Phase transition of SnCl2(H2O)x(D2O)2-x as studied by high resolution heat capacity measurement.

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概要

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• The previously published heat capacity data on Sncl<SUB>2</SUB>(H<SUB>2</SUB>O)<I><SUB>x</SUB></I>(D<SUB>2</SUB>O)<SUB>2−<I>x</I></SUB> (<I>x</I>=2.00, 1.97, 1.75, 1.50, 0.96, 0.50, 0.25, 0.03) were analyzed to derive anomalous contribution due to the phase transitions that occur between 218 and 235 K depending on the isotopic composition. The phase transition is of the first-order for <I>x</I>=2.00, 1.97, and 1.75. The entropy discontinuities at the transitions are (0.149±0.005), (0.152±0.005), and (0.133±0.010) J K<SUP>−1</SUP> mol<SUP>−1</SUP>, respectively, out of the total transition entropies of 3.98, 3.90, and 3.89 J K<SUP>−1</SUP> mol<SUP>−1</SUP>. The first-order transition does not occur for the other crystals for which the heat capacity anomaly is rounded. Apparent critical exponent α of the heat capacity was calculated for all of the crystals. They are in the range from 0.43 to 0.80 and have the same value below and above the transition temperature for each of the crystals in agreement with the spatial two dimensionality of the crystal structure. No evidence was found for crossing-over to the three dimensional ordering. Change of the transitional behavior with the isotopic composition was discussed in analogy with the liquid-vapor critical phenomenon. An argument based on the crystallographic symmetry of the actual crystal and the corresponding dimer lattice was advanced for this interpretation of the unusual isotope effect.

• 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

• MATSUO Takasuke

  Department of Chemistry and Microcalorimetry Research Center, Faculty of Science, Osaka University

• Tatsumi Masami

  Department of Chemistry, Faculty of Science, Osaka University

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