The Young-Laplace equation for a solid-liquid interface

The Journal of Chemical Physics
P Montero de HijesC Vega

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). This 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 interface, they do not coincide, as hypothesized by Gibbs.

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Citations

Jan 21, 2021·Physical Review. E·I Sanchez-BurgosE Sanz
Jan 23, 2021·Physical Review Letters·Valentino BiancoCarlos Vega
Mar 1, 2021·The Journal of Chemical Physics·Kaihang ShiKeith E Gubbins

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