Incommensurate phase transitions and anomalous lattice heat capacities of biphenyl.
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概要
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Heat capacities of crystalline biphenyl were measured between 3 and 300 K by adiabatic calorimetry and some thermodynamic functions including the calorimetric standard entropy were tabulated. Thermodynamic properties of the successive phase transitions were determined; for the twist transition at (40.4±0.2) K, Δ<SUB>trs</SUB><I>H</I>=(5.02±0.08) J·mol<SUP>−1</SUP> and Δ<SUB>trs</SUB><I>S</I>=(0.129±0.003) J·K<SUP>−1</SUP>·mol<SUP>−1</SUP>, and for the lock-in transition at (16.8±0.1) K, Δ<SUB>trs</SUB><I>H</I>=(0.15±0.02) J·mol<SUP>−1</SUP> and Δ<SUB>trs</SUB><I>S</I>=(0.009±0.001) J·K<SUP>−1</SUP>·mol<SUP>−1</SUP>. Anomalously large heat capacities at low temperatures were analyzed based on lattice dynamics calculation, and the crossover of the low temperature heat capacities of biphenyl and <I>p</I>-terphenyl was attributed to the greater activity of the twisting mode in biphenyl. The relation of the bond flexibility to the incommensurability is discussed through the comparison of the low temperature heat capacities of biphenyl, <I>p</I>-terphenyl, and 4,4′-difluorobiphenyl.
- 公益社団法人 日本化学会の論文
著者
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Saito Kazuya
Department Of Aeronautics And Astronautics Graduate School Kyoto University
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Chihara Hideaki
Department Of Chemistr Faculty Of Science Osaka University
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Atake Tooru
Department of Chemistry and Chemical Thermodynamics Laboratory, Faculty of Science, Osaka University
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Saito Kazuya
Department of Chemistry and Chemical Thermodynamics Laboratory, Faculty of Science, Osaka University
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