Metal dissolution reduction reactions

We have seen in Section 26.2.1 that thermodynamics (i.e., equilibrium half-cell potentials) can be used to determine which of two half-cell reactions proceeds spontaneously in the anodic or cathodic direction when the two reactions occur on the same piece of metal or on two metal samples that are in electrical contact with one another. The half-cell reaction with the higher equilibrium potential will always be at the cathode. Thus, under standard conditions any metal dissolution (corrosion) reaction with an E° less than 0.0 V vs. SHE will be driven by proton reduction while metal dissolntion reactions with an E° less than -e1.23 V vs. SHE will be driven by dissolved... 

Corrosion in open circuit conditions requires a counter reaction to consume the electrons, which are produced by metal dissolution. Important reactions are hydrogen evolution and oxygen reduction. Fe + reduction is another. [Fe(CN)6] reduction is a simple outer sphere reaction, which may be used for basic corrosion studies. In most cases, one tries for simplicity to study metal dissolution and the redox reactions separately with the use of a potentiostat. In the following, the hydrogen evolution and the oxygen reduction reaction are discussed separately. 

The passive state of a metal can, under certain circumstances, be prone to localized instabilities. Most investigated is the case of localized dissolution events on oxide-passivated surfaces [51, 106, 107, 108, 109, 110, ill, 112, 113, 114, 115, 116, 117 and 118]. The essence of localized corrosion is that distinct anodic sites on the surface can be identified where the metal oxidation reaction (e.g. Fe —> Fe + 2e ) dominates, surrounded by a cathodic zone where the reduction reaction takes place (e.g. 2Fi + 2e —> Fi2). The result is the fonnation of an active pit in the metal, an example of which is illustrated in figure C2.8.6(a) and (b). 

Anodic or cathodic inhibitors This classification is based on whether the inhibitor causes increased polarisation of the anodic reaction (metal dissolution) or of the cathodic reaction, i.e. oxygen reduction (near-neutral solutions) or hydrogen discharge (acid solutions). 

The explicit aims of boiler and feed-water treatment are to minimise corrosion, deposit formation, and carryover of boiler water solutes in steam. Corrosion control is sought primarily by adjustment of the pH and dissolved oxygen concentrations. Thus, the cathodic half-cell reactions of the two common corrosion processes are hindered. The pH is brought to a compromise value, usually just above 9 (at 25°C), so that the tendency for metal dissolution is at a practical minimum for both steel and copper alloys. Similarly, by the removal of dissolved oxygen, by a combination of mechanical and chemical means, the scope for the reduction of oxygen to hydroxyl is severely constrained. 

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. 

In general, corrosion of metal is always accompanied by dissolution of a metal and reduction of an oxidant such as a proton in acidic solution and dissolved oxygen in a neutral solution. That is, metal corrosion is not a single electrode reaction, but a complex reaction composed of the oxidation of metal atoms and the reduction of oxidants. 

For the corresponding equations in alkaline solutions, see Chapter 9. The metal surface attains a mixed potential corrosion potential, such that the anodic current of the metal dissolution is exactly balanced by the cathodic current of one or more reduction reactions. The corrosion potential is given by Eq. (11.41), and the corrosion current density by Eq. (11.42). 

Figure 11-7 shows the polarization curve of an iron electrode in an acidic solution in which the anodic reaction is the anodic transfer of iron ions for metal dissolution (Tafel slope 40 mV/decade) the cathodic reaction is the cathodic transfer of electrons for reduction of hydrogen ions (Tafel slope 120 mV /decade) across the interface of iron electrode. 

Fig. 13. (a) Schematic representation of the formation of mixed potential, M, at an inert electrode with two simultaneous redox processes (I) and (II) with formal equilibrium potentials E j and E2. Observed current density—potential curve is shown by the broken line, (b) Representation of the formation of corrosion potential, Econ, by simultaneous occurrence of metal dissolution (I), hydrogen evolution, and oxygen reduction. Dissolution of metal M takes place at far too noble potentials and hence does not contribute to EC0Ir and the oxygen evolution reaction. The broken line shows the observed current density—potential curve for the system. 

