Corrosion reactions dissolved oxygen

Water Treatment. Sodium sulfite is an agent in the reduction of chlorine or oxygen in water. Dissolved oxygen in boiler water tends to enhance pitting and other types of corrosion. In boilers operated at below 4.82 MPa (700 psi), a residual concentration of 30 ppm of sodium sulfite is generally effective. Catalytic amounts of cobalt are often added to accelerate the reaction of oxygen with sulfite (321,322) (see Water, industrial water treatment). 

The production of hydroxide ions creates a localized high pH at the cathode, approximately 1—2 pH units above bulk water pH. Dissolved oxygen reaches the surface by diffusion, as indicated by the wavy lines in Figure 8. The oxygen reduction reaction controls the rate of corrosion in cooling systems the rate of oxygen diffusion is usually the limiting factor. 

Oxygen corrosion of steel doubles for every 35-55°F (20-30°C) rise in temperature, beginning near room temperature. Corrosion is nearly proportional to temperature up to about 180°F (80°C) in systems open to the air. Although reaction rates increase with temperature, dissolved oxygen is driven from solution as temperatures increase. As temperatures approach boiling, corrosion rates fall to very low values, since dissolved-oxygen concentration also decreases as water temperature rises (Fig. 5.4). 

Aluminum alloys are essentially unaffected by dissolved oxygen in pure water up to 350°F (180°C). Although much of aluminum s corrosion resistance is due to the presence of an adherent oxide film, oxygen is not necessary to form the layer. Direct reaction with water can pro-... 

The deleterious effect of sulfur dioxide and sulfites in domestic water is increased corrosivity owing to the lowered pH. However, oxidation of sulfite to sulfate in aqueous solutions uses dissolved oxygen, and lliis may retard corrosion. While llte oxichition of sulfite and sulfiirous acid to sulfate and sulfuric acid in the atmosphere is an environmental concern, this reaction is too... 

In view of the importance of the hydronium ion, HjO, and dissolved oxygen as electron acceptors in corrosion reactions, some values of the redox potentials E and chemical potentials n for the equilibria... 

During the operation of the cell (or during the direct interaction of zinc metal and cupric ions in a beaker) the zinc is oxidised to Zn and corrodes, and the Daniell cell has been widely used to illustrate the electrochemical mechanism of corrosion. This analogy between the Daniell cell and a corrosion cell is perhaps unfortunate, since it tends to create the impression that corrosion occurs only when two dissimilar metals are placed in contact and that the electrodes are always physically separable. Furthermore, although reduction of Cu (aq.) does occur in certain corrosion reactions it is of less importance than reduction of HjO ions or dissolved oxygen. 

The hydrogen evolution reaction (h.e.r.) and the oxygen reduction reaction (equations 1.11 and 1.12) are the two most important cathodic processes in the corrosion of metals, and this is due to the fact that hydrogen ions and water molecules are invariably present in aqueous solution, and since most aqueous solutions are in contact with the atmosphere, dissolved oxygen molecules will normally be present. 

Corrosion reactions involving two simultaneous cathodic processes have already been referred to, and it is now appropriate to consider the graphical method of representing the corrosion rate. It should be noted that although the simultaneous reduction of HjO and dissolved oxygen occurs frequently this does not exhaust the possibilities, and reactions such as Fe - Fe, -> Cu, CI2 Cl may accompany either or both of the... 

Fig. 1.34 Corrosion and passivation of Fe-18Cr-SNi stainl s steel. Potentiosiatic anodic curve JKLM, hydrogen evolution reaction, curve Hl low concentration of dissolved oxygen, curve t> FG, high concentration of dissolved oxygen, curve AflC (Section 3...

