It is known that the kinetics of redox reactions occurring on the surfaces of passive metals depend upon the properties of the passive film, ostensibly due to quantum mechanical tunnelling (QMT) of electrons and holes between the metal and the redox couple at the barrier layer/solution (bl/s) interface. In this paper, the tunnelling probability is used to inter-convert the exchange current densities for the redox reactions occurring at the bl/s interface and on the hypothetical bare metal surface. We review our previous work on combining QMT theory with the point defect model (PDM), which provides an analytical expression for the bl thickness as a function of voltage. By combining QMT theory and the PDM, we derive a modified form of the generalized Butler-Volmer equation that requires as input only the kinetic parameters for the redox reaction on the hypothetical bare surface and parameters contained in the PDM. The application of the theory is illustrated with reference to the corrosion of carbon steel in concrete pore solution, to calculating the corrosion potential of, and crack growth rate in, sensitized type 304 SS in boiling water reactor (BWR) coolant circuits, and the use of hydrogen oxidation on platinum to determine the thickness of the bl as a function of voltage and temperature. This illustrates a new, powerful technique for probing the formation of passive films on metal surfaces.

众所周知，在被动金属表面发生的氧化还原反应的动力学取决于被动膜的特性，表面上看，这是由于电子的量子机械隧穿（QMT）和金属与氧化还原对之间在阻挡层/解决方案（bl / s）界面。在本文中，隧穿概率用于对在bl / s界面和假设的裸金属表面上发生的氧化还原反应的交换电流密度进行相互转换。我们回顾了先前将QMT理论与点缺陷模型（PDM）相结合的工作，该模型为bl厚度随电压的变化提供了解析表达式。通过结合QMT理论和PDM，我们推导了广义Butler-Volmer方程的修改形式，该形式仅需要输入假设的裸露表面上的氧化还原反应的动力学参数和PDM中包含的参数作为输入。结合碳素在混凝土孔隙溶液中的腐蚀，计算沸水反应堆（BWR）冷却剂回路中敏化型304 SS的腐蚀潜力和裂纹扩展速率，以及该方法的应用说明了该理论的应用。氢在铂上的氧化过程，以确定bl的厚度与电压和温度的关系。这说明了一种用于探测金属表面钝化膜形成的新的强大技术。结合碳素在混凝土孔隙溶液中的腐蚀，计算沸水反应堆（BWR）冷却剂回路中敏化型304 SS的腐蚀潜力和裂纹扩展速率，以及该方法的应用说明了该理论的应用。氢在铂上的氧化过程，以确定bl的厚度与电压和温度的关系。这说明了一种用于探测金属表面钝化膜形成的新的强大技术。结合碳素在混凝土孔隙溶液中的腐蚀，计算沸水反应堆（BWR）冷却剂回路中敏化型304 SS的腐蚀潜力和裂纹扩展速率，以及该方法的应用说明了该理论的应用。氢在铂上的氧化过程，以确定bl的厚度与电压和温度的关系。这说明了一种用于探测金属表面钝化膜形成的新的强大技术。