Phase Separation in Complex Mixtures with Many Components: Analytical Expressions for Spinodal Manifolds

Abstract

The phase behavior is investigated for systems composed of a large number of macromolecular components N, with N ≥ 2. Liquid–liquid phase separation is modeled using a virial expansion up to the second order of the concentrations of the components. Formal analytical expressions for the spinodal manifolds in N dimensions are derived, which simplify their calculation (by transforming the original problem into inequalities that can be evaluated numerically using linear programming techniques). In addition, a new expression is obtained to calculate the critical manifold and composition of the coexisting phases. The present analytical procedure complements previous attempts to handle spinodal decomposition for many components using a statistical approach based on random matrix theory. The results are relevant for predicting the effects of polydispersity on phase behavior in fields like polymer or food science and liquid–liquid phase separation in the cytosol of living cells.