Effect of Confinement on Freezing of CCl4 in Cylindrical Pores

Abstract

We report experimental and molecular simulation results on the freezing and melting of fluids confined within cylindrical pores. Dielectric relaxation spectroscopy was used to determine the experimental melting points of carbon tetrachloride confined within multi-walled carbon nanotubes. Molecular simulations in the grand canonical ensemble and free energy calculations were performed for the same system to determine the structure and thermodynamic stability of the confined phases, as well as the temperatures and the order of the phase transitions. Both simulations and experiments show evidence of a rich phase behavior in confinement, with a number of inhomogeneous phases that are stable over extended temperature ranges. Multiple transition temperatures both above and below the bulk melting point were obtained from experiments and simulations, with good agreement between both series of results.