Redefining the Electrochemical Kinetics of Redox Reactions on Passive Metals

The kinetics of redox reactions are described by specifying a standard exchange current density and a transfer coefficient that locates the position along the reaction coordinate at which the activated complex (transition state) occurs. However, this formulation was originally developed to describe charge transfer reactions on bare metal surfaces. In the case of a passive metal, however, the barrier layer of the passive film represents a barrier to the quantum mechanical tunneling of charge carriers (electrons and electron holes) between the metal and the redox reaction center and theory shows that this barrier has a profound effect upon the tunneling probability and hence upon the values of the exchange current density and the Tafel constant. In this presentation, the role of quantum-mechanical tunneling of charge carriers through the barrier oxide layer on a passive metal, in determining the electrochemical kinetic parameters is explored theoretically. The exchange current density for a redox reaction occurring on the passive metal surface is assumed to be the product of the exchange current density on the bare metal surface and the quantum mechanical tunneling probability (QMTP) of charge carriers through the barrier layer, which is inversely proportional to the exponential of the barrier thickness and the tunneling constant that in turn is proportional to the square root of the product of barrier height and the effective electron mass. The QMTP is used to redefine the exchange current density for the cathodic reaction (e.g., reduction of oxygen), as measured on the passive surface, to that on the (hypothetical) bare metal alone. Thus, knowing the voltage, the barrier layer thickness can be calculated from the Point Defect Model (PDM), which in turn can be used to estimate the QMTP for that particular set of conditions. Then, the exchange current density for the redox reaction on the passive metal surface is calculated and used, if the barrier height and the effective electron mass are constants, in the generalized Butler-Volmer equation to describe the current/voltage characteristics of the redox reaction. In doing so, it becomes evident that the kinetics of a redox reaction are fully determined by specifying a (hypothetical) exchange current density and transfer coefficient of the reaction on the bare metal (“hypothetical” because the bare metal condition may not be realizable experimentally), the QMTP, the electric field strength within the barrier layer, the polarizability of the barrier layer/solution interface, and the potential of zero thickness of the barrier layer. The application of this theory is illustrated with respect to the hydrogen electrode reaction (HER) on passive carbon steel and on aluminum and in predicting the corrosion potentials of stainless steels and nickel alloys in the primary coolant circuits of water-cooled nuclear reactors.