Cementation, the process by which a metal is reduced from solution by the dissolution of a less-noble metal, has been used for centuries as a means for extraction of metals from solution, and is probably the oldest of the hydrometallurgical processes. It is also known by other terms such as metal displacement or contract reduction, and is widely used in the recovery of metals such as silver, gold, selenium, cadmium, copper and thallium from solution and the purification of solutions such as those used in the electrowinning of zinc. The electrochemical basis for these reactions has been well established414 and, as in leaching reactions, comprises the anodic dissolution of the less-noble metal coupled to the cathodic reduction of the more-noble metal on the surface of the corroding metals. Therefore, in the well-known and commercially exploited44 cementation of copper from sulfate solution by metallic iron, the reactions are... 

The most simple way of preparing sodium caprolactam consists in dissolving the sodium metal in molten caprolactam. Although the solutions thus obtained are capable to induce a rapid polymerization, we meet with complications arising from the presence of reduction products formed such as hexamethyleneimine (53,69,80,81) and 6-aminohexanol (59,69). These by-products affect the course of the subsequent polymerization as they react with the active centers. The ratio neutralization/reduction in the alkali metal reaction with caprolactam depends strongly on the temperature. According to Hamann (41) and Yumoto (101) the reduction reaction takes place to 75% and 10—20% respectively. In order to suppress the reduction it is recommended to maintain the temperature during the dissolution of the sodium metal below 100° (42). 

The pH of the solution can also play an important role. For nitrate reduction, reaction was faster in lower pH solutions (Horold et al. 1993 Liidtke et al. 1998) however, acidic solutions can dissolve the catalyst metal and negate the effects of the faster rates. The Cu in the bimetallic nitrate-reducing catalyst dissolved at pH values < 5 and deactivation was observed (Horold et al. 1993) Pd dissolution in a monometallic catalyst became significant below a pH of 4. (Munakata et al. 1998)... 

The anodic reaction is an oxidation reaction producing electrons in the anode, while the cathodic reaction is a reduction reaction consuming electrodic electrons at the cathode interface. We shall consider, as an example, an electrochemical cell consisting of a metallic zinc electrode and a metallic copper electrode, in which the anodic reaction of zinc ion transfer (zinc dissolution) is coupled with the cathodic reaction of copper ion transfer (copper deposition) as shown in the following processes ... 

The most simple Pourbaix diagram is that for water shown in Fig. 7. All Pourbaix diagrams contain the two lines that bound the regions of stability for water, known as the reversible hydrogen and reversible oxygen lines, and labeled as a and b, respectively. For corrosionists the importance of these lines should not be underestimated. As noted in the introduction, for metal dissolution to occur, a reduction reaction must occur. In aqueous solution, the most common reduction reactions are the reduction of dissolved oxygen and the reduction of water... 

Metallic corrosion occurs because of the coupling of two different electrochemical reactions on the material surface. If, as assumed in the discussion of iron dissolution kinetics above, only iron oxidation and reduction were possible, the conservation of charge would require that in the absence of external polarization, the iron be in thermodynamic equilibrium. Under those conditions, no net dissolution would occur. In real systems, that assumption is invalid, and metallic dissolution occurs with regularity, keeping corrosionists employed and off the street. 

Chromates are particularly effective inhibitors, and there appear to be several components to inhibition. Chromate in solution inhibits metal dissolution and oxygen reduction reactions. It also slows metastable pitting, the transition to stable pitting, and, when present in sufficient concentration, the growth stage of pitting and crevice corrosion. 

Corrosion inhibitor - corrosion inhibitors are chemicals which are added to the electrolyte or a gas phase (gas phase inhibitors) which slow down the - kinetics of the corrosion process. Both partial reactions of the corrosion process may be inhibited, the anodic metal dissolution and/or the cathodic reduction of a redox-system [i]. In many cases organic chemicals or compounds after their reaction in solution are adsorbed at the metal surface and block the reactive centers. They may also form layers with metal cations, thus growing a protective film at the surface like anodic oxide films in case of passivity. Benzo-triazole is an example for the inhibition of copper cor-... 

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