Electrochemical mechanisms

It follows that corrosion is an electrochemical reaction in which the metal itself is a reactant and is oxidised (loss of electrons) to a higher valency state, whilst another reactant, an electron acceptor, in solution is reduced (gain of electrons) to a lower valency state. This may be regarded as a concise expression of the electrochemical mechanism of corrosion . 

The essential features of the electrochemical mechanism of corrosion were outlined at the beginning of the section, and it is now necessary to consider the factors that control the rate of corrosion of a single metal in more detail. However, before doing so it is helpful to examine the charge transfer processes that occur at the two separable electrodes of a well-defined electrochemical cell in order to show that since the two half reactions constituting the overall reaction are interdependent, their rates and extents will be equal. 

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. 

It follows from the electrochemical mechanism of corrosion that the rates of the anodic and cathodic reactions are interdependent, and that either or both may control the rate of the corrosion reaction. It is also evident from thermodynamic considerations (Tables 1.9 and 1.10) that for a species in solution to act as an electron acceptor its redox potential must be more positive than that of the M /M equilibrium or of any other equilibrium involving an oxidised form of the metal. 

The conductivity of the soil i important as it is evident from the electrochemical mechanism of corrosion that this can be rate-controlling a high conductivity will be conducive of a high corrosion rate. In addition the conductivity of the soil is. important for stray-currenit corrosion (see Section 10.5), and for cathodic protection (Chapter 10). 

We conclude that corrosion is a chemical reaction (equation 10.1) occurring by an electrochemical mechanism (equations 10.2) and (10.3), i.e. by a process involving electrical and chemical species. Figure 10.1 is a schematic representation of aqueous corrrosion occurring at a metal surface. 

Before considering the principles of this method, it is useful to distinguish between anodic protection and cathodic protection (when the latter is produced by an external e.m.f.). Both these techniques, which may be used to reduce the corrosion of metals in contact with electrolytes, depend upon the electrochemical mechanisms that result from changing the potential of a metal. The appropriate potential-pH diagram for the Fe-H20 system (Section 1.4) indicates the magnitude and direction of the changes in the potential of iron immersed in water (pH about 7) necessary to make it either passive or immune in the former case the stability of the metal depends on the formation of a protective film of metal oxide (passivation), whereas in the latter the metal itself is thermodynamically stable and egress of metal ions from the lattice into the solution is thus prevented. 

Paints used for protecting the bottoms of ships encounter conditions not met by structural steelwork. The corrosion of steel immersed in sea-water with an ample supply of dissolved oxygen proceeds by an electrochemical mechanism whereby excess hydroxyl ions are formed at the cathodic areas. Consequently, paints for use on steel immersed in sea-water (pH 8-0-8-2) must resist alkaline conditions, i.e. media such as linseed oil which are readily saponified must not be used. In addition, the paint films should have a high electrical resistance to impede the flow of corrosion currents between the metal and the water. Paints used on structural steelwork ashore do not meet these requirements. It should be particularly noted that the well-known structural steel priming paint, i.e. red lead in linseed oil, is not suitable for use on ships bottoms. Conventional protective paints are based on phenolic media, pitches and bitumens, but in recent years high performance paints based on the newer types of non-saponifiable resins such as epoxies. 

Any fundamental classification of corrosion control must be based on the electrochemical mechanism of corrosion, and Evans diagrams may be constructed (Fig. 1.27, Section 1.4) illustrating... 

Many anodic oxidations involve an ECE pathway. For example, the neurotransmitter epinephrine can be oxidized to its quinone, which proceeds via cyclization to leukoadrenochrome. The latter can rapidly undergo electron transfer to form adrenochrome (5). The electrochemical oxidation of aniline is another classical example of an ECE pathway (6). The cation radical thus formed rapidly undergoes a dimerization reaction to yield an easily oxidized p-aminodiphenylamine product. Another example (of industrial relevance) is the reductive coupling of activated olefins to yield a radical anion, which reacts with the parent olefin to give a reducible dimer (7). If the chemical step is very fast (in comparison to the electron-transfer process), the system will behave as an EE mechanism (of two successive charge-transfer steps). Table 2-1 summarizes common electrochemical mechanisms involving coupled chemical reactions. Powerful cyclic voltammetric computational simulators, exploring the behavior of virtually any user-specific mechanism, have... 

TABLE 2-1 Electrochemical Mechanisms Involving Coupled Chemical Reactions... 

Microwave measurements are typically performed at frequencies between 8 and 40 Gc/s. The sensitivity with which photogenerated charge carriers can be detected in materials by microwave conductivity measurements depends on the conductivity of the materials, but it can be very high. It has been estimated that 109-1010 electronic charge carriers per cubic centimeter can be detected. Infrared radiation can, of course, also be used to detect and measure free electronic charge carriers. The sensitivity for such measurements, however, is several orders of magnitude less and has been estimated to be around 1015 electronic charge carriers per cubic centimeter.1 Microwave techniques, therefore, promise much more sensitive access to electrochemical mechanisms. 

