A theoretically correct mixing rule for cubic equations of state

Abstract

AbstractA new mixing rule developed for cubic equations of state equates the excess Helmholtz free energy at infinite pressure from an equation of state to that from an activity coefficient model. Use of the Helmholtz free energy insures that the second virial coefficient calculated from the equation of state has a quadratic composition dependence, as required by statistical mechanics. Consequently, this mixing rule produces the correct low‐ and high‐density limits without being density‐dependent.As a test, the mixing rule is used for ternary mixtures of cyclohexane + benzene + water, ethanol + benzene + water and carbon dioxide + n‐propane + water, and all the constituent binaries. The new mixing rule and a simple cubic equation of state can be used for the accurate correlation of vapor‐liquid and liquid‐liquid equilibria for binary mixtures. Using the parameters obtained from binary systems, the phase behavior of ternary mixtures can be predicted. Also, unlike previous empirical mixing rules, this theoretically based mixing rule is equally applicable and accurate for simple mixtures containing hydrocarbons and inorganic gases and mixtures containing polar, aromatic and associating species over a wide range of pressures. This mixing rule makes it possible to use a single equation of state model with equal accuracy for mixtures usually described by equations of state and for those traditionally described by activity coefficient models. It is the correct bridge between these two classes of models.