Ensemble inequivalence in the design of mixtures with super-Gibbs phase coexistence.

Abstract

Designing the phase behavior of multicomponent mixtures is a rich area with many potential applications. One key question is how more than M+1 phases, as would normally be allowed by Gibbs' phase rule at generic temperature in a mixture of M molecular species, can be made to coexist in equilibrium. While such "super-Gibbs" phase coexistence is possible in the grand-canonical ensemble by tuning interactions among the M species, there is no straightforward equivalence in the canonical ensemble: Only a subset of the grand-canonical phases will generically be realized. Here, we show that, upon further design of interface tensions, it is possible to stabilize a super-Gibbs number of phases also in the experimentally relevant canonical ensemble, thus effectively restoring equivalence to the grand-canonical one. Using a graph-theoretical approach, we determine a sufficient set of inequalities for the interfacial tensions for which all grand-canonical phases are realized. We illustrate the design method for a two-component mixture with four coexisting phases and point out the route for generalizing this to a higher number of components.