NDLI: Thermodynamic behavior of complexation process between dibenzo-18-crown-6 and K$^{+}$, Ag$^{+}$, NH4+, and Hg$^{2+}$ cations in ethylacetate-dimethylformamide binary media

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Thermodynamic behavior of complexation process between dibenzo-18-crown-6 and K$^{+}$, Ag$^{+}$, NH4+, and Hg$^{2+}$ cations in ethylacetate-dimethylformamide binary media

Content Provider	Springer Nature Link
Author	Rounaghi, G. H. Zavar, M. H. Mohammad Zadeh Kakhki, R.
Copyright Year	2008
Abstract	The complexation reactions between K$^{+}$, Ag$^{+}$, NH4+, and Hg$^{2+}$ cations and the macrocyclic ligand, dibenzo-18-crown-6 (DB18C6), were studied in ethylacetate (EtOAc)-dimethylformamide (DMF) binary mixtures at different temperatures using the conductometric method. The conductance data show that the stochiometry of all the complexes is 1:1. A non-linear behavior was observed for the variation of log K $_{f}$ of the complexes versus the composition of binary mixed solvents, which was discussed in terms of heteroselective solvation and solvent-solvent interactions in binary solutions. It was found that the stability order of the complexes changes with changing the composition of the mixed solvents. The sequence of stabilities for the K$^{+}$, Ag$^{+}$, NH4+, and Hg$^{2+}$ complexes with DB18C6 in EtOAc-DMF binary solutions (mol. % DMF 25.0) and (mol. % DMF 50.0) at 25°C is (DB18C6-Ag)$^{+}$ > (DB18C6-K)$^{+}$ > (DB18C6-Hg)$^{2+}$ > (DB18C6-NH$_{4}$)$^{+}$, but in the cases of pure DMF and a binary solution of EtOAc-DMF (mol. % DMF 75.0) is (DB18C6-K)$^{+}$ > (DB18C6-Hg)$^{2+}$ > (DB18C6-Ag)$^{+}$ ≈ (DB18C6-NH$_{4}$)$^{+}$. The values of thermodynamic quantities (ΔH co, ΔS co) for these complexation reactions have been determined from the temperature dependence of the stability constants, and the results show that the thermodynamics of the complexation reactions is affected by the nature and composition of the mixed solvents and, in all cases, positive values of ΔS co characterize the formation of these complexes. In addition, the experimental results show that the values of entropies for the complexation reactions between K$^{+}$, Ag$^{+}$, NH4+, and Hg$^{2+}$ cations and DB18C6 in EtOAc-DMF binary solutions do not change monotonically with the solvent composition.
Starting Page	167
Ending Page	171
Page Count	5
File Format	PDF
ISSN	10703284
Journal	Russian Journal of Coordination Chemistry
Volume Number	34
Issue Number	3
e-ISSN	16083318
Language	English
Publisher	SP MAIK Nauka/Interperiodica
Publisher Date	2011-01-19
Publisher Place	Dordrecht
Access Restriction	One Nation One Subscription (ONOS)
Subject Keyword	Inorganic Chemistry Physical Chemistry
Content Type	Text
Resource Type	Article
Subject	Chemistry Chemical Engineering

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