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Modern Thermodynamics for Chemists and Biochemists$
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Dennis Sherwood and Paul Dalby

Print publication date: 2018

Print ISBN-13: 9780198782957

Published to Oxford Scholarship Online: August 2018

DOI: 10.1093/oso/9780198782957.001.0001

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Phase equilibria

Phase equilibria

(p.467) 15 Phase equilibria
Modern Thermodynamics for Chemists and Biochemists

Dennis Sherwood

Paul Dalby

Oxford University Press

This chapter extends the discussion of gas phase equilibria to phase equilibria. The central concept is the vapour pressure, and the key proof is that the criterion for phase equilibrium is the equality of the molar Gibbs free energies, or chemical potentials, of each phase. This then leads to the Clapeyron and Clausius-Clapeyron equations. A notable feature of this chapter is the discussion of non-ideal gases, answering the question “Given that, by definition, an ideal gas can never liquefy, what is it about a real gas that enables the gas to change phase into a liquid?”. A unique feature of this discussion is the rigorous analysis of the Gibbs free energy of a van der Waals gas under compression, and the proof of the ‘Maxwell construction’.

Keywords:   vapour pressure, phase change, solid, liquid, vapour, vaporisation, liquefaction, sublimation, melting, Clapeyron equation, Clausius-Clapeyron equation, ideal gas, real gas, van der Waals equation, critical temperature, Maxwell construction

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