Attackable electrodes

Wo can hence consider conjointly the case of attackable electrodes with that of the presence of metal ions in the electrolyte at unattaekable electrodes, and contrast this with the reduction by hydrogen at unattaekable electrodes. 

At attackable electrodes, like zinc, lead, and tin, the red tion generally proceeds further than at unattackable electro< 1 such as platinum, nickel, and mercury. The attempts utilize technically these properties of the cathode metals i a series of nitro-bodies led to important patents. 

The electrode potential of aluminium would lead us to expect attack by water. The inertness to water is due to the formation of an unreactive layer of oxide on the metal surface. In the presence of mercury, aluminium readily forms an amalgam (destroying the original surface) which is. therefore, rapidly attacked by water. Since mercury can be readily displaced from its soluble salts by aluminium, contact with such salts must be avoided if rapid corrosion and weakening of aluminium structures is to be prevented. 

Bromine has a lower electron affinity and electrode potential than chlorine but is still a very reactive element. It combines violently with alkali metals and reacts spontaneously with phosphorus, arsenic and antimony. When heated it reacts with many other elements, including gold, but it does not attack platinum, and silver forms a protective film of silver bromide. Because of the strong oxidising properties, bromine, like fluorine and chlorine, tends to form compounds with the electropositive element in a high oxidation state. 

The interelectrode insulators, an integral part of the electrode wall stmcture, are required to stand off interelectrode voltages and resist attack by slag. Well cooled, by contact with neighboring copper electrodes, thin insulators have proven to be very effective, particularly those made of alumina or boron nitride. Alumina is cheaper and also provides good anchoring points for the slag layer. Boron nitride has superior thermal conductivity and thermal shock resistance. 

Atmospheric corrosion is electrochemical ia nature and depends on the flow of current between anodic and cathodic areas. The resulting attack is generally localized to particular features of the metallurgical stmcture. Features that contribute to differences ia potential iaclude the iatermetaUic particles and the electrode potentials of the matrix. The electrode potentials of some soHd solutions and iatermetaUic particles are shown ia Table 26. Iron and sUicon impurities ia commercially pure aluminum form iatermetaUic coastitueat particles that are cathodic to alumiaum. Because the oxide film over these coastitueats may be weak, they can promote electrochemical attack of the surrounding aluminum matrix. The superior resistance to corrosion of high purity aluminum is attributed to the small number of these constituents. 

Figure 4-3a indicates the ideal case of a mixed electrode in free corrosion. Such situations do not arise in soils or aqueous media. Usually the attack is locally nonuniform (see Fig. 4-3b) in which the current balance is not equalized at small regions along the surface. This is a case of free corrosion without extended corro-... 

In this section the interaction of a metal with its aqueous environment will be considered from the viewpoint Of thermodynamics and electrode kinetics, and in order to simplify the discussion it will be assumed that the metal is a homogeneous continuum, and no account will be taken of submicroscopic, microscopic and macroscopic heterogeneities, which are dealt with elsewhere see Sections 1.3 and 20.4). Furthermore, emphasis will be placed on uniform corrosion since localised attack is considered in Section 1.6. 

It can be seen from Table 1.16 that differences in composition (nature or concentration) of the environment can lead to localised attack, and in Section 1.4 it was shown how differences in the activity of silver ions can give rise to a reversible concentration cell in which the silver electrodes in contact with the solution containing the lower and higher concentration of Ag ions are the anode and cathode, respectively. Concentration cells of this type are rare in practice, but can occur during the corrosion of copper and copper alloys. 

As may be seen from the diagram, silver in highly alkaline solution corrodes only within a narrow region of potential, provided complexants are absent. It is widely employed to handle aqueous solutions of sodium or potassium hydroxides at all concentrations it is also unaffected by fused alkalis, but is rapidly attacked by fused peroxides, which are powerful oxidising agents and result in the formation of the AgO ion Table 6.6 gives the standard electrode potentials of silver systems. 

Ruthenium, iridium and osmium Baths based on the complex anion (NRu2Clg(H20)2) are best for ruthenium electrodeposition. Being strongly acid, however, they attack the Ni-Fe or Co-Fe-V alloys used in reed switches. Reacting the complex with oxalic acid gives a solution from which ruthenium can be deposited at neutral pH. To maintain stability, it is necessary to operate the bath with an ion-selective membrane between the electrodes . 

The experiment may also be repeated using a platinum (indicator) electrode and a tungsten wire reference electrode. If the tungsten electrode has been left idle for more than a few days, the surface must be cleaned by dipping into just molten sodium nitrate (CARE ). The salt should be only just at the melting point or the tungsten will be rapidly attacked it should remain in the melt for a few seconds only and is then thoroughly washed with distilled water. 

Not only the electrolyte, but also the electrodes, directly or indirectly exert a chemical attack, either by an oxidation or reduction potential of the electrode material itself or by the generation of soluble oxidizing or reducing substances. 

Perhaps the most important single function of the solution environment is to control the mode of decomposition of reaction intermediates and hence the final products. This is particiflarly true in the case of electrode reactions producing carbonium ion intermediates since the major products normally arise from their reaction with the solvent. It is, however, possible to modify the product by carrying out the electrolysis in the presence of a species which is a stronger nucleophile than the solvent and, in certain non-nucleophilic solvents, products may be formed by loss of a proton or attack by the intermediate on further starting material if it is unsaturated. The major reactions of carbonium ions are summarized in Fig. 6. 

Reactive radicals may be generated at the electrodes in contact with the membranes, attacking the membranes. 

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