After this step, the understanding of microwave electrochemical mechanisms deepened rapidly. G. Schlichthorl went to the laboratory of L. Peter to combine potential-modulated microwave measurements with impedance measurements, while our efforts focused on laser pulse-induced microwave transients under electrochemical conditions. It is hoped that the still relatively modest knowledge provided will stimulate other groups to participate in the development of microwave photoelectrochemistry. 

Becker, R. 0. Electrochemical Mechanisms and the Control of Biological Growth Processes 10... 

Xanthate compounds are widely used as collectors in flotation. Their function is to render the mineral surface hydrophobic and thus facilitate bubble attachment. The adsorption of xanthates onto sulfide minerals occurs via an electrochemical mechanism involving the reduction of oxygen and the anodic adsorption of xanthate. 

Corrosion (from Latin corrodere, gnaw to pieces ) of metals is the spontaneous chemical (oxidative) destruction of metals under the elfect of their environment. Most often it follows an electrochemical mechanism, where anodic dissolution (oxidation) of the metal and cathodic reduction of an oxidizing agent occur as coupled reactions. Sometimes a chemical mechanism is observed. 

The individual steps of the multistep chemical reduction of COj with the aid of NADPHj require an energy supply. This supply is secured by participation of ATP molecules in these steps. The chloroplasts of plants contain few mitochondria. Hence, the ATP molecules are formed in plants not by oxidative phosphorylation of ADP but by a phosphorylation reaction coupled with the individual steps of the photosynthesis reaction, particularly with the steps in the transition from PSII to PSI. The mechanism of ATP synthesis evidently is similar to the electrochemical mechanism involved in their formation by oxidative phosphorylation owing to concentration gradients of the hydrogen ions between the two sides of internal chloroplast membranes, a certain membrane potential develops on account of which the ATP can be synthesized from ADP. Three molecules of ATP are involved in the reaction per molecule of COj. 

The electrochemical mechanism can be well explained with the mineral pyrite. The collector ion is xanthate ion (CT), a member in the anodic sulfydryl collectors group. Two electrochemical reactions occur on the surface of the pyrite. There is the formation of dixanthogen (C2) by anodic oxidation of xanthate ion (CT) on the surface of pyrite coupled with cathodic reduction of adsorbed oxygen. These reactions are shown below ... 

The principal evidence in favor of the electrochemical mechanism is the observation that metal deposition can occur, albeit at a much reduced rate, in a two-compartment cell. When one of the compartments contains only the metal ions and the other only the sodium hypophosphite, metal deposition occurs on the electrode in the first compartment, being driven by hypophosphite oxidation at the electrode in the other half-cell [36, 37],... 

The electrochemical mechanism was rejected by Salvago and Cavallotti [26] on the basis that it does not explain several features of electroless deposition of ferrous metals it does not account for the isotopic composition of the H2 gas evolved it does not explain the effect of the various solution components on reaction rate and it does not account for the homogeneous decomposition of very active solutions or the fact that they can give deposition on insulating surfaces. These authors put forward a chemical mechanism, involving various hydrolyzed nickel species, which they claim explains the observed behavior of the system ... 

This mechanism is based on the known importance of hydroxides in other deposition reactions, such as the anomalous codeposition of ferrous metal alloys [38-39], Salvago and Cavallotti claim an analogy with the mechanism of Ni2 + reduction from colloids in support of their proposed mechanism. There is no direct evidence for the hydrolyzed species, however. Furthermore, the mechanism does not explain two experimentally observed facts Ni deposition will proceed if the Ni2 + and the reducing agent are in separate compartments of a cell [36, 37] and P is not deposited in the absence of Ni2 +. The chemical mechanism does not take adequate account of the role of the surface state in catalysis of the reaction. It has no doubt been the extreme oversimplification, by some, of the electrochemical mechanism that has led other investigators to reject it. 

Mital et al. [40] studied the electroless deposition of Ni from DMAB and hypophosphite electrolytes, employing a variety of electrochemical techniques. They concluded that an electrochemical mechanism predominated in the case of the DMAB reductant, whereas reduction by hypophosphite was chemically controlled. The conclusion was based on mixed-potential theory the electrochemical oxidation rate of hypophosphite was found, in the absence of Ni2 + ions, to be significantly less than its oxidation rate at an equivalent potential during the electroless process. These authors do not take into account the possible implication of Ni2+ (or Co2+) ions to the mechanism of electrochemical reactions of hypophosphite. 

This mixed chemical/electrochemical mechanism has been critized by Randin [41], who points out that the main characteristics of the process are accommodated by a number of mechanisms, including the one described. 

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