Mechanism and Activation Parameters $({\Delta}H^{\neq},\;{\Delta}S^{\neq}$ and ${\Delta}V^{\neq})$ of Electron Transfer Reaction Between $Co^{II}CyDTA\;and\;Fe^{III}$CN Complex Ions

Co(II)-CyDTA와 Fe(III)-CN 착이온간의 전자이동반응에서 활성화파라미터 $({\Delta}H^{\neq},\;{\Delta}S^{\neq}$ 및 ${\Delta}V^{\neq})$ 와 반응메카니즘

The spectra of the $Co^{II}CyDTA$(CyDTA: cyclohexyldiaminetetraacetic acid) complex have been measured in aqueous solution of pH = 6-13.2. The red shift of the spectrum in the more basic solution was ascribed to the transformation of $CoCyDTA^{2-}$ into $CoCyDTA(OH)^{3-}$. The equilibrium constant, $K_{OH} = [CoCyDTA(OH)^{3-}]/[CoCyDTA^{2-}][OH^-]$ was $75M^{-1}$ at $40^{\circ}C$. The electron transfer reactions of $CoCyDTA^{2-}$ and $CoCyDTA(OH)^{3-}$ with $Fe(CN)_6^{3-}$ have been studied using spectrophotometric technique in the range of pH applied to the determination of equilibrium constant. The pseudo first-order rate constants observed ($k_{obs}$) were not changed upto pH = 10.8, but increased with increasing pH in the range of pH = $10.8{\sim}13.0$. The rate law reduced in the range of pH = 6-13 was $k_{obs} = (k_3[CoCyDTA^{2-}] + k_4[CoCyDTA(OH)^{3-}])/(1+K_1[CoCyDTA^{2-}])$. The rate constants of the reactions (3a) and (3b), $k_3$ and $k_4$ respectively have been determined to be 0.529 and $4.500M^{-1}sec^{-1}$ at $40^{\circ}C$. The activation entropies (147{\pm}1.1JK^{-1} mol^{-1}$ at pH = 10.8) and activation volumes $(6.25cm^3mol^{-1}, pH = 10.8)$ increased with increasing pH, while the activation enthalpy (12.44 ${\pm}$ 0.20 kcal/mole) was independent of pH. Using the pH effect on the rate constants, the activation entropies and the activation volumes, the mechanism of the electron transfer reaction for $Co^{II}-Fe^{III}$ system was discussed.

Co(II)-CyDTA 착물의 흡수스펙트럼을 pH = $6.0{\sim}13.2$의 수용액에서 측정하였다. 흡수에너지는 pH가 증가할수록 낮은 에너지로 이동하였고, 이 현상은 $CoCyDTA^{2-}$와 $CoCyDTA(OH)^{3-}$간의 평형상수 $K_{OH} = [CoCyDTA(OH)^{3-}]/[CoCyDTA^{2-}][OH^-]$로 설명할 수 있었고, 그 값은 $40^{\circ}C$에서 $75M^{-1}$이었다. Co(II)-CyDTA와 Fe(III)-CN 착이온간의 전자이동반응은 $K_{OH}$ 측정과 같은 용액조건에서 분광광도법을 이용하여 고찰하였다. 측정한 $k_{obs}$는 pH = 10.8까지는 거의 일정하였으나 pH > 10.8에서는 pH의 증가에 따라 증가하였다. pH = $6.0{\sim}13.0$에서 적용할 수 있는 속도법칙은 $k_{obs} = (k_3[CoCyDTA^{2-}] + k_4[CoCyDTA(OH)^{3-}])/(1+K_1[CoCyDTA^{2-}])$이었다. 반응 (3a)와 (3b)의 속도상수 $k_3$와 $k_4$는 $40^{\circ}C$에서 각각 $0.529M^{-1}sec^{-1}$와 $4.500M^{-1}sec^{-1}$이었다. 활성화엔트로피(147{\pm}1.1JK^{-1} mol^{-1}, pH = 10.8)$와 활성화체적$(6.25cm^3mol^{-1}, pH = 10.8)$은 pH가 증가할수록 증가하였지만, 활성화엔탈피$(12.44{\pm}0.20 kcal mol^{-1})$는 pH의 영향을 받지 않았다. 속도상수, 활성화엔트로피, 활성화체적에 대한 pH의 영향을 각각이용하여 Co(II)-Fe(III)의 전자이동 반응메카니즘을 논의하였다.