different single reactions, like unimolecular dissociation, Diels-Alder-, rearrangement-, polymerization- and Menshutkin-reactions but also on complex homogeneous and heterogeneous catalytic reactions are presented and discussed. 

Bertucco, A., and Vetter, G., Thermodynamic Properties at High Pressure, Chapter 2 in High Pressure Process technology Fundamentals and Applications, Elsevier Science, Amsterdam, NL, 2001. 

---