: Rational selection of multiphase systems as required in bioseparation equipment and sequences in bioseparation processes beneüts tremendously from the availability of accurate and reliable thermodynamic data and predictive models. In this paper, we comment on a general methodology to correlate limiting thermodynamic properties which are of use in a wide variety of existing separation processes, including crystallization, aqueous-organic and aqueous two-phase system extraction, ion exchange, sorption and membrane processes. It is also demonstrated that this approach helps in developing quantitative insight into complex heterogeneous systems such as CO 2 -extraction with organic solvents. It is shown that the parameters in this general methodology aided can be obtained from a limited number of experiments, translated across the boundaries of diþ erent separation techniques and be predicted from data that are commonly found in the characterization of the ünal products. In addition, some drawbacks and pittfalls of this approach are addressed.1999 Society of Chemical Industry (