Origin of the enthalpy features of water in 1.8 nm pores of MCM-41 and the large Cp increase at 210 K

被引:27
作者
Johari, G. P. [1 ]
机构
[1] McMaster Univ, Dept Mat Sci & Engn, Hamilton, ON L8S 4L7, Canada
关键词
enthalpy; freezing; latent heat; liquid-liquid transformations; melting; nanoporous materials; silicon compounds; specific heat; water; NEUTRON-SCATTERING; SUPERCOOLED WATER; GLASS-TRANSITION; HEAT-CAPACITY; STRUCTURAL RELAXATION; ALPHA-GLASS; SILICA-GEL; BETA-GLASS; X-RAY; ICE;
D O I
10.1063/1.3103950
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
It is shown that exothermic and endothermic features of dH(m)/dt observed on heating rapidly precooled and slowly precooled states of water in 1.8 nm pores of MCM-41 and the unusually large increase in the specific heat in the 210-230 K range [M. Oguni, Y. Kanke, S. Namba, and AIP Conf, Proc. 982, 34 (2008)] are inconsistent with kinetic unfreezing of a disordered solid, or glass softening. The exotherm is attributable to the melt's gradual conversion to distorted icelike structures and the endotherm to the reverse process until their fractional amounts reach a reversible equilibrium on heating. The large increase in C-p,C-m with T is attributed to the latent heat, similar to that seen on premelting of fine grain crystals. The available calorimetric data on freezing and melting and the pore-size dependence of the features support this interpretation. The findings also put into question a conclusion from neutron scattering studies that in 1.8 nm pores water undergoes a structural and kinetic transition at similar to 225 K while remaining a liquid.
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页数:6
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