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- W1976482102 abstract "The extraction equilibrium of the hydronium-uranium(VI)-dicyclohexano-24-crown-8 complex was carried out in the crown ether1,2-dichloroethaneHCl aqueous solution system at different temperatures. The extraction complex has the overall composition (L)2·(H3O+·χH2O)2·UO2Cl42− (L = dicyclohexano-24-crown-8). The values of the extraction equilibrium constants (Kex) increase steadily with a decrease in temperature: 13.5 (298 K), 7.96 (301 K), 4.20 (303 K) and 2.07 (305 K). A plot of log Kex against 1/T shows a straight line. The value of the enthalpy change, ΔH°, was calculated from the slope and equals −212 kJ mol−1. The value of the entropy change, ΔS°, was calculated from ΔH° and Kex and equals −690 J K−1 mol−1, whereas ΔG° = −6.45 kJ mol−1. Comparing these thermodynamic parameters with those of the dicyclohexano-18-crown-6 isomer A [1] (ΔS° = −314 J K−1 mol−1, ΔH° = −101 kJ mol−1 and ΔG° = −8.37 kJ mol−1), it can be seen that ΔH° and ΔS° are more negative for the former than for the latter, and both are enthalpy-stabilized complexes. The molecular structure of the complex has the feature that there are two H5O2+ ions in it, in contrast to the H3O+ ions in the dicyclohexano-18-crown-6 isomer A complex [1]. Each of the H5O2+ ions is held in the crown ether cavity by four hydrogen bonds. The H5O2+ ion has a central bond. The uranium atom forms UO2Cl42− as a counterion away from the crown ether. The formation of this complex is in good agreement with more negative entropy change and less negative free energy change, as mentioned above." @default.
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- W1976482102 date "1988-09-01" @default.
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- W1976482102 title "Thermodynamics and coordination characteristics of the hydronium-uranium(VI)-dicyclohexano-24-crown-8 extraction complex" @default.
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- W1976482102 doi "https://doi.org/10.1016/s0020-1693(00)90582-6" @default.
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