Aqueous Solutions and Soil

Surface films are formed by corrosion on practically all commercial metals and consist of solid corrosion products (see area II in Fig. 2-2). It is essential for the protective action of these surface films that they be sufficiently thick and homogeneous to sustain the transport of the reaction products between metal and medium. With ferrous materials and many other metals, the surface films have a considerably higher conductivity for electrons than for ions. Thus the cathodic redox reaction according to Eq. (2-9) is considerably less restricted than it is by the transport of metal ions. The location of the cathodic partial reaction is not only the interface between the metal and the medium but also the interface between the film and medium, in which the reaction product OH is formed on the surface film and raises the pH. With most metals this reduces the solubility of the surface film (i.e., the passive state is stabilized). 

Both partial reactions are stimulated on uncovered areas of the metal surface. Coverage of such a region is determined by whether the corrosion product is formed actually on the metal surface or whether it arises initially as solid oxide at some 

Very high pH values are necessary for the reaction in Eq. (4-1), which can only arise as a result of cathodic polarization according to Eq. (2-19) (see Fig. 2-11). No protective films are formed on Fe due to the relatively high solubility of Fe(OH)2, although further oxidation produces solid films  

The oxidation products are almost insoluble and lead to the formation of protective films. They promote aeration cells if these products do not cover the metal surface uniformly. Ions of soluble salts play an important role in these cells. In the schematic diagram in Fig. 4-1 it is assumed that from the start the two corrosion partial reactions are taking place at two entirely separate locations. This process must quickly come to a complete standstill if soluble salts are absent, because otherwise the ions produced according to Eqs. (2-21) and (2-17) would form a local space charge. Corrosion in salt-free water is only possible if the two partial reactions are not spatially separated, but occur at the same place with equivalent current densities. The reaction products then react according to Eq. (4-2) and in the subsequent reactions (4-3a) and (4-3b) to form protective films. Similar behavior occurs in salt-free sandy soils. 

In the presence of dissolved ions, the ion charge at the metal surface can be neutralized by the migration of the counter-ions to the reaction site. The following reactions take place  

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On the other hand, it can be assumed for the oxygen corrosion of steel in aqueous solutions and soils that there is a constant minimum protection current density, 4, in the protective range, U limiting current density for oxygen reduction according to Eq. (4-5) (see Section 2.2.3.2). Then it follows, with V = +1,1 = 2nr, S = 27crs and d = dU from Eq. (24-54), instead of Eq. (24-58) [12-14] ... 

Heim M, Schwenk W. Corrosion in aqueous solutions and soil. In von Baeckmarm W, Schwenk W, Prinz W, eds. Handbook of Cathodic Protection. 1997 139-52. 

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