Differential concentration cell

Microstructural examinations revealed V-shaped openings along the tube seam, some extending into as much as 50% of the tube wall thickness. The incompletely closed seam provided a crevice in which differential concentration cells developed (see Chap. 2, Crevice Corrosion ). The resulting localized corrosion caused the observed pits. 

Chemical removal of deposits and corrosion products revealed the appearance of the groove (Fig. 14.5). The crevice formed by the incompletely fused weld seam fostered the establishment of differential concentration cells (see Chap. 2). This resulted in localized corrosion and eventual perforation through the greatly thinned tube wall at the bottom of the crevice. The tubercle, which is composed of corrosion products, is a simple result of the corrosion process occurring locally within the crevice. 

These potentials are standardised, that is, they only apply to systems at unit activity, 25°C, and latm pressure. Deviation from these conditions will result in quite different values being obtained. For example, if two pieces of zinc are dipped into zinc sulphate solutions of different concentration (the solutions being connected via a salt bridge), a difference in potential will be measurable between the two electrodes. The electrode in the more concentrated solution will be the cathode and that in the dilute solution the anode. This is a differential concentration cell, many examples of which are found in corroding systems. Thus, any electrochemical series may be produced for a given environment, that is metals and alloys may be arranged in order of corrosion resistance to that environment. Table 1 illustrates this point for alloys immersed in flowing seawater [3],... 

Therefore, such a type of corrosion is also called a differential concentration cell. However, not only oxygen, but other elements dissolved in the solution can bring about the concentration ceU. 

Oxygen is essential for corrosion to occur in the pH range commonly found in soils. Soils such as clays restrict oxygen movement therefore, these soils are prone to anaerobic conditions. Often, however, soils such as clays tend to promote galvanic corrosion cells that are caused by differences in oxygen concentration (differential concentration cell corrosion). Bacterial corrosion often occurs in clay soils because anaerobic conditions and organic matter promote bacterial growth. A common type of bacteria that causes... 

Oxygen concentration is held almost constant by water flow outside the crevice. Thus, a differential oxygen concentration cell is created. The oxygenated water allows Reaction 2.2 to continue outside the crevice. Regions outside the crevice become cathodic, and metal dissolution ceases there. Within the crevice. Reaction 2.1 continues (Fig. 2.3). Metal ions migrating out of the crevice react with the dissolved oxygen and water to form metal hydroxides (in the case of steel, rust is formed) as in Reactions 2.3 and 2.4 ... 

Underdeposit corrosion is not so much a single corrosion mechanism as it is a generic description of wastage beneath deposits. Attack may appear much the same beneath silt, precipitates, metal oxides, and debris. Differential oxygen concentration cell corrosion may appear much the same beneath all kinds of deposits. However, when deposits tend to directly interact with metal surfaces, attack is easier to recognize. 

Two sections of steel condenser tubing experienced considerable metal loss from internal surfaces. An old section contained a perforation the newer section had not failed. A stratified oxide and deposit layer overlaid all internal surfaces (Fig. 5.14). Corrosion was severe along a longitudinal weld seam in the older section (Fig. 5.15). Differential oxygen concentration cells operated beneath the heavy accumulation of corrosion products and deposits. The older tube perforated along a weld seam. 

Microstructural examinations revealed that branched cracks originated at shallow pit sites on the external surface. The pits, which may have formed during idle periods from differential oxygen concentration cells formed beneath deposits, acted as stress concentrators. The transverse (circumferential) crack orientation and the localization of cracks along just one side of the tube revealed that bending of the tube was responsible for the stresses involved. 

Concentration cells have two similar electrodes in contact with a solution of differing composition. The two kinds of concentration cells are salt concentration cells and differential aeration cells [186]. 

Differential Aeration Cells. This type of concentration cell is more important in practice than is the salt concentration cell. The cell may be made from two electrodes of the same metal (i.e., iron), immersed completely in dilute sodium chloride solution (Figure 4-433). The electrolyte around one electrode (cathode) is thoroughly aerated by bubbling air. Simultaneously the electrolyte around the other electrode is deaerated by bubbling nitrogen. The difference in oxygen concentration causes a difference in potential. This, in turn, initiates the flow of current. This type of cell exists in several forms. Some of them are as follows [188]. 

Air—Water Interface. This is another good example of a differential aeration cell (Figure 4-436). Here the water at the surface contains more oxygen than the water slightly below the surface. This difference in concentration can cause preferential attack just below the waterline. 

Figure 53.4 Crevice corrosion driven by (a) a differential aeration cell and (b) a differential metal ion concentration cell...

Crevice corrosion of copper alloys is similar in principle to that of stainless steels, but a differential metal ion concentration cell (Figure 53.4(b)) is set up in place of the differential oxygen concentration cell. The copper in the crevice is corroded, forming Cu ions. These diffuse out of the crevice, to maintain overall electrical neutrality, and are oxidized to Cu ions. These are strongly oxidizing and constitute the cathodic agent, being reduced to Cu ions at the cathodic site outside the crevice. Acidification of the crevice solution does not occur in this system. 

At first sight it might appear that differential aeration could be explained in terms of a reversible oxygen concentration cell, for which... 

Fig. 1.48 Examples of differential aeration cells (a) and (b) Differential aeration cells formed by the geometry of a drop of NaCl solution on a steel surface (c) differential aeration cells formed by the geometry of a vertical steel plate partly immersed in a NaCl solution. Increasing concentrations of Na2 CO3 decrease the anodic area (d) until at a sufficient concentration attack is confined to the water line (e) (/) shows the membrane of corrosion products formed at water...

Fig. 1.52 Mechanism of filiform corrosion showing how atmospheric oxygen and watCT enter the active head through the film (lacquer) and how water leaves through the inactive tail. This results in a high concentration of oxygen at the V -shaped interface between the tail and the head, and to a differential aeration cell (after Uhlig )...

In addition to the basic corrosion mechanism of attack by acetic acid, it is well established that differential oxygen concentration cells are set up along metals embedded in wood. The gap between a nail and the wood into which it is embedded resembles the ideal crevice or deep, narrow pit. It is expected, therefore, that the cathodic reaction (oxygen reduction) should take place on the exposed head and that metal dissolution should occur on the shank in the wood. 

Oxygen Concentration Cell see under Differential Aeration. 

Although each form of concentration cell may be considered a discrete form of corrosion, in practice, more than one type may occur simultaneously. These forms of corrosion are all characterized by localized differences in concentration of hydrogen, oxygen, chloride, sulfate, and other minerals, but especially oxygen (producing the so-called differential oxygen concentration cell, or differential-aeration cell). The basic mechanisms surrounding each of these specific forms of concentration cell corrosion are discussed next. 

Under-Deposit Corrosion In the same way that oxygen becomes depleted in a crevice, and a differential-oxygen concentration cell is established, leading to localized corrosion of the oxygen-starved anodic area, so the same phenomenon readily occurs in dirty boilers under deposits, sludge, and other foulants. 

Localized, concentration-cell corrosion (differential aeration corrosion), occurring as Tuberculation corrosion Crevice corrosion Under-deposit corrosion Pitting corrosion All forms of localized, concentration-cell corrosion are indirect attack type corrosion mechanisms. They result in severe metal wastage and can also induce other corrosion mechanisms, e.g. Stress corrosion Corrosion fatigue... 

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