Solution

ID: past-exam-of-the-mathematics-course-of-the-university-of-cambridge/2011/ii/paper-4/34d/iii/solution

At a fixed subcritical temperature, coexistence requires equal pressure and equal chemical potential of the liquid and gas. The Maxwell equal-area construction chooses and the two outer intersection volumes so that
Indeed , and integration by parts gives , so the equal-area condition is exactly equality of chemical potentials.
Let be the two spinodal volumes where . A homogeneous phase is mechanically unstable on , since gives negative compressibility. The negative-slope branches and are metastable homogeneous liquid and gas respectively: they resist small perturbations but a two-phase state has lower free energy. The single-phase stable branches are and . Throughout the coexistence interval , the equilibrium state is a mixture at pressure with its phase fractions chosen to produce the total volume. The preceding figure labels both the formal homogeneous branches and the equilibrium coexistence segment.

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