A conductance study of alkali metal ion-benzo-15-crown-5 complexes in propylene carbonate.
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The formation constants (<I>K</I><SUB>ML<SUP>+</SUP></SUB>) for 1:1 complexes of benzo-15-crown-5 (B15C5) with alkali metal ions at 25 °C, and the enthalpy (Δ<I>H</I>) and entropy changes (Δ<I>S</I>) of the K<SUP>+</SUP>–B15C5 complex in propylene carbonate (PC) have been determined conductometrically. The <I>K</I><SUB>ML<SUP>+</SUP></SUB> series of B15C5 for the alkali metal ions are given in the order Na<SUP>+</SUP>>Li<SUP>+</SUP>>K<SUP>+</SUP>>Rb<SUP>+</SUP>>Cs<SUP>+</SUP>. The selectivity tendency of B15C5 for the alkali metal ions is consistent with the size-fit concept, however, B15C5 shows poor selectivity. Both the Δ<I>H</I> and Δ<I>S</I> values for the complexation reaction of B15C5 with K<SUP>+</SUP> are negative. In the cases of Na<SUP>+</SUP>, K<SUP>+</SUP>, Rb<SUP>+</SUP>, and Cs<SUP>+</SUP>, the size of the moving entity in PC is larger for the B15C5 complex than for the corresponding alkali metal ion, while, in the case of Li<SUP>+</SUP>, that is completely the reverse.
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