Abstract
Mathias P.M., Klotz H.C. and Prausnitz J.M., 1991. Equation-of-state mixing rules for multicomponent mixtures: the problem of invariance. Fluid Phase Equilibria, 67: 31-44. Several researchers have recently extended the usual quadratic mixing rules in equations of state by using higher-order polynomials in component mole fraction. Most of these higher-order polynomials exhibit a serious deficiency for multicomponent systems since they are not invariant when a component is divided into two or more identical subcomponents. In this paper we investigate the source of this deficiency and propose a formulation to overcome it. While our analysis here is illustrated with the Peng-Robinson equation of state, it is applicable to other equations of state and to excess-Gibbs-energy models for calculating activity coefficients.
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