含义Meaning
原电池的标准电动势等于正极(发生还原)与负极(发生氧化)标准还原电势之差。E > 0 的电池反应自发。
A galvanic cell’s standard EMF is the cathode’s standard reduction potential minus the anode’s; E > 0 means the cell reaction is spontaneous.
符号说明Symbols
| 符号Symbol | 含义 Meaning | 单位 Unit |
|---|---|---|
| \(E^\circ\) | 标准电极电势(相对标准氢电极 SHE)standard reduction potential vs SHE | V |
推导Derivation
电极电势只能相对测定,规定标准氢电极 \(E^\circ(\mathrm{H^+/H_2}) = 0\)。
Potentials are relative; the SHE is defined as 0 V.
电池电动势 = 右(正)极电势 − 左(负)极电势;两个半反应相加得电池反应。
EMF = right − left; adding half-reactions gives the cell reaction.
电势是强度量:半反应乘系数时 E° 不变(而 ΔG° 加倍)。
Potentials are intensive: scaling a half-reaction leaves E° unchanged.
适用条件与局限Assumptions & limitations
标准态(1 mol/L、1 bar、指定温度);非标准浓度用能斯特方程。
Standard states only; use the Nernst equation otherwise.
两电极电势相加减时若半反应电子数不同,不能直接相加求“第三个”电势(须经 ΔG° 换算,拉蒂默图)。
To combine half-reactions into a third, go through ΔG° (Latimer diagrams).
例题Worked example
丹尼尔电池 Zn|Zn²⁺||Cu²⁺|Cu:E° = 0.34 − (−0.76) = 1.10 V。
Daniell cell: E° = 0.34 − (−0.76) = 1.10 V.