Fluid phase stability and equilibrium calculations in binary mixtures: Part I: Theoretical development for non-azeotropic mixtures

A framework is proposed for the solution of fluid phase equilibrium (P–T flash) for binary mixtures described by equations of state of general form. The framework is based on decomposing the phase equilibrium problem into sub-problems with more convenient and tractable mathematical and numerical properties. Systematic procedures are used to identify the mapping of the problem in the density and composition space, referred to as the density–composition pattern, at specified temperature and pressure. A series of stability tests is then carried out to explore the existence or non-existence of phases. Once the existence of a phase has been determined, the limits of stability and physical bounds on the problem are used to define the search area for that phase in the density–composition pattern. Finally, all available information from this detailed analysis is used for the solution of phase equilibrium between the phases identified in order to find the stable state at the specified conditions. The features of the proposed approach are exposed in detail through an algorithm for the fluid phase equilibria of the augmented van der Waals equation of state applied to non-azeotropic mixtures.