Evaporation/condensation and chemically reacting phase diagrams: (a) The intersection of the equilibrium lines of evaporation/condensation and the chemical reaction gives the thermodynamic equilibrium point all initial states converge towards. An example of the change in volume fraction is displayed as a black arrow, which is the sum of a chemical (red) and evaporation/condensation component (green). (b) The set of all such points produces a flow field in the phase diagram, all converging at the thermodynamic equilibrium point, displayed for ke/kc = 4. (c) Phase-separated thermodynamic equilibrium states are only achievable for a single reservoir value for each interaction strength. The phase coexistence line separates solvent-poor and solvent-rich states until the critical point (red cross).

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... φ B /φ A is not conserved, and compatible equilibria are no longer achievable. Thermodynamic equilibrium, therefore, always corresponds to a homogeneous state where the conditions of chemical equilibrium (µ A = µ B ) and evaporation-condensation equilibrium (µ C = µ r C ) are fulfilled; see the intersection between the red and green line in Fig. 3a. Any initial state will evolve following a flow field in the phase diagram toward the fixed point of thermodynamic equilib- rium; see Fig. 3b. Each point in this flow diagram has two independent directions that characterize the rates of change in the average volume fractions, which correspond to the chemical turnover flux of constant φ ...

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... to a homogeneous state where the conditions of chemical equilibrium (µ A = µ B ) and evaporation-condensation equilibrium (µ C = µ r C ) are fulfilled; see the intersection between the red and green line in Fig. 3a. Any initial state will evolve following a flow field in the phase diagram toward the fixed point of thermodynamic equilib- rium; see Fig. 3b. Each point in this flow diagram has two independent directions that characterize the rates of change in the average volume fractions, which correspond to the chemical turnover flux of constant φ A + φ B and evaporation-condensation flux of constant φ B /φ A ; see vectors shown in Fig. 3a. Such fluxes, visualized by the length of each ...

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... toward the fixed point of thermodynamic equilib- rium; see Fig. 3b. Each point in this flow diagram has two independent directions that characterize the rates of change in the average volume fractions, which correspond to the chemical turnover flux of constant φ A + φ B and evaporation-condensation flux of constant φ B /φ A ; see vectors shown in Fig. 3a. Such fluxes, visualized by the length of each vector, are set by k e and k c . Gibbs' phase rule (discussed in appendix C) makes the domain of coexisting states inaccessible at thermodynamic equilibrium, such that small changes in reservoir chemical potential µ r C close to the binodal line pronounces significant changes in the ...

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... of each vector, are set by k e and k c . Gibbs' phase rule (discussed in appendix C) makes the domain of coexisting states inaccessible at thermodynamic equilibrium, such that small changes in reservoir chemical potential µ r C close to the binodal line pronounces significant changes in the equilibrium compositions. This behavior is shown in Fig. 3c, where solvent-rich and solvent-poor equilibrium states are separated by the phase coexistence line ending up at the critical point (red cross) in Fig. 3c. Speed-up and slow-down of chemical reactions through evaporation and ...

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... equilibrium, such that small changes in reservoir chemical potential µ r C close to the binodal line pronounces significant changes in the equilibrium compositions. This behavior is shown in Fig. 3c, where solvent-rich and solvent-poor equilibrium states are separated by the phase coexistence line ending up at the critical point (red cross) in Fig. 3c. Speed-up and slow-down of chemical reactions through evaporation and ...

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... p, µ r C }-space and a plane in {T, µ r C }-space, while the homogeneous system has an additional degree of freedom. For a fixed reservoir and a single chemical reaction, the degree of freedom becomes F = 2 − P, such that two-phase coexistence is only achievable for a single point in the phase diagram. This is consistent with the phase diagram in Fig. 3c. ...