Moment free energies for polydisperse systems

Abstract

A polydisperse system contains particles with at least one attribute $σ$ (such as particle size in colloids or chain length in polymers) which takes values in a continuous range. It therefore has an infinite number of conserved densities, described by a density {\em distribution} $ρ(σ)$. The free energy depends on all details of $ρ(σ)$, making the analysis of phase equilibria in such systems intractable. However, in many (especially mean-field) models the {\em excess} free energy only depends on a finite number of (generalized) moments of $ρ(σ)$; we call these models truncatable. We show, for these models, how to derive approximate expressions for the {\em total} free energy which only depend on such moment densities. Our treatment unifies and explores in detail two recent separate proposals by the authors for the construction of such moment free energies. We show that even though the moment free energy only depends on a finite number of density variables, it gives the same spinodals and critical points as the original free energy and also correctly locates the onset of phase coexistence. Results from the moment free energy for the coexistence of two or more phases occupying comparable volumes are only approximate, but can be refined arbitrarily by retaining additional moment densities. Applications to Flory-Huggins theory for length-polydisperse homopolymers, and for chemically polydisperse copolymers, show that the moment free energy approach is computationally robust and gives new geometrical insights into the thermodynamics of polydispersity.