Cathode reaction types

Electrode Anode Reaction Cathode Reaction Type of Fuel Cell/Source... 

Chloiine is pioduced at the anode in each of the three types of electrolytic cells. The cathodic reaction in diaphragm and membrane cells is the electrolysis of water to generate as indicated, whereas the cathodic reaction in mercury cells is the discharge of sodium ion, Na, to form dilute sodium amalgam. 

The mechanism of the cathode reaction for all three types of Mn02 can best be described by two approximately one-electron steps. 

Cathode Reaction. There are many different types of manganese dioxide (18), having varying activity in batteries. The only type suitable for alkaline batteries is y-Mn02, the mineral form of which is nsutite. The chemical composition of has been described (19) by the general formula... 

It has been shown that paint films are so permeable to water and oxygen that they cannot affect the cathodic reaction, and that the anodic reaction may be modified by certain pigments. There are, however, many types of protective paint which do not contain inhibitive pigments. It is concluded that this class of paint prevents corrosion by virtue of its high ionic resistance, which impedes the movement of ions and thereby reduces the corrosion current to a very small value. 

Blocking of reaction sites The interaction of adsorbed inhibitors with surface metal atoms may prevent these metal atoms from participating in either the anodic or cathodic reactions of corrosion. This simple blocking effect decreases the number of surface metal atoms at which these reactions can occur, and hence the rates of these reactions, in proportion to the extent of adsorption. The mechanisms of the reactions are not affected and the Tafel slopes of the polarisation curves remain unchanged. Behaviour of this type has been observed for iron in sulphuric acid solutions containing 2,6-dimethyl quinoline, /3-naphthoquinoline , or aliphatic sulphides . 

Aluminum is directly applied in its metallic form when it serves as battery anode. The battery concepts considered are in general single-use types (primary batteries). The most developed systems belong to the metal-air batteries, using the reduction of atmospheric oxygen as the cathode reaction, e.g., (-) A1 / KOH / 02 (+) or (-) A1 / seawater / 02 (+). The main discharge reactions are ... 

Anodic chlorine evolution by electrolysis of concentrated chloride solutions is used for the large-scale industrial production of chlorine. The cathodic reaction, which is the ionization of molecular chlorine, is used in certain types of batteries. 

In batteries of this type, solntions of lithium salts in thionyl chloride, SOCI2, are nsed as the electrolyte. Exceptionally, this strongly oxidizing solvent also serves as the active material for the cathodic reaction. Thus, during discharge thionyl chloride is electrochemicaUy reduced at a cathode made of carbon materials ... 

The electrons produced in the conduction band as a result of illumination can participate in cathodic reactions. However, since in n-type semiconductors the quasi-Fermi level is just slightly above the Fermi level, the excited electrons participating in a cathodic reaction will almost not increase the energy effect of the reaction. Their concentration close to the actual surface is low hence, it will be advantageous to link the n-type semiconductor electrode to another electrode which is metallic, and not illuminated, and to allow the cathodic reaction to occur at this electrode. It is necessary, then, that the auxiliary metal electrode have good catalytic activity toward the cathodic reaction. 

Analogous effects are seen at p-type semiconductors at which cathodic reactions are accelerated when the electrode is illuminated. For heightened effects, one can combine in a single cell an n- and a p-type semiconductor and allow the anodic reaction to occur at the former and the cathodic reaction to occur at the latter. 

Three general reaction types compare the activation-control reduction processes. In Fig. 25-12, in Case I, the single reversible corrosion potential (anode/cathode intersection) is in the active region. A wide range of corrosion rates is possible. In Case 2, the cathodic curve intersects the anodic curve at three potentials, one active and two passive. If the middle active/passive intersection is not stable, the lower and upper... 

