Cathodic areas

The existence of anode and cathode areas can be seen by the following experiment. A few drops of phenolphthalein are added to a solution of potassium hexacyanoferrate(III) and hydrochloric acid added, drop by drop, until the solution is colourless. (The phenolphthalein turns pink due to hydrolysis of the potassium hexacyano-ferrate(III).) Drops of this solution, about 1 cm in diameter, are now placed on a sheet of freshly abraded steel when pink cathode areas and blue anode areas appear. 

AlliedSignal Cell. A cross section of AUiedSignal s cell is shown in Eigure 3. The cell body is a rectangular steel box on wheels with an outside water-cooling jacket. A central partition divides the box lengthwise. The negative side of the d-c bus is connected directly to the cell container. The interior of the box and the central partition act as the cathodic area of the cell. 

The temperature in the ceU is 40°C. Most electrolyte ceUs are equipped with 24 anodes spaced approximately 10 cm apart, center to center 25 cathode starting sheets are used, one at each end and others evenly spaced between the anodes. Current density is typicaUy 15 mA/cm of cathode area ceU voltage ranges from 0.30 to 0.70 V, and a current efficiency of 90—95% is usuaUy realized. 

A fused-salt electrolysis process has been demonstrated (30). Carbon dioxide is introduced to the cathode area of a melt of 60 wt % LiCl—40 wt % Li2C02 at 550°C. The carbon dioxide reacts with hthium oxide which is produced by electrolysis. Oxygen is released at the anode and carbon plates onto the cathode. The reaction requites a potential of 4.5 V. The reactions ate as follows ... 

Atmospheric corrosion is electrochemical ia nature and depends on the flow of current between anodic and cathodic areas. The resulting attack is generally localized to particular features of the metallurgical stmcture. Features that contribute to differences ia potential iaclude the iatermetaUic particles and the electrode potentials of the matrix. The electrode potentials of some soHd solutions and iatermetaUic particles are shown ia Table 26. Iron and sUicon impurities ia commercially pure aluminum form iatermetaUic coastitueat particles that are cathodic to alumiaum. Because the oxide film over these coastitueats may be weak, they can promote electrochemical attack of the surrounding aluminum matrix. The superior resistance to corrosion of high purity aluminum is attributed to the small number of these constituents. 

The reaction mixture is filtered. The soHds containing K MnO are leached, filtered, and the filtrate composition adjusted for electrolysis. The soHds are gangue. The Cams Chemical Co. electrolyzes a solution containing 120—150 g/L KOH and 50—60 g/L K MnO. The cells are bipolar (68). The anode side is monel and the cathode mild steel. The cathode consists of small protmsions from the bipolar unit. The base of the cathode is coated with a corrosion-resistant plastic such that the ratio of active cathode area to anode area is about 1 to 140. Cells operate at 1.2—1.4 kA. Anode and cathode current densities are about 85—100 A/m and 13—15 kA/m, respectively. The small cathode areas and large anode areas are used to minimize the reduction of permanganate at the cathode (69). Potassium permanganate is continuously crystallized from cell Hquors. The caustic mother Hquors are evaporated and returned to the cell feed preparation system. 

In most aqueous systems, the corrosion reaction is divided into an anodic portion and a cathodic portion, occurring simultaneously at discrete points on metallic surfaces. Flow of electricity from the anodic to the cathodic areas may be generated by local cells set up either on a single metallic surface (because of local point-to-point differences on the surface) or between dissimilar met s. 

The crevice shape markedly affects corrosion. Crevices so tight that water may not enter are entirely immune to attack. In misting environments or alternately wet-diy environments, the crevice holds water and may allow continued attack even when neeu by surfaces eire dry. In sea water, the severity of attack in stainless steel crevices depends on the ratio of the crevice area to the cathodic surface area outside the crevice. If the cathodic area is large relative to crevice eirea, corrosion is promoted. 

Correct application of this principle can lead to what would appear to he peculiar recommendations. For example, if just one member of a couple is to be coated, it should be the noble member. Most coating systems leave holidays or tiny openings where the metal is exposed. If the active metal is coated, the area of exposure at the holidays can be quite small compared to the area of the noble metal, resulting in an unfavorable area ratio. On the other hand, if the noble metal is coated, the holidays provide a small cathodic area and hence a highly favorable area ratio with respect to the active metal. Similarly, if dissimilar metal fasteners must be used, they should be noble relative to the metals being fastened (see Case History 16.1). 

Objects with extended concentration cells can be individual lengths of pipeline and storage tanks if the makeup of the soil over the surface changes. The distance between anodic and cathodic areas can lie between a few centimeters and a few kilometers. 

