标准电极电势是可逆电极在标准状态及平衡态时的电势,也就是标准态时的平衡电势,记作、或,上标表示标准态。标准状态的溶质活度每公升1莫爾,气体压强10萬Pa,温度一般為298K。
虽然电池的电动势可以直接测定,但单一可逆电极的标准电极电势却只有相对值没有绝对值,而且随温度、浓度和压强而变。电极电势的基准是标准氢电极:标准状态的H⁺/H₂电极电势定为0V,即,其他电极电势的值在此基础上获得。当某半电池和标准氢电池电极相连时为负极,该半电池的半反应的标准电极电势为负值,且绝对值与电池电动势相等;若为正极则相反。这样求得的值称作还原电势,总反应的标准电极电势也就是两个半反应标准电极电势的差,Eo為正时反应自发。
任何温度下标准氢电极的标准电极电势值都为0,但其他电极电势值会受到温度影响。以Ni/NiO电极为例,它可以用作高温伪参比电极,电极电势在0至400°C大致符合以下公式:[1]
- ,T为温度
标准电极电势可以实验或热力学计算获得。,标准氢电极的反应自由能是零,水合氢离子和水合电子的标准生成自由能也是零,这样便可计算众多无法用实验测得的标准电极电势值(如氟气)。标准电极电势沒有加成性,要想求相加得到的第三反应的标准电极电势,还需要借助上述公式来求解。
标准电极电势不随半反应的方向和计量系数改变,但它受到浓度和反应物形态影响。非标态的电极电势值可以能斯特方程求得。标准电极电势值只是热力学数据,不可用于预测反应速率和其他动力学性质,而且它的值在水溶液体系中测定,不可用于其他溶剂或高温时的反应。
- 能斯特方程:
标准电极电势有很大的实用价值,可用来判断氧化剂与还原剂的相对强弱,判断氧化还原反应的方向,计算原电池的电动势、反应自由能、平衡常数,计算其他半反应的标准电极电势,等等。将半反应按电极电势由低到高排序,可以得到标准电极电势表,可十分简明判断氧还反应的方向。
標準電極電勢表
表中電極電勢以以下條件測得((s):固體;(l):液體;(g):氣體;(aq):水溶液;(Hg):汞齊):
单击頂栏箭咀可将数据按元素符号、反應物、產物或标准电极电势值排序。
参见
参考资料
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外部链接
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