Calorimetric Study of Glassy State. IX. Thermodynamic Properties of Stannous Chloride Dihydrate and Dideuterate Crystals : Appendix: High Temperature Entropy Calculation
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The heat capacity of SnCl<SUB>2</SUB>·2H<SUB>2</SUB>O and SnCl<SUB>2</SUB>·2D<SUB>2</SUB>O crystals, substances with layer structure, was measured from 13 to 300 K. Anomalies due to ordering of the hydrogen (deuterium) position were observed at <I>T</I><SUB>C</SUB>(H<SUB>2</SUB>O)=217.94 K and at <I>T</I><SUB>c</SUB>(D<SUB>2</SUB>O)=234.47±0.05 K. The total entropy change of the transition was estimated to be 4.6 J K<SUP>−1</SUP> mol<SUP>−1</SUP> for both compounds. An exact calculation of the high temperature entropy based on the two-dimensional lattice model gave 3.13 J K<SUP>−1</SUP> mol<SUP>−1</SUP>. The critical indices α<SUB>±</SUB> of the divergent heat capacity anomalies are as follows: α<SUB>+</SUB>(H<SUB>2</SUB>O)=0.53, α<SUB>−</SUB>H<SUB>2</SUB>O)=0.48, α<SUB>+</SUB>(D<SUB>2</SUB>O)=0.57, α<SUB>−</SUB>(D<SUB>2</SUB>O)=0.54. Another heat capacity anomaly was found at 140–160 K where the heat capacity values depended on the thermal history of the specimen. The enthalpy relaxation observed at the temperature region was analysed by use of the first-order rate equation, giving the activation enthalpies <I>ΔH</I><SUB>a</SUB>(H<SUB>2</SUB>O)=49.9 kJ mol<SUP>−1</SUP> and <I>ΔH</I><SUB>a</SUB>(D<SUB>2</SUB>O)=49.8 kJ mol<SUP>−1</SUP>. The concept of long-range-ordered glassy state was introduced for description of the non-equilibrium state of the present substances below 140 K. A general consideration of the relation between molecular relaxation and phase change in terms of the Deborah number is presented.
著者
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Oguni Masaharu
Department of Chemistry and Chemical Thermodynamics Laboratory, Faculty of Science, Osaka University
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Matsuo Takasuke
Department of Chemistry and Chemical Thermodynamics Laboratory, Faculty of Science, Osaka University
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Nagle Johan
Department of Physics, Carnegie-Mellon University
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Suga Hiroshi
Department of Chemistry and Chemical Thermodynamics Laboratory, Faculty of Science, Osaka University
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