The Young-Laplace equation for a solid-liquid interface
arXiv:2401.12606 · doi:10.1063/5.0032602
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.
References in corpus (7)
- Determination of phase diagrams via computer simulation: Methodology and applications to water, electrolytes and proteins
- A perspective on the interfacial properties of nanoscopic liquid drops
- Evidence for the role of fluctuations in the thermodynamics of nanoscale drops and the implications in computations of the surface tension
- Finite size effects on liquid-solid phase coexistence and the estimation of crystal nucleation barriers
- Seeding Approach to nucleation in the NVT ensemble: the case of bubble cavitation in overstretched Lennard Jones fluids
- Interfacial free energy and Tolman length of curved liquid-solid interfaces from equilibrium studies
- Free Energy Barriers for Crystal Nucleation from Fluid Phases