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The second Gibbs paradox
1Yusuf Hamied Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, United Kingdom.
The Journal of Chemical Physics
|March 4, 2026
Summary
This study explains Gibbs's second paradox regarding chemical potential in heterogeneous systems. It proposes that understanding point defects in critical nuclei is key to resolving this surface tension-related equilibrium puzzle.
Area of Science:
- Physical Chemistry
- Materials Science
- Thermodynamics
Background:
- J. Willard Gibbs's work on heterogeneous equilibrium presents a paradox concerning chemical potential at interfaces.
- The paradox arises when surface free-energy density differs from mechanical surface tension for a crystallite in fluid equilibrium.
Purpose of the Study:
- To interpret Gibbs's and Mullins's approaches to the "second Gibbs paradox."
- To clarify the chemical potential of a nucleus by considering point defects.
Main Methods:
- Interpretation of existing theories by Gibbs and Mullins.
- Focus on the role of vacancies and interstitials in critical nuclei.
Main Results:
- A framework is presented that accounts for vacancies and interstitials.
- The chemical potential of a nucleus is clarified through a consistent treatment of point defects.
Conclusions:
- A consistent treatment of point defects is essential for understanding the chemical potential of nuclei.
- This interpretation aims to be more accessible to scientists focusing on atomic and molecular perspectives.
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