Industrial & Engineering Chemistry Research, Vol.52, No.28, 9690-9697, 2013
Calculations of Complex Phase Equilibrium by Semigrand Canonical Ensemble
The recently developed method of semigrand canonical (sGC) ensemble (Tang, Y. J. Chem. Phys. 2012, 136, 034505) was employed to calculate phase equilibria for binary mixtures. The calculations cover vapor liquid equilibria (VLE), liquid liquid equilibria (LLE), solid liquid equilibria (SLE), and solid solid equilibria (SSE). The thermodynamic models in this study include cubic and noncubic equations of state, the activity coefficient model, and the alloy-based model. On the basis of extensive calculations and comparisons with classical methods, we conclude that the sGC method is universal for calculating complex phase equilibria. In particular, it is very robust in cases of multiple vdW loops with and without intersections, which are often difficult and require special treatments for classical methods. The phase stability characteristics of the sGC method are also addressed.