Abstract
Thermodynamics of complexation of cesium cation by dibenzo-24-crown-8 was studied in three binary solvent mixtures: acetonitrile-nitromethane (AN/NM),N,N-dimethylformamide-nitromethane (DMF/NM) and acetonitrile-propylene carbonate (AN/PC) using the133Cs-NMR technique. In all cases the variation of the formation constant,K f, with the solvent composition was monotonic:K f increased as the mole-% of the solvent of low donicity was increased. The temperature dependence ofK f indicated that the complexes are generally enthalpy stabilized, but entropy destabilized. The enthalpy and entropy of complexation reactions are quite sensitive to the solvent composition. However, their variation with solvent composition was not monotonic but showed maxima or minima at the isosolvation points of the cation or the complexed cation. In all cases an enthalpy-entropy compensating effect was observed.
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Steffens, J.E., Khazaeli, S. Thermodynamics of cesium cation complexation with dibenzo-24-crown-8 in mixed nonaqueous solvents. J Incl Phenom Macrocycl Chem 22, 171–186 (1995). https://doi.org/10.1007/BF00707081
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DOI: https://doi.org/10.1007/BF00707081