Low-temperature heat capacities of confined liquid benzene, implying the behavior of ordinary bulk liquids.
Isobaric heat capacities C p of benzene confined in silica MCM-41 mesopores with average diameters equal to and smaller than 2.9 nm were measured by precise adiabatic calorimetry. The confined benzene samples revealed no thermal anomaly due to crystallization/fusion and vitrified at low temperatures. The C p curves displayed a hump and a considerably quick decrease on the low-temperature side of the hump as the pore diameter increased. The enthalpy-relaxation effects observed on intermittent heating showed that the anomaly of the C p hump and quick decrease is not assigned to a glass transition. The bend in the temperature dependence of density reported previously was interpreted as corresponding to the quick decrease in C p . We concluded that the anomalous C p and density behaviors originated from the ordering/excitation in the configurational state, close to the ground state, of confined molecular aggregate and proposed a scenario that explains the general C p curves of ordinary bulk supercooled liquids in equilibrium at low temperatures below the glass-transition temperatures.
Research Center for Structural Thermodynamics, Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043, Japan.
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Nagoe
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Oguni
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Fujimori