Abstract

The complexation reactions between Mg2+,Ca2+,Sr2+ and Ba2+ metal cations with macrocyclic ligand, dicyclohexano-18-crown-6 (DCH18C6) were studied in methanol (MeOH)–water (H2O) binary mixtures at different temperatures using conductometric method . In all cases, DCH18C6 forms 1:1 complexes with these metal cations. The values of stability constants of complexes which were obtained from conductometric data show that the stability of complexes is affected by the nature and composition of the mixed solvents. While the variation of stability constants of DCH18C6-Sr 2+ and DCH18C6-Ba2+versus the composition of MeOH–H2O mixed solvents is monotonic, an anomalous behavior was observed for variations of stability constants of DCH18C6-Mg2+ and DCH18C6-Ca2+ versus the composition of the mixed solvents. The values of thermodynamic parameters (ΔH c °, ΔS c °) for complexation reactions were obtained from temperature dependence of formation constants of complexes using the van’t Hoff plots. The results show that in most cases, the complexation reactions are enthalpy stabilized but entropy destabilized and the values of thermodynamic parameters are influenced by the nature and composition of the mixed solvents. The obtained results show that the order of selectivity of DCH18C6 ligand for metal cations in different concentrations of methanol in MeOH–H2O binary system is: Ba2+>Sr2+>Ca2+> Mg2+.

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