Grüße chemweazle,
Zur Redoxelektrode mit pH-Wertabhängigkeit des Elektrodengleichgewichts
Dichromat-Cr(III)-Elektrode, diese kann nur im sauren Millieu arbeiten, da Dichromationen nur in saurer, wäßriger Lösung oxidieren können.
Schreibweise : Cr(3+) , Cr2O7(2-) |
14 H(+)(aq) + Cr2O7(2-)(aq) + 6 e(-)(Metall) ⇌ 2 Cr(3+)(aq) + (Metall, ( 6 + ) )
Für die Halbzelle, Redoxelektrode, Dichromat-Cr(III)-Elektrode
$$E_{Cr(III), Cr_{2}O_{7}^{2-}} = E_{Cr(III), Cr_{2}O_{7}^{2-}}^{0} + \frac{0,059V}{6}\cdot log_{10}\left[\dfrac{\left(\dfrac{c(H^{+})}{Cst.}\right)^{14}\cdot \red{\left(\dfrac{c(Cr_{2}O_{7}^{2-})}{Cst.}\right)}}{\green{\left(\dfrac{c(Cr^{3+})}{Cst.}\right)}}\right]$$
$$\left(\dfrac{c(H^{+})}{Cst.}\right)^{14} = \left(\dfrac{c(10^{-pH})}{Cst.}\right)^{14} = \left(\dfrac{c(10^{-14\cdot pH})}{Cst.}\right)$$
$$\red{\left(\dfrac{c(Cr_{2}O_{7}^{2-})}{Cst.}\right)} = \red{| c(Cr_{2}O_{7}^{2-} |}$$
$$\green{\left(\dfrac{c(Cr^{3+})}{Cst.}\right)} = \green{| c(Cr^{3+}) |}$$
$$E_{Cr(III), Cr_{2}O_{7}^{2-}} = E_{Cr(III), Cr_{2}O_{7}^{2-}}^{0} + \frac{0,059V}{6}\cdot (- 14pH )+ \frac{0,059V}{6}\cdot log_{10}\left[\dfrac{\red{\left(\dfrac{c(Cr_{2}O_{7}^{2-})}{Cst.}\right)}}{\green{\left(\dfrac{c(Cr^{3+})}{Cst.}\right)}}\right]$$
$$E_{Cr(III), Cr_{2}O_{7}^{2-}} = E_{Cr(III), Cr_{2}O_{7}^{2-}}^{0} + \frac{0,059V}{6}\cdot log_{10}\left[\dfrac{\red{| c(Cr_{2}O_{7}^{2-} |}}{\green{| c(Cr^{3+}) |}}\right] - \frac{0,059V\cdot 14}{6}\cdot pH$$
$$E_{Cr(III), Cr_{2}O_{7}^{2-}} = E_{Cr(III), Cr_{2}O_{7}^{2-}}^{0} + \frac{0,059V}{6}\cdot \left[log_{10}\left(\dfrac{\red{| c(Cr_{2}O_{7}^{2-} |}}{\green{| c(Cr^{3+}) |}}\right) - 14pH\right]$$
mit
$$E_{Cr(III), Cr_{2}O_{7}^{2-}}^{0} = 1,33V$$
$$E_{Cr(III), Cr_{2}O_{7}^{2-}} = E_{Cr(III), Cr_{2}O_{7}^{2-}}^{0} + \frac{0,059V}{6}\cdot \left[log_{10}\left(\dfrac{\red{0,05}}{\green{0,2}}\right) - 14\cdot 2\right]$$
$$\frac{0,05}{0,2} = \frac{5}{20} = \frac{1}{4}$$
$$log_{10}(1) - log_{10}(4) \approx 0 - 0,6021 = - 0,6021$$
$$E_{Cr(III), Cr_{2}O_{7}^{2-}} = 1,33V + \frac{0,059V}{6}\cdot \left[ - 0,621 - 28 \right]$$
$$E_{Cr(III), Cr_{2}O_{7}^{2-}} \approx + 1,33V + - 0,28V = +1,05V$$