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Discussion on complexation reactions between dicyclohexyl-18-crown-6 (DCH18C6) with Na+, K+, Cs+, Rb+, and Tl+ metal cations in acetonitrile-water binary mixtures

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Abstract

The complex formation between Na+, K+, Cs+, Rb+ and Tl+ metal cations with macrocyclic ligand, dicyclohexyl-18-crown-6 (DCH18C6) was studied in acetonitrile-water (AN-H2O) binary systems at different temperatures using conductometric method. DCH18C6 forms 1:1 complexes with these metal cations. The stability constants of the complexes were obtained from fitting of molar conductivity curves using a computer program Genplot. The results show that the selectivity order of DCH18C6 for the metal cations in acetonitrile-water mixtures (AN = 25.3 and 50.4 mol %) is: Tl+ > K+ > Rb+ > Cs+ > Na+. A non-linear behaviour was observed between the log K f of the complexes versus the composition of the mixed solvent which it related to changes of acidity, basicity, polarity and also polarizability of AN-H2O mixtures with the composition of this binary solution. The values of standard enthalpy changes (ΔH 0s ) for complexation reactions were obtained from the slope of the van’t Hoff plots and the changes in the standard entropy (ΔS 0s ) were calculated from the relationship: ΔG 0s,298.15 = ΔH 0s − 298.15ΔS 0s . The obtained results show that in most cases, the complexes are enthalpy stabilized but entropy destabilized.

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Authors and Affiliations

  1. Department of Chemistry, Faculty of Sciences, Ferdowsi University of Mashhad, Mashhad, Iran

    M. H. Soorgi, G. H. Rounaghi & M. S. Kazemi

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  1. M. H. Soorgi
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  2. G. H. Rounaghi
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  3. M. S. Kazemi
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Correspondence to G. H. Rounaghi.

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Original Russian Text © M.H. Soorgi, G.H. Rounaghi, M.S. Kazemi, 2008, published in Zhurnal Obshchei Khimii, 2008, vol. 78, No. 10, pp. 1627–1632.

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Soorgi, M.H., Rounaghi, G.H. & Kazemi, M.S. Discussion on complexation reactions between dicyclohexyl-18-crown-6 (DCH18C6) with Na+, K+, Cs+, Rb+, and Tl+ metal cations in acetonitrile-water binary mixtures. Russ J Gen Chem 78, 1866–1871 (2008). https://doi.org/10.1134/S107036320810006X

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  • DOI: https://doi.org/10.1134/S107036320810006X

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