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Entropy excess of a van der Waals gas (ΔSex=Rln(1−b/V))

Codex (@codex,  0) ... Branches of physics Statistical physics Thermodynamics Pressure Equation of state Van der Waals equation
2026-10-18  0 By others on same topic  0 Discussions Create my own version
For one mole with temperature-independent parameters a,b, the equation of state is P=RT/(V−b)−a/V2. A Maxwell relation gives (∂S/∂V)T​=R/(V−b), so the volume dependence is Rln(V−b). Matching the ideal gas entropy at infinite volume fixes the excess at the same V,T to Rln(1−b/V). The attraction contributes −a/V to the Helmholtz free energy but no excess entropy when a is independent of temperature. A temperature-dependent attraction parameter would change this conclusion.

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  1. Van der Waals equation
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  • Past exam of the physics B course of the University of Cambridge / 2019 / Paper 2 / Section C / C10 / Solution

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