Over potential passivation

Nuclear Reactors. Nuclear power faciUties account for about 20% of the power generated in the United States. Although no new plants are plaimed in the United States, many other countries, particularly those that would otherwise rely heavily on imported fuel, continue to increase their nuclear plant generation capacity. Many industry observers predict that nuclear power may become more attractive in future years as the price of fossil fuels continues to rise and environmental regulations become more stringent. In addition, advanced passive-safety reactor designs may help allay concerns over potential safety issues. 

There has been much recent information on the dangers of passive tobacco smoke. Concern could also be expressed over potential problems of passive marijuana smoke, although intoxication is rarely reported from passive inhalation of marijuana. However, there are numerous reports of cannabis metabolites detected in the urine of the passive inhaler. THC metabolites may be present in the urine up to 2 months after heavy chronic use. 

The optimum process would ideally involve the use of soluble anodes, as the over-potential required to drive the deposition process will be small. This is especially important with ionic liquids because the ohmic loss across the cell can be significant. In aqueous solutions the use of soluble anodes is not often possible due to passivation of the electrode surface at the operating pH. 

Fig. I9M The effect of increasing the concentration of chloride ions on the passive current and on the range of potential over which passivity can be observed, for nickel in 0.5 M H.50. Data from Piron, Koutsoiikos and Nobe, Corrosion, 25, 151, il969).

The surface films discussed in this section reach a steady state when they are thick enough to stop electron transport. Hence, as the surface films become electrically insulating, the active electrodes reach passivation. In the case of monovalent ions such as lithium, the surface films formed in Li salt solutions (or on Li metal) can conduct Li-ions, and hence, behave in general as a solid electrolyte interphase (the SEI model ). See the basic equations 1-7 related to ion transport through surface films in section la above. The potentiodynamics of SEI electrodes such as Li or Li-C may be characterized by a Tafel-like behavior at a high electrical field and by an Ohmic behavior at the low electrical field. The non-uniform structure of the surface films leads to a non-uniform current distribution, and thereby, Li dissolution from Li electrodes may be characterized by cracks, and Li deposition may be dendritic. The morphology of these processes, directed by the surface films, is dealt with later in this chapter. When bivalent active metals are involved, their surface films cannot conduct the bivalent ions. Thereby, Mg or Ca deposition is impossible in most of the commonly used polar aprotic electrolyte solutions. Mg or Ca dissolution occurs at very high over potentials in which the surface films are broken. Hence, dissolution of multivalent active metals occurs via a breakdown and repair of the surface films. 

Fe can be active or passive. In the active region, the current for Fe dissolution bears an exponential relationship with the potential difference, which is denoted by the solid curve (i) at low over-potentials. If the oxygen reduction is the counter-reaction, then the system will shift to a potential where the electrons required for the mass transfer controlled cathodic reaction exactly balance those generated by the dissolution of the metal. This is shown by the position A . 

Fig. 1.39 Schematic anodic polarisation curve for a metal. Region AB describes active dissolution of the metal. BC is the active/passive transition, with passivation commencing at B. Passivation is complete only at potentials higher than C. The metal is passive over the range CD...

In general, a uniform distribution of potential over a regular-shaped passivated surface can be readily obtained by anodic protection. It is much more difficult to protect surface irregularities, such as the recessions around sharp slots, grooves or crevices since the required current density will not be... 

In the potential region where nonequilibrium fluctuations are kept stable, subsequent pitting dissolution of the metal is kept to a minimum. In this case, the passive metal apparently can be treated as an ideally polarized electrode. Then, the passive film is thought to repeat more or less stochastically, rupturing and repairing all over the surface. So it can be assumed that the passive film itself (at least at the initial stage of dissolution) behaves just like an adsorption film dynamically formed by adsorbants. This assumption allows us to employ the usual double-layer theory including a diffuse layer and a Helmholtz layer. 

Unlike the cathodic reaction, anodic oxidation (ionization) of molecular hydrogen can be studied for only a few electrode materials, which include the platinum group metals, tungsten carbide, and in alkaline solutions nickel. Other metals either are not sufficiently stable in the appropriate range of potentials or prove to be inactive toward this reaction. For the materials mentioned, it can be realized only over a relatively narrow range of potentials. Adsorbed or phase oxide layers interfering with the reaction form on the surface at positive potentials. Hence, as the polarization is raised, the anodic current will first increase, then decrease (i.e., the electrode becomes passive see Fig. 16.3 in Chapter 16). In the case of nickel and tungsten... 

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