Scale effects in the latent heat of melting in nanopores

J Chem Phys. 2013 Jul 28;139(4):044701. doi: 10.1063/1.4813004.

Abstract

The curvature of a liquid vapor interface has long been known to change the equilibrium vapor pressure. It has also been shown that a capillary structure will affect the temperature at which both freezing and vaporization of a substance will occur. However, describing interfacial effects on the latent heat of a phase change has proven more difficult. Here, we present a classical thermodynamic model for how the latent heat of melting changes as the size of the particles undergoing the transition decreases. The scale dependence for the surface tension is taken into consideration using a Tolman length correction. The resulting model is tested by fitting to published experimental data for the latent heat of melting for benzene, heptane, naphthalene, and water contained in nano-porous glass. In all cases the model fits the data with a R(2) ≥ 0.94.