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KMID : 1059519850290030239
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Journal of the Korean Chemical Society
1985 Volume.29 No. 3 p.239 ~ p.246
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Thermodynamic Properties for the Chemical Reactions of [Cu(dl-trans-[14]-diene)]2+ with S2O32-, SCN-, I- and NO2-
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Park Yu-Chul
Byun Jong-Chul
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Abstract
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The equilibria of chemical reaction between [Cu(dl-trans-[14]-diene)]2+ and Ln-(S2O32-, SCN-, I-, NO2-) ions were studied by the spectrophotometric method in the range of 15 to 35℃ and 1 to 1500bar. The equilibrium constants(K) for Ln- = S2O32-, SCN-, I- and NO2- ions at 25℃ and 1500bar were 3.0, 1.9, 0.6 and 0.5, respectively. The values of K decreased with increasing pressure and temperature. From the temperature effect on equlibrium constant, the thermodynamic parameters(△G°, △H°, △S°) of reaction were evaluated and the reactions of [Cu(dl-trans-[14]-diene)]2+ ion with S2O32-, SCN- and I- except NO2- ion were exothermic. The volume changes of reaction(△V) had positive values for all the used anions. The values of △V in cm3/mole for S2O32- ion at 1,500, 1,000 and 1,500bar were 26, 22, 19 and 16, and those for S2O32-, SCN-, I- and NO2- ions at atmospheric pressure 26, 30, 64 and 45, respectively. Bonding character between Cu(Ⅱ)-complex ion and Ln- was discussed by comparing both the equlibrium constants experimentally determined and those calculated according to Fuoss's ion-pair equation in case of S2O32- ion.
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