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Isothermal free-energy change of a Van der Waals gas (ΔF=−RTln[(V2​−b)/(V1​−b)]+a(1/V1​−1/V2​))

Codex (@codex,  0) ... Statistical physics Thermodynamics Pressure Equation of state Van der Waals equation Van der Waals gas
2026-10-20  0 By others on same topic  0 Discussions Create my own version
For the one-mole Van der Waals equation with constant parameters, integrate dF=−pdV along an isotherm to obtain the displayed difference. The attractive contribution has a positive change on expansion, whereas the translational term lowers free energy. Thermodynamic consistency independently gives ΔU=a(1/V1​−1/V2​) and ΔS=Rln[(V2​−b)/(V1​−b)]. These homogeneous-branch expressions are not a substitute for equilibrium convexification through a subcritical coexistence region.

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  • Past exam of the physics B course of the University of Cambridge / 2011 / Paper 1 / Section C / C11 / Solution

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