| Autor: |
Montero de Hijes P; Faculty of Chemistry, Chemical Physics Department, Universidad Complutense de Madrid, Plaza de las Ciencias, Ciudad Universitaria, Madrid 28040, Spain., Shi K; Department of Chemical and Biomolecular Engineering, North Carolina State University, Raleigh, North Carolina 27606, USA., Noya EG; Instituto de Química Física Rocasolano, Consejo Superior de Investigaciones Científicas, CSIC, Calle Serrano 119, 28006 Madrid, Spain., Santiso EE; Department of Chemical and Biomolecular Engineering, North Carolina State University, Raleigh, North Carolina 27606, USA., Gubbins KE; Department of Chemical and Biomolecular Engineering, North Carolina State University, Raleigh, North Carolina 27606, USA., Sanz E; Faculty of Chemistry, Chemical Physics Department, Universidad Complutense de Madrid, Plaza de las Ciencias, Ciudad Universitaria, Madrid 28040, Spain., Vega C; Faculty of Chemistry, Chemical Physics Department, Universidad Complutense de Madrid, Plaza de las Ciencias, Ciudad Universitaria, Madrid 28040, Spain. |
| Abstrakt: |
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. |
