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The Young-Laplace equation for a solid-liquid interface
P Montero de Hijes1, K Shi2, E G Noya3
1Faculty of Chemistry, Chemical Physics Department, Universidad Complutense de Madrid, Plaza de las Ciencias, Ciudad Universitaria, Madrid 28040, Spain.
The Journal of Chemical Physics
|November 21, 2020
Summary
This study clarifies the thermodynamic pressure for solid-liquid interfaces, showing that using thermodynamic pressure, not mechanical pressure, yields a positive interfacial free energy, consistent with nucleation studies.
Area of Science:
- Thermodynamics
- Materials Science
- Physical Chemistry
Background:
- The Young-Laplace equation is typically applied to fluid-fluid interfaces.
- Applying it to solid-liquid interfaces presents challenges in defining pressure and interfacial free energy.
- Previous studies suggest discrepancies in pressure definitions for solid-liquid systems.
Purpose of the Study:
- To investigate the application of the Young-Laplace equation to solid-liquid interfaces.
- To determine the correct pressure definition for calculating interfacial free energy in solid-liquid systems.
- To reconcile simulation results with established thermodynamic principles.
Main Methods:
- Utilizing computer simulations of hard sphere systems to model solid clusters in a liquid.
- Analyzing the pressure difference between the solid cluster and the external liquid.
- Applying Gibbsian thermodynamics to define interfacial free energy using appropriate pressure terms.
Main Results:
- Computer simulations indicate lower internal pressure within solid clusters compared to the external liquid pressure.
- This pressure difference initially suggests a negative interfacial free energy.
- Using the thermodynamic pressure, as proposed by Tolman, results in a positive interfacial free energy.
- The calculated positive interfacial free energy values align well with prior nucleation study results.
Conclusions:
- The distinction between mechanical and thermodynamic pressure is crucial for solid-liquid interfaces, unlike fluid-fluid interfaces.
- The correct application of Gibbsian thermodynamics requires the use of thermodynamic pressure for curved solid-liquid interfaces.
- This approach resolves discrepancies and provides accurate interfacial free energy values, supporting Gibbs' hypothesis.
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