Reliable Computation of Phase Stability and Equilibrium from the SAFT Equation of State

In recent years, molecularly-based equations of state, as typified by the SAFT (statistical associating fluid theory) approach, have become increasingly popular tools for the modeling of phase behavior. However, whether using this, or even much simpler models, the reliable calculation of phase behavior from a given model can be a very challenging computational problem. A new methodology is described that is the first completely reliable technique for computing phase stability and equilibrium from the SAFT model. The method is based on interval analysis, in particular an interval Newton/generalized bisection algorithm, which provides a mathematical and computational guarantee of reliability, and is demonstrated using nonassociating, self-associating, and cross-associating systems. New techniques are presented that can also be exploited when conventional point-valued solution methods are used. These include the use of a volume-based problem formulation, in which the core thermodynamic function for phase equilibrium at constant temperature and pressure is the Helmholtz energy, and an approach for dealing with the internal iteration needed when there are association effects. This provides for direct, as opposed to iterative, determination of the derivatives of the internal variables.