Anode cathodic protection reactions

This anodic reaction results in the local increase of the halide (e.g., Cl-) concentration and in the decrease of pH inside the pit. On the other hand, the pit growth is accompanied by the cathodic protective reaction (occurring outside the growing pit), namely by the reduction of oxygen to hydroxyl ions ... 

These three passive systems are important in the technique of anodic protection (see Chapter 21). The kinetics of the cathodic partial reaction and therefore curves of type I, II or III depend on the material and the particular medium. Case III can be achieved by alloying additions of cathodically acting elements such as Pt, Pd, Ag, and Cu. In principle, this is a case of galvanic anodic protection by cathodic constituents of the microstructure [50]. 

An important consequence of ion migration is the formation of cells where the coated surface acts as a cathode and the exposed metal at the damage acts as an anode (see Section 4.3). The reason for this is that at the metal/coating interface, the cathodic partial reaction of oxygen reduction according to Eq. (2-17) is much less restricted than the anodic partial reaction according to Eq. (2-21). The activity of such cells can be stimulated by cathodic protection. 

The electrolysis protection process using impressed current aluminum anodes allows uncoated and hot-dipped galvanized ferrous materials in domestic installations to be protected from corrosion. If impressed current aluminum anodes are installed in water tanks, the pipework is protected by the formation of a film without affecting the potability of the water. With domestic galvanized steel pipes, a marked retardation of the cathodic partial reaction occurs [15]. Electrolytic treatment alters the electrolytic characteristics of the water, as well as internal cathodic protection of the tank and its inserts (e.g., heating elements). The pipe protection relies on colloidal chemical processes and is applied only to new installations and not to old ones already attacked by corrosion. 

By contrast, if additional electrons were introduced at the metal surface, the cathodic reaction would speed up (to consume the electrons) and the anodic reaction would be inhibited metal dissolution would be slowed down. This is the basis of cathodic protection. 

Fig. 10.2 Schematic illustration of partial cathodic protection of steel in an aerated environment. Note that one of the anodic reactions shown in Fig. 10.1 has been annihilated by providing two electrons from an external source an excess of OH ", ions over Fe now exists at...

It will be seen that the impressed current electrode discharges positive current, i.e. it acts as an anode in the cell. There are three generic types of anode used in cathodic protection, viz, consumable, non-consumable and semi-consumable. The consumable electrodes undergo an anodic reaction that involves their consumption. Thus an anode made of scrap iron produces positive current by the reaction ... 

The thermodynamic and electrode-kinetic principles of cathodic protection have been discussed at some length in Section 10.1. It has been shown that, if electrons are supplied to the metal/electrolyte solution interface, the rate of the cathodic reaction is increased whilst the rate of the anodic reaction is decreased. Thus, corrosion is reduced. Concomitantly, the electrode potential of the metal becomes more negative. Corrosion may be prevented entirely if the rate of electron supply is such that the potential of the metal is lowered to the value where it is found that anodic dissolution does not occur. This may not necessarily be the potential at which dissolution is thermodynamically impossible. 

Environment Reduce kinetics of cathodic reaction Lower potential of metal Cathodic inhibition Reduce a , reduce O2 concentration or concentration of oxidising species lower temperature, velocity agitation Cathodically protect by sacrificial anodes or impressed current sacrificially protect by coatings, e.g. Zn, Al or Cd on steel Formation of calcareous scales in waters due to increase in pH additions of poisons (As, Bi, Sb) and organic inhibitors to acids... 

The presence of a protective SEI or surface layer prevents those irreversible reactions of electrolytes on anode/cathode surfaces that are otherwise favored by thermodynamics. Like the chemical process in the bulk electrolyte, the reactivity of the surface films formed in state-of-the-art electrolytes is negligible at room temperature. However, during long-term storage and cycling, their stability is still under question. 

Corrosion control using external polarization usually operates by reducing the driving force for the metal dissolution reaction, as in cathodic protection. For passivating metals, an alternative is to reduce the kinetics of the dissolution process by raising the potential. This is known as anodic protection and has been... 

Therefore let us instead consider the more practical case of the tertiary current distribution. Based on the dependency of the Wagner number on polarization slope, we would predict that a pipe cathodically protected to a current density near its mass transport limited cathodic current density would have a more uniform current distribution than a pipe operating under charge transfer control. Of course the cathodic current density cannot exceed the mass transport limited value at any location on the pipe, as said in Chapter 4. Consider a tube that is cathodically protected at its entrance with a zinc anode in neutral seawater (4). Since the oxygen reduction reaction is mass transport limited, the Wagner number is large for the cathodically protected pipe (Fig. 12a), and a relatively uniform current distribution is predicted. However, if the solution conductivity is lowered, the current distribution will become less uniform. Finite element calculations and experimental confirmations (Fig. 12b) confirm the qualitative results of the Wagner number (4). 

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