The solvent extraction of uni- and bivalent metal picrates by dibenzo-24-crown-8.
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The overall extraction equilibrium constants (<I>K</I><SUB>ex</SUB>) for the 1:1:1 and 1:1:2 complexes of dibenzo-24-crown-8 (DB24C8) with several uni- and bivalent metal picrates between benzene and water have been determined at 25 °C. The <I>K</I><SUB>ex</SUB> sequences of the uni- and bivalent metal ions with DB24C8 are Tl<SUP>+</SUP>>Cs<SUP>+</SUP>>Ag<SUP>+</SUP>>Rb<SUP>+</SUP>>K<SUP>+</SUP>>Na<SUP>+</SUP>>>Li<SUP>+</SUP> and Ba<SUP>2+</SUP>>>Pb<SUP>2+</SUP>>>Sr<SUP>2+</SUP>>Ca<SUP>2+</SUP>, respectively. DB24C8 shows the highest selectivity for Ba<SUP>2+</SUP> among all the alkali and alkaline earth metal ions, but no selectivity for the alkali metal ions. The extractability of DB24C8 for the alkali metal ions is not sensitive to the ratio of the ionic size to the cavity size of DB24G8. The plots of log<I>K</I><SUB>ex</SUB> values vs. reciprocal crystal ionic radii of the alkali and alkaline earth metals give straight lines, indicating that these straight lines are related to Born's formula of solvation free energy.
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