Concentration cell, 6.36

Cells need not necessarily contain a reference electrode to obtain meaningfiil results as an example, if the two electrodes in figure A2.4.12 are made from the same metal, M, but these are now in contact with two solutions of the same metal ions, M but with differing ionic activities, which are separated from each other by a glass frit that pennits contact, but impedes diffusion, then the EMF of such a cell, temied a concentration cell, is given by... 

In order to describe any electrochemical cell a convention is required for writing down the cells, such as the concentration cell described above. This convention should establish clearly where the boundaries between the different phases exist and, also, what the overall cell reaction is. It is now standard to use vertical lines to delineate phase boundaries, such as those between a solid and a liquid or between two innniscible liquids. The junction between two miscible liquids, which might be maintained by the use of a porous glass frit, is represented by a single vertical dashed line, j, and two dashed lines, jj, are used to indicate two liquid phases... 

In fact, some care is needed with regard to this type of concentration cell, since the assumption implicit in the derivation of A2.4.126 that the potential in the solution is constant between the two electrodes, caimot be entirely correct. At the phase boundary between the two solutions, which is here a semi-pemieable membrane pemiitting the passage of water molecules but not ions between the two solutions, there will be a potential jump. This so-called liquid-junction potential will increase or decrease the measured EMF of the cell depending on its sign. Potential jumps at liquid-liquid junctions are in general rather small compared to nomial cell voltages, and can be minimized fiirther by suitable experimental modifications to the cell. 

There ate three basic technology options for making solar cells with do2ens of variations on each. These approaches ate conveniently grouped as follows thick (- 300 fiTo) crystalline materials, concentrator cells, and thin (- 1 fiva) semiconductor films. 

Biological Corrosion The metabohc activity of microorganisms can either directly or indirectly cause deterioration of a metal by corrosion processes. Such activity can (1) produce a corrosive environment, (2) create electrolytic-concentration cells on the metal surface, (3) alter the resistance of surface films, (4) have an influence on the rate of anodic or cathodic reaction, and (5) alter the environment composition. 

Insoluble corrosion prodiic ts may be completely impeivious to the corroding liquid and, therefore, completely protective or they may be quite permeable and allow local or general corrosion to proceed unhindered. Films that are nonuniform or discontinuous may tend to localize corrosion in particular areas or to induce accelerated corrosion at certain points by initiating electrolytic effects of the concentration-cell type. Films may tend to retain or absorb moisture and thus, by delaying the time of drying, increase the extent of corrosion resulting from exposure to the atmosphere or to corrosive vapors. 

Cleaning Specimens after Test Before specimens are cleaned, their appearance should be observed and recorded. Locations of deposits, variations in types of deposits, and variations in corrosion produces are extremely important in evaluating localized corrosion such as pitting and concentration-cell attack. 

Depth of localized corrosion should be reported for the actual test period and not interpolated or extrapolated to an annual rate. The rate of initiation or propagation of pits is seldom uniform. The size, shape, and distribution or pits should oe noted. A distinction should be made between those occurring underneath the supporting devices (concentration cells) and those on the surfaces that were freely exposed to the test solution. An excellent discussion of pitting corrosion has been pubhshed [Corro.sion, 25t (January 1950)]. 

Local variations in temperature and crevices that permit the accumulation of corrosion products are capable of allowing the formation of concentration cells, with the result of accelerated local corrosion. 

The three major forms of concentration cell corrosion are crevice corrosion, tuberculation, and underdeposit attack. Each form of corrosion is common in cooling systems. Many corrosion-related problems in the cooling water environment are caused by these three forms of wastage. The next three chapters—Chap. 2, Crevice Corrosion, Chap. 3, Tuberculation, and Chap. 4, Underdeposit Corrosion — will discuss cooling water system corrosion problems. 

Attack associated with nonuniformity of the aqueous environments at a surface is called concentration cell corrosion. Corrosion occurs when the environment near the metal surface differs from region to region. These differences create anodes and cathodes (regions differing in electrochemical potential). Local-action corrosion cells are established, and anodic areas lose metal by corrosion. Shielded areas are particularly susceptible to attack, as they often act as anodes (Fig. 2.1). Differences in concentration of dissolved ions such as hydrogen, oxygen, chloride, sulfate, etc. eventually develop between shielded and nearby regions. 