In contrast to acidic electrolytes, chemical dissolution of a silicon electrode proceeds already at OCP in alkaline electrolytes. For cathodic potentials chemical dissolution competes with cathodic reactions, this commonly leads to a reduced dissolution rate and the formation of a slush layer under certain conditions [Pa2]. For potentials slightly anodic of OCP, electrochemical dissolution accompanies the chemical one and the dissolution rate is thereby enhanced [Pa6]. For anodic potentials above the passivation potential (PP), the formation of an anodic oxide, as in the case of acidic electrolytes, is observed. Such oxides show a much lower dissolution rate in alkaline solutions than the silicon substrate. As a result the electrode surface becomes passivated and the current density decreases to small values that correspond to the oxide etch rate. That the current density peaks at PP in Fig. 3.4 are in fact connected with the growth of a passivating oxide is proved using in situ ellipsometry [Pa2]. Passivation is independent of the type of cation. Organic compounds like hydrazin [Sul], for example, show a behavior similar to inorganic ones, like KOH [Pa8]. Because of the presence of a passivating oxide the current peak at PP is not observed for a reverse potential scan. 

Fig. 8-90. Normalized cathodic cur> rent of redox reactions of hydrated redox particles as a function of standard redox potential at n-type electrodes of zinc oxide / (n, cqx) = normalized cathodic reaction current n, = concentration of interfacial electrons Cqx = concentration of oxidant particles au = arbitrary unit. [From Morrison, 1969,1980.]...

Figure 8-42 illustrates the anodic and cathodic polarization curves observed for an outer-sphere electron transfer reaction with a typical thick film on a metallic niobium electrode. The thick film is anodically formed n-type Nb206 with a band gap of 5.3 eV and the redox particles are hydrated ferric/ferrous cyano-complexes. The Tafel constant obtained from the observed polarization curve is a- 0 for the anodic reaction and a" = 1 for the cathodic reaction these values agree with the Tafel constants for redox electron transfers via the conduction band of n-lype semiconductor electrodes already described in Sec. 8.3.2 and shown in Fig. 8-27. 

Figure 10-24 shows schematically the electron levels and the polarization curves for a cathodic hole iivjection in an n-type and a p-type electrode of the same semiconductor. The range of potential where the cathodic reaction occurs on the n-type electrode is more cathodic (more negative) than the range of potential for the cathodic reaction on the p-type electrode. The difference between the polarization potential aEd) (point N in the figure) of the n-type electrode and the polarization potential p (i) (point P in the figure) of the p-type electrode at a constant cathodic current i is equivalent to the difference between the Fermi level n r of interior electrons and the quasi-Fermi level of interfacial holes in... 

Figure 10-25 shows an energy diagram of a photoelectrol3ddc cell for decomposing water this cell is composed of a metallic cathode and an n-type semiconductor anode, on which the following anodic and cathodic reactions, Eqns. 10-53(a) and 10-53(b), proceed ... 

Type of fuel cell Conducting ion Anode reaction Cathode reaction... 

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. 

The simplest design of electrochemical cell has two electrodes dipping into the solution containing the substrate and the supporting electrolyte. A cell of this type is suitable for the Kolbe oxidation of carboxylate ions (see p. 316) where the anode reaction is given by Equation 1.1 and the cathode reaction is the evolution of hydrogen (Equation 1.2). Both the substrate and the hydrocarbon product are inert... 

Since the products of the electrolysis of aqueous NaCl will react if they come in contact with each other, an essential feature of any chloralkali cell is separation of the anode reaction (where chloride ion is oxidized to chlorine) from the cathode reaction (in which OH- and H2 are the end products). The principal types of chloralkali cells currently in use are the diaphragm (or membrane) cell and the mercury cell. 

The Leclanche cell, the inexpensive disposable flashlight-type cell, has been on the market for over 100 years, yet its chemistry is not completely understood. The cell consists of an outer zinc shell that acts as the anode (seen by the external circuit as the source of electrons and hence the negative terminal) and oxidizes away during operation of the cell, a carbon rod or disk that serves as the cathodic current collector (positive terminal), and a moist paste of manganese dioxide, ammonium chloride, and zinc chloride that fills the cell and acts as both the electrolyte and the source of the cathodic reaction (reduction of MnIV). Usually, graphite in the form of carbon black is added to the paste to increase the electrical conductivity. The basic reactions are... 

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. 

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