A conductance study of the complexation reaction of dibenzo-24-crown-8 with alkali metal ions in propylene carbonate and methanol.
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概要
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The formation constants (<I>K</I><SUB>ML<SUP>+</SUP></SUB>) for 1: 1 complexes of dibenzo-24-crown-8 (DB24C8) with alkali metal ions (Na<SUP>+</SUP>, K<SUP>+</SUP>, Rb<SUP>+</SUP>, and Cs<SUP>+</SUP>) in propylene carbonate (PC) and methanol have been determined conductometrically at different temperatures in order to obtain the values of the enthalpy (Δ<I>H</I>) and entropy changes (Δ<I>S</I>). The complexation reactions between DB24C8 and the alkali metal ions in PC and methanol are all exothermic, and the Δ<I>S</I> values of these systems are all negative. In the case of the PC system, there is no considerable difference in Δ<I>S</I> among the alkali metal ions (Na<SUP>+</SUP>, K<SUP>+</SUP>, Rb<SUP>+</SUP>, and Cs<SUP>+</SUP>); thus, the <I>K</I><SUB>ML<SUP>+</SUP></SUB> sequences depend entirely on the −Δ<I>H</I> sequences. Since, in methanol, the −Δ<I>H</I> and −Δ<I>S</I> values for K<SUP>+</SUP> are nearly equal to those for Cs<SUP>+</SUP>, and since the largest −Δ<I>H</I> value for Rb<SUP>+</SUP> is balanced by the largest −Δ<I>S</I> value, DB24C8 shows no selectivity for the alkali metal ions (K<SUP>+</SUP>, Rb<SUP>+</SUP>, and Cs<SUP>+</SUP>) in methanol.
- 公益社団法人 日本化学会の論文
著者
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Takeda Yasuyuki
Department Of Chemistry Faculty Of Science Chiba University
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Yano Hisao
Department of Chemistry, Faculty of Science, Chiba University
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