Finally, pitting may be viewed as a special form of concentration cell corrosion. Most alloys that are susceptible to crevice corrosion also pit. However, many metals may pit but not show crevice attack. Further, although sharing many common features with concentration cell corrosion, pitting is sufficiently different to warrant a separate categorization. 

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 ... 

Figure 2.3 Later stage as in Fig. 2.2 when an oxygen concentration cell is established between regions inside and outside the crevice. Oxygen has been depleted inside the crevice.

As rust accumulates, oxygen migration is reduced through the corrosion product layer. Regions below the rust layer become oxygen depleted. An oxygen concentration cell then develops. Corrosion naturally becomes concentrated into small regions beneath the rust, and tubercles are born. 

The use of dispersants is highly recommended in systems containing silt, sand, oil, grease, biological material, and/or other foreign material. Not only does increased dispersion generally increase the effectiveness of chemical inhibition, it also prevents nucleation of oxygen concentration cells beneath foulants. 

Deposits cause corrosion both directly and indirectly. If deposits contain corrosive substances, attack is direct interaction with the aggressive deposit causes wastage. Shielding of surfaces below deposits produces indirect attack corrosion occurs as a consequence of surface shielding provided by the deposit. Both direct and indirect attack may involve concentration cell corrosion, but indirect attack almost always involves this form of corrosion. 

Concentration cell corrosion is caused by chemical concentration differences between areas contacting metal surfaces. An electrochemical cell is established by virtue of the difference between chemical compositions in the water on, and adjacent to, corroding areas. 

Figure 4.1 A) Oxygen concentration cell corrosion beneath a deposit (B) Oxy-...

Severe concentration cell corrosion involves segregation of aggressive anions beneath deposits. Concentrations of sulfate and chloride, in particular, are deleterious. Acid conditions may be established beneath deposits as aggressive anions segregate to these shielded regions. Mineral acids, such as hydrochloric and sulfuric, form by hydrolysis. The mechanism of acid formation is discussed in Chap. 2. 

Almost all cooling water system deposits are waterborne. It would be impossible to list each deposit specifically, but general categorization is possible. Deposits are precipitates, transported particulate, biological materials, and a variety of contaminants such as grease, oil, process chemicals, and silt. Associated corrosion is fundamentally related to whether deposits are innately aggressive or simply serve as an occluding medium beneath which concentration cells develop. An American... 

Silt, sand, concrete chips, shells, and so on, foul many cooling water systems. These siliceous materials produce indirect attack by establishing oxygen concentration cells. Attack is usually general on steel, cast iron, and most copper alloys. Localized attack is almost always confined to strongly passivating metals such as stainless steels and aluminum alloys. 

Substituting one alloy for another may be the only viable solution to a specific corrosion problem. However, caution should be exercised this is especially true in a cooling water environment containing deposits. Concentration cell corrosion is insidious. Corrosion-resistant materials in oxidizing environments such as stainless steels can be severely pitted when surfaces are shielded by deposits. Each deposit is unique, and nature can be perverse. Thus, replacement materials ideally should be tested in the specific service environment before substitution is accepted. 

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. 

Wastage was caused by classic long-term underdeposit corrosion. The combined effects of oxygen concentration cells, low flow, and contamination of system water with high chloride- and sulfate-concentration makeup waters caused corrosion. 

Zinc is susceptible to attack from oiQ gen concentration cells. Shielded areas or areas depleted in oxygen concentration tend to corrode, forming voluminous, white, friable corrosion products. Once the zinc layer is breached, the underlying steel becomes susceptible to attack and is severely wasted locally (Figs. 5.12 and 5.13). 

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. 

Passive corrosion caused by chemically inert substances is the same whether the substance is living or dead. The substance acts as an occluding medium, changes heat conduction, and/or influences flow. Concentration cell corrosion, increased corrosion reaction kinetics, and erosion-corrosion can he caused by biological masses whose metabolic processes do not materially influence corrosion processes. Among these masses are slime layers. 

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