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arXiv · 2401.12606

The Young-Laplace equation for a solid-liquid interface

P. Montero de Hijes·K. Shi·E. G. Noya·E. E. Santiso·K. E. Gubbins·E. Sanz·C. Vega
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Abstract

The application of the Young-Laplace equation to a solid-liquid interface is considered. Computer simulations show that the pressure inside a solid cluster of hard spheres is smaller than the external pressure of the liquid (both for small and large clusters). That would suggest a negative value for the interfacial free energy. We show that in a Gibbsian description of the thermodynamics of a curved solid-liquid interface in equilibrium, the choice of the thermodynamic (rather than mechanical) pressure is required, as suggested by Tolman for the liquid-gas scenario. With this definition, the interfacial free energy is positive, and the values obtained are in excellent agreement with previous results from nucleation studies. Although for a curved fluid-fluid interface there is no distinction between mechanical and thermal pressures (for a sufficiently large inner phase), in the solid-liquid they do not coincide, as hypothesized by Gibbs.

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P. Montero de Hijes, K. Shi, E. G. Noya, E. E. Santiso, K. E. Gubbins, E. Sanz, C. Vega. 2024-01-23. The Young-Laplace equation for a solid-liquid interface. https://doi.org/10.1063/5.0032602

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