Abstract

Heat capacity of controlled amounts of water in Vycor's 2 nm radius pores has been determined in real time during the course of water's isothermal nanoconfinement from bulk state at 358 K, by using temperature-modulated calorimetry. As water transfers from bulk to nanopores via the vapor phase, its heat capacity per molecule increases asymptotically toward a limiting value of 1.4 times the heat capacity of bulk water for 1.8 wt % water in Vycor and 1.04 times for 10.0 wt %. The observations indicate that vibrational and configurational contributions to the heat capacity are highest when the amount of water is insufficient to completely cover the pore wall, and they decrease as more water is present in the nanopores and water clusters form. The heat capacity of water in completely filled nanopores approaches the value for bulk water, thus indicating that the heat capacity varies with the water molecules' position in the nanopores.

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