A simple AC calorimeter for specific heat measurement of liquids confined in porous materials: A study of hydrated Vycor

Abstract : Nanometric confinement of fluids in porous media is a classical way to stabilize metastable states. Calorimetric studies give insight on the behavior of confined liquids compared to bulk liquids. We have developed and built a simple quasi-adiabatic AC calorimeter for heat capacity measurement of confined liquids in porous media in a temperature range between 150 K and 360 K. Taking the fully hydrated porous medium as a reference, we address the thermal behavior of water as a monolayer on the surface of a porous silica glass (Vycor). For temperature ranging between 160 K and 325 K, this interfacial water shows a surprisingly large heat capacity. We describe the interfacial Hbond network in the framework of a mean field percolation model, to show that at 160 K interfacial water experiences a transformation from low density amorphous ice to a heterogeneous system where transient low and high density water patches coexist. The fraction of each species is controlled by the temperature. We identify the large entropy of the interfacial water molecules as the cause of this behaviour.