雙極電化學方案
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
E
o
{\displaystyle E^{o}}
、
E
0
{\displaystyle E^{0}}
或
E
⊖
{\displaystyle E^{\ominus }}
,上标
⊖
{\displaystyle \ominus }
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
ϕ
⊖
(
H
+
/
H
2
)
=
0
V
{\textstyle \phi ^{\ominus }(H^{+}/H_{2})=0V\,}
,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]
E
0
(
T
)
=
−
0.0003
T
+
0.1414
{\displaystyle E^{0}(T)=-0.0003T+0.1414\,}
,T为温度
标准电极电势可以实验或热力学 计算获得。
Δ
G
⊖
=
−
n
F
E
⊖
{\textstyle \Delta G^{\ominus }=-nFE^{\ominus }\,}
,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:
E
half-cell
=
E
0
−
R
T
n
F
ln
{
red
}
{
oxd
}
{\displaystyle E_{\text{half-cell}}=E^{0}-{\frac {RT}{nF}}\ln {\frac {\{{\text{red}}\}}{\{{\text{oxd}}\}}}}
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
^ R.W. Bosch, D.Feron, and J.P. Celis, "Electrochemistry in Light Water Reactors", CRC Press, 2007.
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^ 4.0 4.1 4.2 4.3 Bratsch, S. G. (1989). Journal of Physical Chemistry Reference Data Vol. 18, pp. 1–21. 引用错误:带有name属性“Bra”的<ref>
标签用不同内容定义了多次
^ 5.0 5.1 Vanýsek, Petr (2006). "Electrochemical Series," in Handbook of Chemistry and Physics: 87th Edition (页面存档备份 ,存于互联网档案馆 ) (Chemical Rubber Company). 引用错误:带有name属性“Van”的<ref>
标签用不同内容定义了多次
^ 6.00 6.01 6.02 6.03 6.04 6.05 6.06 6.07 6.08 6.09 6.10 6.11 6.12 6.13 6.14 6.15 6.16 6.17 6.18 6.19 6.20 6.21 6.22 6.23 6.24 6.25 6.26 6.27 6.28 6.29 6.30 Vanýsek, Petr (2007). “Electrochemical Series” (页面存档备份 ,存于互联网档案馆 ), in Handbook of Chemistry and Physics: 88th Edition (页面存档备份 ,存于互联网档案馆 ) (Chemical Rubber Company). 引用错误:带有name属性“van88”的<ref>
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^ 11.0 11.1 11.2 Ca Sr Ba一價[11] 與兩價間的標準電極電勢 正好有規律關係,因此可以估計近似值
^ 12.00 12.01 12.02 12.03 12.04 12.05 12.06 12.07 12.08 12.09 12.10 12.11 12.12 12.13 12.14 12.15 12.16 12.17 12.18 12.19 12.20 12.21 12.22 12.23 12.24 12.25 12.26 12.27 12.28 12.29 12.30 12.31 12.32 12.33 12.34 Standard Redox Potential Table . [2012-01-14 ] . (原始内容存档 于2021-02-06).
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^ Greenwood and Earnshaw, p. 1263
^ Standard Redox Potential Table . [2012-01-14 ] . (原始内容存档 于2021-02-06).
^ Standard Redox Potential Table . [2012-01-14 ] . (原始内容存档 于2021-02-06).
^ Vanýsek, Petr (2007). “Electrochemical Series” (页面存档备份 ,存于互联网档案馆 ), in Handbook of Chemistry and Physics: 88th Edition (页面存档备份 ,存于互联网档案馆 ) (Chemical Rubber Company).
^ 引用错误:没有为名为van92
的参考文献提供内容
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^ Lide, David R. (编), CRC Handbook of Chemistry and Physics 87th, Boca Raton, FL: CRC Press, 2006, ISBN 0-8493-0487-3
^ Lide, David R. (编), CRC Handbook of Chemistry and Physics 87th, Boca Raton, FL: CRC Press, 2006, ISBN 0-8493-0487-3
^ Lide, David R. (编), CRC Handbook of Chemistry and Physics 87th, Boca Raton, FL: CRC Press, 2006, ISBN 0-8493-0487-3
^ Lide, David R. (编), CRC Handbook of Chemistry and Physics 87th, Boca Raton, FL: CRC Press, 2006, ISBN 0-8493-0487-3
^ 24.0 24.1 Lide, David R. (编), CRC Handbook of Chemistry and Physics 87th, Boca Raton, FL: CRC Press, 2006, ISBN 0-8493-0487-3
^ Ti Zr Hf 的標準電極電勢 變化較規律,因此可估計 Rf的標準電極電勢
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^ 31.0 31.1 由−0.454和(2×−0.499+−0.508)÷3=−0.502推算出。
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