Calorimetric Study of the Glassy State. VI. Phase Changes in Crystalline and Glassy-Crystalline 2,3-Dimethylbutane

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概要

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• 2,3-Dimethylbutane has two crystalline phases, high temperature form (crystal-I) and low temperature form (crystal-II). On account of the supercooling effect of crystal-I, its <I>glassy crystalline</I> state (non-equilibrium frozen-in state) is established below <I>T<SUB>g</SUB></I> (76 K) by rapid cooling. The heat capacities for various phases were determined from 13 to 300 K from principal interest in the thermodynamic properties of the glassy crystal. The transition temperature from crystal-II to crystal-I and melting point were determined to be 136.02 K and 145.05 K, respectively. The heats of transition and of fusion were determined to be 6427 J mol<SUP>−1</SUP> and 788 J mol<SUP>−1</SUP>, respectively. From these data, the residual entropy and <I>T</I><SUB>2</SUB> temperature were determined to be 7.4 JK<SUP>−1</SUP> mol<SUP>−1</SUP> and 65 K, respectively. We also calculated the ratio of <I>T<SUB>g</SUB></I> to <I>T</I><SUB>2</SUB> for several glassy crystals known hitherto, which amounts to 1.15–1.20. The stabilization effect was studied by the measurement of the change of the configurational enthalpy in the glassy crystalline state. Also, we discovered a new meta-stable intermediate phase (crystal-III) in the course of irreversible transition from the supercooled crystal-I to crystal-II. The thermal properties of this phase were also studied and its residual entropy was determined to be 2.7 JK<SUP>−1</SUP> mol<SUP>−1</SUP>.

• 公益社団法人 日本化学会の論文

著者

• Seki Syuzo

  Department Of Chemistry Faculity Of Science Osaka University

• Suga Hiroshi

  Department Of Chemistry Faculty Of Science Osaka University

• Adachi Keiichiro

  Department of Chemistry, Faculty of Science, Osaka University

• Suga Hiroshi

  Department of Chemistry and Chemical Thermodynamics Laboratory, Faculty of Science, Osaka University

• Seki Syûzô

  Department of Chemistry and Chemical Thermodynamics Laboratory, Faculty of Science, Osaka University

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