Kinetics cathodic partial reaction

These three passive systems are important in the technique of anodic protection (see Chapter 21). The kinetics of the cathodic partial reaction and therefore curves of type I, II or III depend on the material and the particular medium. Case III can be achieved by alloying additions of cathodically acting elements such as Pt, Pd, Ag, and Cu. In principle, this is a case of galvanic anodic protection by cathodic constituents of the microstructure [50]. 

A discussion of the applicability of the MPT model to a particular electroless system ideally presumes knowledge of the kinetics and mechanisms of the anodic and cathodic partial reactions, and experimental verification of the interdependence or otherwise of these reactions. However, the study of the kinetics, catalysis, and mechanistic aspects of electroless deposition is an involved subject and is discussed separately. 

Thus, from the kinetic aspects, the cathodic partial reaction is an electrochemical reaction [Eq. (8.14)] that is preceded by a chemical reaction [Eq. (8.13)]. Paunovic (31)... 

Relationships of other type are observed in the case where both the conjugated reactions proceed through the same band (Fig. 13b). For example, the cathodic reaction (42b) can take place with the participation of valence electrons rather than conduction electrons, as was assumed above. Thus, reduction of an oxidizer leads to the injection of holes into the semiconductor, which are used then in the anodic reaction of semiconductor oxidation. In other words, the cathodic partial reaction provides the anodic partial reaction with free carriers of an appropriate type, so that in this case corrosion kinetics is not limited by the supply of holes from the bulk of a semiconductor to its surface. Here the conjugated reactions are in no way independent ones. 

Figure 13 shows schematically the current- and partial current-potential behavior of p-GaP ((a) and (b)) and n-GaP ((c) and (d)) in alkaline Fe(CN) solutions. In Fig. 13 (a) and (c), the partial current density at rest-potential or under open-circuit, and hence the etch rate, is limited by the cathodic partial reaction rate. This is the case for (111) GaP (for which the cathodic reaction is under kinetic control) and for (ITT) GaP at low Fe(CN) concentrations (for which the cathodic reaction is under diffusion control). In Fig. 13 (b) and (d), the partial current density at rest-potential or under open-circuit is limited by the anodic partial reactioi rate, which is limited by the OH diffusion rate (see Sec. 2.1) this is the case for (111) GaP at... 

The copper thus corrodes without any external current. The open circuit potential of a mixed electrode undergoing corrosion, is called the corrosion potential (in the literature it is sometimes also called the free corrosion potential). The corrosion potential has a value that lies in between the equilibrium potentials of the partial electrode reactions. In contrast to the equilibrium potential, which is a thermodynamic quantity, the corrosion potential is determined by kinetics its value depends on the rates of both the anodic and the cathodic partial reactions present. 

The anodic partial reaction (hypophosphite) and the cathodic partial reaction (nickel) obey Tafel kinetics ... 

The corrosion rate depends on the electrode kinetics of both partial reactions. If all of the electrochemical parameters of the anodic and cathodic partial reactions are known, in principle the rate may be predicted. According to Faraday s law, a linear relationship exists between the metal dissolution rate at any potential Vm the partial anodic current density for metal dissolution... 

Most corrosion phenomena are of electrochemical nature. They imply two or more electrode reactions the oxidation of a metal (anodic partial reaction) and the reduction of an oxidizing agent (cathodic partial reaction). To imderstand corrosion reactions one needs to study electrochemical thermodynamics and electrochemical kinetics of the partial reactions. For example, the corrosion of zinc in an acid environment proceeds according to the overall reaction ... 

The corrosion potential always lies between the equilibrium potentials of the respective anodic and cathodic partial reactions. Its exact value is determined by the kinetics of the partial reactions. 

Corrosion cells not only are formed when two different metals are in contact with each other but also can be the result of differences in the corrosive environment. A typical example is differential aeration cells, which are due to differences in accessibility of oxygen to the surface of a metal. Because the value of the corrosion potential depends on the kinetics of the anodic as well as the cathodic partial reactions, a different accessibility of oxygen results in a difference in corrosion potential and hence in the establishment of a corrosion cell. 

It is not appropriate here to consider the kinetics of the various electrode reactions, which in the case of the oxygenated NaCl solution will depend upon the potentials of the electrodes, the pH of the solution, activity of chloride ions, etc. The significant points to note are that (a) an anode or cathode can support more than one electrode process and b) the sum of the rates of the partial cathodic reactions must equal the sum of the rates of the partial anodic reactions. Since there are four exchange processes (equations 1.39-1.42) there will be eight partial reactions, but if the reverse reactions are regarded as occurring at an insignificant rate then... 

Figures 1.27a to d show how the Evans diagram can be used to illustrate how the rate may be controlled by either the polarisation of one or both of the partial reactions (cathodic, anodic or mixed control) constituting corrosion reaction, or by the resistivity of the solution or films on the metal surface (resistance control). Figures 1. lie and/illustrate how kinetic factors may be more significant than the thermodynamic tendency ( , u) and how provides no information on the corrosion rate.

When the laws of the partial reactions are preserved throughout the entire range of potentials (Butler, 1924), a general kinetic equation that is valid for both the anodic and cathodic currents can be written... 

Donahue [37] was one of the first to discuss interactions between partial reactions in electroless systems, specifically electroless Ni with NaH2PC>2 reducing agent, where mention was made of an interaction between H2PO2 ions and the cathodic Ni2+ reduction reaction with a calculated reaction order of 0.7. Donahue also derived some general relationships that may be used as diagnostic criteria in determining if interactions exist between the partial reactions in an electroless solution. Many electroless deposition systems have been reported to not follow the MPT model. However, mention of these solutions may be best left to a discussion of the kinetics and mechanism of electroless deposition, since a study of the latter is usually necessary to understand the adherence or otherwise of an electroless solution to the MPT model. 

Kinetics, The major factors determining the rate of the partial cathodic reaction are concentrations of metal ions and ligands, pH of the solution, and type and concentration of additives. These factors determine the kinetics of partial cathodic reaction in a general way, as given by the fundamental electrochemical kinetic equations discussed in Chapter 6. 

Three anodic partial reactions are considered active dissolution of two metals M and M with different kinetics in the absence of their ions in bulk solution and decomposition of water with the evolution of oxygen. The kinetics of the latter process is so slow on most corroding metals that only at very negative potentials can oxygen present in the solution be electroreduced and this eventually becomes limited by mass transport due to the limited solubility of oxygen in water. At even more negative potentials, hydrogen evolution takes place on the electrode surface. The cathodic reduction of some metal ions present on the electrode surface as a consequence of corrosion is also considered in Fig. 13(b). 

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-... 

The experimental evidence described above clearly shows that the cathodic and anodic partial reactions interact with each other, and that such interactions are an essential part of the mechanism of electroless copper deposition. It should be noted that the interdependence of partial reactions has also been demonstrated by Bindra et al. [127], based on their results of kinetic and mechanistic analysis. 

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