Determination of the oxygen and hydrogen overvoltage in concentrated alkali hydroxide solutions
Determination of the oxygen and hydrogen overvoltage in concentrated alkali hydroxide solutions
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DOI：
10.1016/0360-3199(85)90062-x
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发表时间：
1985
影响因子：
7.2
通讯作者：
J. Balej
中科院分区：
文献类型：
--
作者：
J. Balej
电解水分解近年来变得越来越重要，因为它有望实现经济生产，并且不会对氢作为化学物质产生不利的环境影响，特别是大规模地作为拟在不久的将来引入的新型能源系统的能量载体。氢和氧过电压的可靠测量对于碱性水电解系统的开发具有重要意义。本文根据相关热力学参数的最新值，通过使用特别合适的 Hg/HgO/OH− 以及可逆氢参比电极，在温度范围 20–200°C、总压力范围 1–200 bar、浓度范围 0–18mKOH 或 0–25mNaOH 下，推导出测量氧和氢过电压的精确方程。在 25 和 75°C 和大气压下，对于 1–17.6mNaOH 和 6–12mKOH，电池 Hg/HgO/NaOH（或 KOH）(m)/H2 的平衡电位差的理论计算值和实验测量值之间非常一致。还推导了在上述温度、压力和碱金属氢氧化物浓度范围内的标准条件和实际条件下水电解的平衡电压的方程。
Electrolytic water splitting has gained importance in recent years because of its promise of economic production without adversive environmental impact of hydrogen as a chemical, and particularly on a large scale, as an energy carrier for novel energy systems proposed for introduction in the near future. Reliable measurements of hydrogen and oxygen overvoltages are of key significance in the development of alkaline water electrolysis systems. In this paper, on the basis of the most recent values of the relevant thermodynamic parameters, precise equations were derived for measuring oxygen and hydrogen overvoltages by using the particularly suitable Hg/HgO/OH−as well as reversible hydrogen reference electrodes in the temperature range 20–200°C, overall pressure range 1–200 bar, and concentration range 0–18mKOH or 0–25mNaOH. Very good agreement was found between the theoretically computed and experimentally measured values of the equilibrium potential difference of the cell Hg/HgO/NaOH (or KOH) (m)/H2for 1–17.6mNaOH and 6–12mKOH at 25 and 75°C and at atmospheric pressure. Equations were also derived for the equilibrium voltage of water electrolysis under standard and actual conditions in the temperature, pressure and alkali hydroxide concentration ranges mentioned above.