ABSOLUTE HALF-CELL POTENTIAL - A SIMPLE DIRECT MEASUREMENT
ABSOLUTE HALF-CELL POTENTIAL - A SIMPLE DIRECT MEASUREMENT
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DOI：
10.1103/physreva.36.1396
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发表时间：
1987-08-01
影响因子：
2.9
通讯作者：
HANSEN, GJ
中科院分区：
文献类型：
--
作者：
HANSEN, WN;HANSEN, GJ
从简单的热力学角度讨论了绝对半电池势的概念，并将其定义为半电池反应的-ΔG/ne，将电子视为其他单个化学物种。在电子的标准参考状态被视为在无穷远处静止的自由电子的情况下，绝对半电池电势仅仅是半电池引线中的电子的费米能级。该电势可以简单地用开尔文探针通过确定相对于半电池引线的费米能级的电解质上的真空电势水平来测量。由于探头不能绝对确定电位，因此必须使用功函数已知的材料进行校准。使用该过程，我们获得标准氢半电池的E abs（SHE）= 4.456±0.025 eV，假设我们在校准中使用的Hg具有4.495 eV的功函数。
The concept of the absolute half-cell potential is discussed from a simple thermodynamic point of view and defined as-ΔG/ne for the half-cell reaction, treating the electron like other individual chemical species. With the standard reference state of the electron taken as the free electron at rest at infinity, the absolute half-cell potential is simply the Fermi level of the electrons in the half-cell lead wire. This potential can be simply measured with a Kelvin probe by determining the vacuum potential level over the electrolyte relative to the Fermi level of the half-cell lead. Since the probe cannot determine potentials absolutely, it must be calibrated using a material whose work function is known. Using this procedure we obtain for the standard hydrogen half-cell, E abs (SHE)= 4.456±0.025 eV, assuming our Hg as used in calibration has a work function of 4.495 eV.