Gibbs free energy of mixing

ID: gibbs-free-energy-of-mixing

The Gibbs free energy of mixing compares the final mixture's Gibbs free energy with that of its initially separate components at the same temperature and pressure. For an ideal solution, subtract the pure-component reference from :
For one mole of the chosen A/B ideal solution at and ,
The individual chemical potential changes are for A and for B. Weighting these by and reproduces the total Gibbs free energy of mixing.
Figure 1.
Chosen ideal binary model: entropy gain and Gibbs energy decrease
. At the same stipulated temperature , one mole of the invented A/B ideal solution has positive entropy of mixing and negative Gibbs free energy of mixing at every interior composition. The marked example gives approximately and . Dashed markers show the extrema at equal mole fractions; both functions vanish at the pure endpoints. These are calculated mixing quantities at a common initial/final pressure, not measured data or a vapor composition plot. Details.
If ideality holds in a neighborhood of the specified temperature and pressure, differentiation at fixed component amounts gives
Thus the ideal mixing Gibbs free energy decrease comes entirely from the entropy increase; the mixing enthalpy and volume changes vanish. Ideality at a single isolated state alone does not determine temperature or pressure derivatives.[ref]
The same formula rules out spontaneous separation into two liquid thermodynamic phases within this model. Per mole, the mixing Gibbs free energy has
Adding the pure-component reference contributions changes only a term linear in . The total molar Gibbs free energy is therefore a strictly convex function: a separated pair of different compositions has a larger composition-weighted Gibbs free energy than the uniform sample with the same inventory. Such phase separation requires physics beyond this ideal solution model.

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