Abstract
Polarographic studies of reduction of Ni(Ⅱ)-CN complex on Hg-electrode have indicated that $Ni(CN)_4^{2-}$ is reduced by two paths, via one electron process Ni(CN)42- + e [1]↔[2] Ni(CN)43- =(eq) Ni(CN)2- + 2CN- and via two electron process Ni(CN)42- + 2e [3]→ 1/2[Ni(CN)33-]2 + CN- of which reduction [1] must be faster than reduction [3]. At very dilute cyanide concentration (0.004 to 0.01 M) cathodic wave is practically responsible for reaction [1] and two cyanide ions appear to contribute to the reaction. As increasing cyanide ion concentration the rate of oxidation reaction [2] catalysed by Hg increases and reaction [1] and [2] approach to equilibrium. Therefore, reaction [3] represents the cathodic wave at high concentration of cyanide (above 0.2 M). This mechanism can also explain the fact that limiting current at $[CN^-]$ = 8 M is approximately twice of that at 0.004 M CN.
水銀滴下電極에 있어서 Ni(II)-CN complex의 還元反應은 두가지 經路를 밟고 있는데, 一電子還元일때는 Ni(CN)42- + e [1]↔[2] Ni(CN)43- =(eq) Ni(CN)2- + 2CN- 그리고 二電子還元일 때는 Ni(CN)42- + 2e [3]--> 1/2[Ni(CN)33-]2 + CN- 이다. 反應 [1]이 反應[3]에 比하여 빠르게 일어나고 있다. $CN^-$濃度가 묽을 때 (0.004∼0.01M)의 還元波는 反應[1]에 依해 나타나며 이때 $CN^-$ 두個가 關與하게 된다. $CN^-$ 濃度가 增加하면 反應[2]는 빨라져서 反應[1]과 [2]는 平衡狀態에 到達하게 된다. $CN^-$濃度 0.2M 以上에서는 反應[3]에 依한 二電子還元으로 電極反應을 하게 되는데 이 反應機構는 $CN^-$濃度 0.004M일 때보다 8M때의 限界電流値가 約 2倍가 되는 現象도 說明할 수 있게 된다.