Prediction of vapor-liquid equilibria from the corresponding states principle

• Published in: AIChE journal 1962-09, Vol.8 (4), p.482-489
• Main Authors: Leland Jr, Thomas W., Chappelear, Patsy S., Gamson, Bernard W.
• Format: Article
• Language: English
• ISSN: 0001-1541; 1547-5905
• DOI: 10.1002/aic.690080412

A new ideal K value is defined which does not depend on the Lewis and Randall ideal solution rule but is derived only from composition dependent pseudo criticals and the corresponding states principle. Properties of the liquid and vapor mixtures are evaluated from either experimentally measured properties of closely related pure substances or from generalized tables of thermodynamic properties. A derivation of an improved pseudocritical expression applicable to liquids which may be approximated by simple spherical molecules is presented. The derivation illustrates the assumptions involved and points the way for a possible extension of the technique to more complex molecules. There are some advantages to this approach. It does not require the troublesome extrapolation of liquid properties into regions where no liquid can exist, a fact which is characteristic of K value calculations from the ideal solution rule. It is especially useful for systems in which an equation of state is not available for all of the components present. It avoids the difficulties in defining combination rules for complicated equations of state. Even for systems including very complex or moderately polar molecules it provides a base for subsequent empirical modification. This base follows the correct isotherm of In K vs. In P up to the actual critical of the system without the difficulties associated with defining a convergence pressure or evaluating the extremely large activity coefficient corrections to the ideal solution rule in the critical region. For mixtures of simple molecules the calculated ideal K value is within about 10% of the experimental value in both the low pressure and in the critical region. The entire calculation may be expressed completely analytically for use on a digital computer and may be coupled with an equilibrium flash calculation so that the ideal K values may be determined from a given overall composition, temperature, and pressure.