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  • Print publication year: 2014
  • Online publication date: May 2018

Appendix B - Fluid equations of state


The text considers the ideal gas and van der Waals equations of state in some detail. In addition to these, we summarize here several more-accurate equations of state. This appendix presents but a small fraction of such equations. A more comprehensive discussion of the quality of such equations is given in [118].

Note that all fluid equations of state reduce to the general ideal gas at low densities. For small deviations from ideal behavior, the virial expansion is the most reliable. However, it is not appropriate for predicting vapor–liquid equilibria. The cubic equations of state are straightforward to use and computationally simple. However, some sacrifice must be made for accuracy. Of these, the Peng–Robinson, Soave–Redlich–Kwong, and Schmidt–Wenzel equations are usually superior. However, all cubic equations are suspect near the critical region. For an excellent review of many such equations, see [5]. If computational ease should be sacrificed for accuracy, the Benedict–Webb–Rubin and the Anderko–Pitzer equations are usually more accurate.

The parameters in the cubic PVT equations of state are usually determined from the critical properties of a fluid, and these equations are given. Critical values for a few substances are given in Table D.3 in Appendix D. More values can be found from the NIST web page. If the critical values of a substance are not known, they may be estimated from group methods on the basis of the chemical structure of the substance. These methods are reviewed in [102].