ELECTROCHEMICAL POLARIZATION .1. A THEORETICAL ANALYSIS OF THE SHAPE OF POLARIZATION CURVES
ELECTROCHEMICAL POLARIZATION .1. A THEORETICAL ANALYSIS OF THE SHAPE OF POLARIZATION CURVES
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DOI：
10.1149/1.2428496
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发表时间：
1957-01-01
影响因子：
3.9
通讯作者：
GEARY, AL
中科院分区：
文献类型：
--
作者：
STERN, M;GEARY, AL
在低过电压值下，非腐蚀电极的塔菲尔行为偏差主要是由于氧化还原系统的反向反应，以及在高过电压下对浓度和/或电阻极化的影响。这进一步表明，通过几个实验点放置直线的做法是极其危险的，而不加区别地引入“断裂”则与所描述的电极动力学相反。描述了由腐蚀电极引起的进一步的复杂性。在这种情况下，必须考虑形成腐蚀对的两个氧化还原系统的正反反应。这种腐蚀金属的局部极化图的表示比以前文献中使用的更基本，从而提供了影响腐蚀速度和极化曲线形状的各种因素的更清晰的图景。通过对腐蚀电极的处理类似于对非腐蚀电极的处理，描述了腐蚀电极的电位与外加电流的线性关系区域。推导了该线性区域的斜率与腐蚀速率和塔菲尔斜率之间的关系式。这一关系为腐蚀金属的电化学研究提供了一种重要的新的实验方法，因为在某些情况下，干扰反应阻碍了在较高电流密度下测定T~FEL斜率。极化测量是研究各种电化学现象的重要研究工具。这些测量结果适合于研究腐蚀现象和金属沉积的反应机理和动力学。尽管它们具有广泛的适用性和广泛的用途，但在偏振测量的解释中仍然存在相当大的不确定性。一些不确定的因素包括正确的标绘方法
At low overvoltage values, deviations from Tafel behavior for a noncorroding electrode are due primarily to the reverse reaction of the oxidation-reduction system, and at high overvoltages to concentration and/or resistance polarization. It is shown further that the practice of placing straight lines through a few experimental points is extremely hazardous, while the indiscriminate introduction of" breaks" is contrary to the electrode kinetics described. Further complexities arising from a corroding electrode are described. In this instance, the forward and reverse reactions of both of the oxidation-reduction systems forming the corrosion couple must be considered. This representation of the local polarization diagram of a corroding metal is more fundamental than that used previously in the literature, and thus provides a clearer picture of the various factors which affect the corrosion rate and the shape of polarization curves. A region of linear dependence of potential on applied current is described for a corroding electrode by treating it in a manner analogous to that for a noncorroding electrode. An equation is derived relating the slope of this linear region to the corrosion rate and Tafel slopes. This relation provides an important new experimental approach to the study of the electrochemistry of corroding metals since, in some instances, interfering reactions prevent determination of T~ fel slopes at higher current densities.Polarization measurements are an important research tool in investigations of a variety of electrochemical phenomena. Such measurements pernfit studies of the reaction mechanism and the kinetics of corrosion phenomena and metal deposition. In spite of their wide applicability and extensive use, considerable uncertainty in the interpretation of polarization measurements still exists. Some of the uncertainties include the proper method of plotting