Thermodynamic Properties for the Chemical Reactions of [Cu(dl-trans-[14]-diene)]2+ with S2O32-, SCN-, I- and NO2- 


Vol. 29,  No. 3, pp. 239-246, Jun.  1985


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  Abstract

[Cu(dl-trans-[14]-diene)]2+ 착이온과 음이온(Ln = S2O32-, SCN-, I-, NO2-)사이의 화학평형 관계를 온도 15 ~ 35℃, 압력 1 ~ 1500bar 범위에서 분광광도법으로 연구하였다. S2O32-, SCN-, I-, NO2-일때 평형상수 K는 25℃, 1500bar에서 각각 3.0, 1.9, 0.6 및 0.5이었다. K값은 온도와 압력이 증가함에 따라 감소하였다. K에 대한 온도 영향으로 부터 열역학적 파라메터(△G°, △H°, △S°)를 계산하였으며, 이 결과 NO2-이온을 제외한 다른 이온(S2O32-, SCN-, I-)에서는 모두 발열반응으로 나타났다. K에 대한 압력 영향에서 얻은 반응체적변화(△V)는 각 음이온에서 모두 양의 값이었다. S2O32- 이온일 때 1,500, 1,000 및 1,500bar에서의 △V(cm3/mole)는 각각 26,22,19 및 16이었고, 상압에서 S2O32-, SCN-, I- 및 NO2-이온일 때 △V(cm3/mole)는 각각 26, 30, 64 및 45이었다. S2O32-이온인 경우 Fuoss식에 의하여 계산한 평형상수와 실험치를 비교하여 Cu(Ⅱ) 착이온과 Ln-간의 결합성을 고찰하였다. 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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  Cite this article

[IEEE Style]

Y. Park and J. Byun, "Thermodynamic Properties for the Chemical Reactions of [Cu(dl-trans-[14]-diene)]2+ with S2O32-, SCN-, I- and NO2-," Journal of the Korean Chemical Society, vol. 29, no. 3, pp. 239-246, 1985. DOI: .

[ACM Style]

Yu-Chul Park and Jong-Chul Byun. 1985. Thermodynamic Properties for the Chemical Reactions of [Cu(dl-trans-[14]-diene)]2+ with S2O32-, SCN-, I- and NO2-. Journal of the Korean Chemical Society, 29, 3, (1985), 239-246. DOI: .

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