Year: 2025
Type: article
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.
Source: Physical review. E
DOI: 10.1103/z6v8-pmm9
Authors: Filipe C. Thewes, Peter Sollich
Language: English
Subfield: Biomedical Engineering
Field: Engineering
Domain: Physical Sciences
Open Access status: hybrid
Funder: Deutsche Forschungsgemeinschaft
Award: G7804945674
OpenAlex ID: W4413503453