Pits occur as small areas of localized corrosion and vary in size, frequency of occurrence, and depth. Rapid penetration of the metal may occur, leading to metal perforation. Pits are often initiated because of inhomogeneity of the metal surface, deposits on the surface, or breaks in a passive film. The intensity of attack is related to the ratio of cathode area to anode ai ea (pit site), as well as the effect of the environment. Halide ions such as chlorides often stimulate pitting corrosion. Once a pit starts, a concentration-cell is developed since the base of the pit is less accessible to oxygen. 

Choose the metal or alloy so that the anode area is larger than the cathode area. 

Figure 4-458. Diagram of polarization of local cathode by a film of hydrogen gas bubbles (cathodic area to right of anode is polarized). (From Ref. [208].)...

Finally, it is important to point out that although in localised corrosion the anodic and cathodic areas are physically distinguishable, it does not follow that the total geometrical areas available are actually involved in the charge transfer process. Thus in the corrosion of two dissimilar metals in contact (bimetallic corrosion) the metal of more positive potential (the predominantly cathodic area of the bimetallic couple) may have a very much larger area than that of the predominantly anodic metal, but only the area adjacent to the anode may be effective as a cathode. In fact in a solution of high resistivity the effective areas of both metals will not extend appreciably from the interface of contact. Thus the effective areas of the anodic and cathodic sites may be much smaller than their geometrical areas. 

Thus localised attack usually involves a corrosion cell consisting of a large cathodic area and a small anodic area, and since must equal /, the effect will become more pronounced the higher the rate of the cathodic process and the larger the effective area of the cathode. 

Bimetallic corrosion in atmospheres is confined to the area of the less noble metal in the vicinity of the bimetallic joint, owing to the high electrolytic resistance of the condensed electrolyte film. Electrolytic resistance considerations limit the effective anodic and cathodic areas to approximately equal size and therefore prevent alleviation of atmospheric galvanic corrosion through strict application of the catchment area principle. 

The most commonly observed effect of current flow is the development of alkaline conditions at the cathode. On bare metal this alkaline zone may exist only at the metal surface and may often reach pH values of 10 to 12. When the soil solution contains appreciable calcium or magnesium these cations usually form a layer of carbonate or hydroxide at the cathodic area. On coated lines the cations usually move to holidays or breaks in the coating. On failing asphalt or asphalt mastic type coatings, masses of precipitated calcium and magnesium often form nodules or tubercles several centimetres in diameter. 

Since metals are electronic conductors, the anodic and cathodic reactions will not necessarily occur at the same site, and anodic and cathodic areas can develop as in aqueous solutions. For example, wash-line attack is often a feature of corrosion by fused salts in contact with air. 

The rate of water flow is also most important. This determines the supply of oxygen to the rusting surface, and may remove corrosion products that would otherwise stifle further rusting. A plentiful oxygen supply to the cathodic areas will stimulate corrosion, but so may smaller supplies at a slow rate of flow, if this leads to the formation of differential aeration cells (see Section 1.6). 

The corrosion rates for both maraging steel and the low alloy steels in seawater are similar initially, but from about 1 year onwards the maraging steels tend to corrode more slowly as indicated in Fig. 3.32. The corrosion rates for both low alloy and maraging steel increase with water velocity . During sea-water exposure the initial attack was confined to local anodic areas, whereas other areas (cathodic) remained almost free from attack the latter were covered with a calcareous deposit typical of cathodic areas in sea-water exposure. In time, the anodic rust areas covered the entire surface. ... 

Feitknecht has examined the corrosion products of zinc in sodium chloride solutions in detail. The compound on the inactive areas was found to be mainly zinc oxide. When the concentration of sodium chloride was greater than 0-1 M, basic zinc chlorides were found on the corroded parts. At lower concentrations a loose powdery form of a crystalline zinc hydroxide appeared. A close examination of the corroded areas revealed craters which appeared to contain alternate layers and concentric rings of basic chlorides and hydroxides. Two basic zinc chlorides were identified, namely 6Zn(OH)2 -ZnClj and 4Zn(OH)2 ZnCl. These basic salts, and the crystalline zinc hydroxides, were found to have layer structures similar in general to the layer structure attributed to the basic zinc carbonate which forms dense adherent films and appears to play such an important role in the corrosion resistance of zinc against the atmosphere. The presence of different reaction products in the actual corroded areas leads to the view that, in addition to action between the major anodic and cathodic areas as a whole, there is also a local interaction between smaller anodic and cathodic elements. 

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