초록
Nickel(Ⅱ)-8-hydroxyquinolinate의 용매추출에 대한 반응속도와 메카니즘을 분광광도법으로 연구하였다. 유기상 chloroform에 있는 8-hydroxyquinoline(HOx) 농도와 물층의 pH값을 변화시켜 가면서 흡광도를 측정하였으며, 흡광도 데이터를 해석하여 반응속도가 oxine농도에 대하여는 1차, [$H^+$]에 대하여는 -1차임을 알 수 있었다. 따라서 추출 반응의 속도결정단계는 1 : 1 금속킬레이트인 $NiOx^+$의 생성단계이며, 속도식은 다음과 같다. -d[$Ni^{2+}$]/dt = k[Ni$^{2+}$][Ox$^-$]=k'[Ni$^{2+}$][HOx]$_0$/[H$^+$]. 이 식의 k'값은 log [Ni$^{2+}$]$_0$/[Ni$^{2+}$]$_t$와 시간을 도시한 기울기로부터 구하였으며, 속도상수 k값은 k' = k ${\times}$ K$_{HOx}$ / K$_{D,HOx}$를 써서 계산하였다. 온도에 따른 속도상수의 변화로부터 계산한 활성화에너지 $E_a$ = 6.26 kcal/mol이었고, 활성화 파라미터인 ${\Delta}$G$^{\neq}_{298}$ = 6.59 kcal/mol, ${\Delta}$H$^{\neq}_{298}$ = 5.67 kcal/mol, ${\Delta}$S$^{\neq}_{298}$8 = -3.09 eu/mol이었다.
Kinetics and mechanism on the solvent extraction of nickel(Ⅱ) with 8-hydroxyquinoline (HOx) was studied spectrophotometrically. Absorbance variation was measured by changing the 8-hydroxyquinoline concentration in the chloroform organic phase and the pH values in the aquous phase. By analyzing absorbance data the reaction rate was found to be the first order for 8-hydroxyquinoline concentration and the inverse first one for [H$^+$]. Therefore the rate determining step of the extraction reaction is the formation of the one-to-one metal chelate NiOx$^+$ and the rate equation is as follows; -d[Ni$^{2+}$]/dt = k[Ni$^{2+}$][Ox$^-$] = k'[Ni$^{2+}$][HOx]$_0$/[H$^+$]. The value of k' was evaluated from the slope of plot of log [Ni$^{2+}$]$_0$/[Ni$^{2+}$]$_t$ versus time and the rate constant k was calculated according to the equation k' = k ${\times}$ K$_{HOx}$ / K$_{D,HOx}$. From the temperature dependence of the extraction rate, the activation energy E$_a$ = 6.26 kcal/mol is calculated, and activation parameters, ${\Delta}$G$^{\neq}_{298}$ = 6.59 kcal/mol, ${\Delta}$H$^{\neq}_{298}$ = 5.68 kcal/mol, ${\Delta}$S$^{\neq}_{298}$ = -3.09 eu/mol are estimated.