From these two examples, which as will be seen subsequently, present a very oversimplified picture of the actual situation, it is evident that macroheterogeneities can lead to localised attack by forming a large cathode/small anode corrosion cell. For localised attack to proceed, an ample and continuous supply of the electron acceptor (dissolved oxygen in the example, but other species such as the ion and Cu can act in a similar manner) must be present at the cathode surface, and the anodic reaction must not be stifled by the formation of protective films of corrosion products. In general, localised attack is more prevalent in near-neutral solutions in which dissolved oxygen is the cathode reactant thus in a strongly acid solution the millscale would be removed by reductive dissolution see Section 11.2) and attack would become uniform. 

Most cases of practical bimetallic corrosion in solutions occur under conditions when the solution contains dissolved oxygen. Accordingly, the primary cathodic reaction is the reduction of dissolved oxygen... 

For diffusion controlled corrosion reactions e.g. dissolved oxygen reduction, and the effect of temperature which increases diffusion rates, then by substituting viscosity and the diffusion coefficients at appropriate temperatures into the Reynolds No. and Schmidt No., changes in corrosion rate can be calculated. 

Dissolved oxygen reduction process Corrosion processes governed by this cathode reaction might be expected to be wholly controlled by concentration polarisation because of the low solubility of oxygen, especially in concentrated salt solution. The effect of temperature increase is complex in that the diffusivity of oxygen molecules increases, but solubility decreases. Data are scarce for these effects but the net mass transport of oxygen should increase with temperature until a maximum is reached (estimated at about 80°C) when the concentration falls as the boiling point is approached. Thus the corrosion rate should attain a maximum at 80°C and then decrease with further increase in temperature. 

This represents a special case of high-level turbulence at a surface by the formation of steam and the possibility of the concentration of ions as water evaporates into the steam bubbles . For those metals and alloys in a particular environment that allow diffusion-controlled corrosion processes, rates will be very high except in the case where dissolved gases such as oxygen are the main cathodic reactant. Under these circumstances gases will be expelled into the steam and are not available for reaction. However, under conditions of sub-cooled forced circulation, when cool solution is continually approaching the hot metal surface, the dissolved oxygen... 

Of the dissolved gases occurring in water, oxygen occupies a special position as it stimulates the corrosion reaction. Carbon dioxide is scarcely less important this constituent must, however, be considered in relation to other constituents, especially calcium hardness. 

Although Table 2.16 shows which metal of a couple will be the anode and will thus corrode more rapidly, little information regarding the corrosion current, and hence the corrosion rate, can be obtained from the e.m.f. of the cell. The kinetics of the corrosion reaction will be determined by the rates of the electrode processes and the corrosion rates of the anode of the couple will depend on the rate of reduction of hydrogen ions or dissolved oxygen at the cathode metal (Section 1.4). 

Sulphur dioxide in the air originates from the combustion of fuel and influences rusting in a number of ways. For example, Russian workers consider that it acts as a cathodic depolariser , which is far more effective than dissolved oxygen in stimulating the corrosion rate. However, it is the series of anodic reactions culminating in the formation of ferrous sulphate that are generally considered to be of particular importance. Sulphur dioxide in the air is oxidised to sulphur trioxide, which reacts with moisture to form sulphuric acid, and this in turn reacts with the steel to form ferrous sulphate. Examination of rust Aims formed in industrial atmospheres have shown that 5% or more of the rust is present in the form of iron sulphates and FeS04 4H2 0 has been identified in shallow pits . 

Corrosion may be described as the undesirable reaction of a metal or alloy with its environment and it follows that control of the rate of process may be eflFected by modifying either of the reactants. In corrosion inhibition , additions of certain chemicals are made to the environment, although it should be noted that an aqueous environment can, in some cases, be made less aggressive by other methods, e.g. removal of dissolved oxygen or adjustment of pH. 

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. 

The potential for corrosion as a result of the reactions of noncondensable gases present in steam-water circuits is a major area of risk. The dissolved oxygen (DO) content of MU water is recognized as a primary source of gas entering a boiler system, and effective deaeration of MU and FW is therefore critical. 

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. 

---