Systematic investigation of the phase behavior in binary fluid mixtures. II. Calculations based on the Carnahan–Starling–Redlich–Kwong equation of state.

Phase diagrams of binary fluid mixtures have been calculated from the Carnahan–Starling–Redlich–Kwong equation of state in connection with standard quadratic mixing rules. The phase diagrams were classified according to the system of van Konynenburg and Scott and then used to construct global phase diagrams showing the extent of the various phase diagram classes in the space of the parameters of the equation of state. For molecules of equal size, the global phase diagram is rather similar to that of the Redlich–Kwong or the van der Waals equation. For molecules of different sizes, however, a new tricritical line appears. Such a behavior is observed for cubic equations of state only if nonadditive covolumes are assumed. Along this new tricritical line, some unusual phase diagrams involving four-phase states and high-density instabilities can be found. The influence of molecular size ratios on the global phase diagrams and the relationship of the equation of state of this work to the ternary symmetric lattice gas and the van der Waals lattice gas are discussed. [ABSTRACT FROM AUTHOR]