An official website of the United States government
Coupling between chemical fuel consumption and phase separation can lead to condensation at a nonequilibrium steady state, resulting in phase behaviors that are not described by equilibrium thermodynamics. Theoretical models of such “chemically driven fluids” typically invoke near-equilibrium approximations at small length scales. However, because dissipation occurs due to both molecular-scale chemical reactions and mesoscale diffusive transport, it has remained unclear which properties of phase-separated reaction–diffusion systems can be assumed to be at an effective equilibrium. Here, we use microscopic simulations to show that mesoscopic fluxes are dependent on nonequilibrium fluctuations at phase-separated interfaces. We further develop a first-principles theory to predict nonequilibrium coexistence curves, localization of mesoscopic fluxes near phase-separated interfaces, and droplet size-scaling relations in good agreement with simulations. Our findings highlight the central role of interfacial properties in governing nonequilibrium condensation and have broad implications for droplet nucleation, coarsening, and size control in chemically driven fluids.
more »
« less
Nonequilibrium interfacial properties of chemically driven fluids
Chemically driven fluids can demix to form condensed droplets that exhibit phase behaviors not observed at equilibrium. In particular, nonequilibrium interfacial properties can emerge when the chemical reactions are driven differentially between the interior and exterior of the phase-separated droplets. Here, we use a minimal model to study changes in the interfacial tension between coexisting phases away from equilibrium. Simulations of both droplet nucleation and interface roughness indicate that the nonequilibrium interfacial tension can either be increased or decreased relative to its equilibrium value, depending on whether the driven chemical reactions are accelerated or decelerated within the droplets. Finally, we show that these observations can be understood using a predictive theory based on an effective thermodynamic equilibrium.
more »
« less
- Award ID(s):
- 2143670
- PAR ID:
- 10484802
- Publisher / Repository:
- AIP
- Date Published:
- Journal Name:
- The Journal of Chemical Physics
- Volume:
- 159
- Issue:
- 15
- ISSN:
- 0021-9606
- Page Range / eLocation ID:
- 154101
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Nonequilibrium interfacial thermodynamics has important implications for crucial biological, physical, and industrial-scale transport processes. Here, we discuss a theory of local equilibrium for multiphase multicomponent interfaces that builds upon the “sharp” interface concept first introduced by Gibbs, allowing for a description of nonequilibrium interfacial processes such as those arising in evaporation, condensation, adsorption, etc. By requiring that the thermodynamics be insensitive to the precise location of the dividing surface, one can identify conditions for local equilibrium and develop methods for measuring the values of intensive variables at the interface. We then use extensive, high-precision nonequilibrium molecular dynamics (NEMD) simulations to verify the theory and establish the validity of the local equilibrium hypothesis. In particular, we demonstrate that equilibrium equations of state are also valid out of equilibrium, and can be used to determine interfacial temperature and chemical potential(s) that are consistent with nonequilibrium generalizations of the Clapeyron and Gibbs adsorption equations. We also show, for example, that, far from equilibrium, temperature or chemical potential differences need not be uniform across an interface and may instead exhibit pronounced discontinuities. However, even in these circumstances, we demonstrate that the local equilibrium hypothesis and its implications remain valid. These results provide a thermodynamic foundation and computational tools for studying or revisiting a wide variety of interfacial transport phenomena.more » « less
-
Forming an interface between immiscible fluids incurs a free-energy cost that usually favors minimizing the interfacial area. An emulsion droplet of fixed volume therefore tends to form a sphere, and pairs of droplets tend to coalesce. Surfactant molecules adsorbed to the droplets' surfaces stabilize emulsions by providing a kinetic barrier to coalescence. Here, we show that the pressure exerted by bound surfactant molecules also competes with the droplet's intrinsic surface tension and can reverse the sign of the overall surface free energy. The onset of negative surface tension favors maximizing surface area and therefore favors elongation into a wormlike morphology. Analyzing this system in the Gibbs grand canonical ensemble reveals a phase transition between spherical and wormlike emulsions that is governed by the chemical potential of surfactant molecules in solution. Predictions based on this model agree with the observed behavior of an experimental model system composed of lipid-stabilized silicone oil droplets in an aqueous surfactant solution.more » « less
-
Abstract Kauzmann paradox (KP) suggests that deeply supercooled liquids can have a lower entropy than the corresponding crystalline solids. While this entropy catastrophe has been thoroughly studied via equilibrium thermodynamics, the solidification process occurs far‐from‐equilibrium. By analyzing this process experimentally and theoretically, we show that surface chemical speciation (oxidation‐driven generation and self‐organization of different species of the alloy components) in core‐shell particles (CSPs) can perturb the entropy production to an extent that a continuum equilibrium phase transition is not possible. Speciation of the surface causes divergence of associated stress vectors that generate nonequilibrium fluxes and frustrates homogeneous nucleation hence deep undercooling. The asymmetry of the speciation‐derived surface tensor skews the minimum entropy production criterion. We analyze a set of nonequilibrium models, one showing and one averting the entropy catastrophe. Applying thermodynamic speed limits to these models, we show that the KP takes another form. Deviations from the speed limit diverge the configurational entropy of the glass, but adding an interfacial state avoids the entropy catastrophe with significantly large supercooling.more » « less
-
Abstract Compartments are a fundamental feature of life, based variously on lipid membranes, protein shells, or biopolymer phase separation. Here, this combines self‐assembling bacterial microcompartment (BMC) shell proteins and liquid‐liquid phase separation (LLPS) to develop new forms of compartmentalization. It is found that BMC shell proteins assemble at the liquid‐liquid interfaces between either 1) the dextran‐rich droplets and PEG‐rich continuous phase of a poly(ethyleneglycol)(PEG)/dextran aqueous two‐phase system, or 2) the polypeptide‐rich coacervate droplets and continuous dilute phase of a polylysine/polyaspartate complex coacervate system. Interfacial protein assemblies in the coacervate system are sensitive to the ratio of cationic to anionic polypeptides, consistent with electrostatically‐driven assembly. In both systems, interfacial protein assembly competes with aggregation, with protein concentration and polycation availability impacting coating. These two LLPS systems are then combined to form a three‐phase system wherein coacervate droplets are contained within dextran‐rich phase droplets. Interfacial localization of BMC hexameric shell proteins is tunable in a three‐phase system by changing the polyelectrolyte charge ratio. The tens‐of‐micron scale BMC shell protein‐coated droplets introduced here can accommodate bioactive cargo such as enzymes or RNA and represent a new synthetic cell strategy for organizing biomimetic functionality.more » « less
- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1063/5.0166824
