Zinc anodes, sacrificial

Note that zinc anodes are often used to protect steel and other relatively noble metals cathodically. In this case, the fasteners were acting as unintentional sacrificial anodes, protecting the stainless steel. Simple solutions to the problem would be to insulate the fasteners from the stainless steel electrically or to use stainless steel fasteners. 

Galvanic corrosion is the enhanced corrosion of one metal by contact with a more noble metal. The two metals require only being in electrical contact with each other and exposing to the same electrolyte environment. By virtue of the potential difference that exists between the two metals, a current flows between them, as in the case of copper and zinc in a Daniell cell. This current dissolves the more reactive metal (zinc in this case), simultaneously reducing the corrosion rate of the less reactive metal. This principle is exploited in the cathodic protection (Section 53.7.2) of steel structures by the sacrificial loss of aluminum or zinc anodes. 

As is well known, high-purity zinc corrodes much less rapidly in dilute acids than commercial purity material in the latter instance, impurities (particularly copper and iron) are exposed on the surface of the zinc to give local cathodes with low hydrogen overpotentials this result is of practical significance only in the use of zinc for sacrificial anodes in cathodic protection or for anodes in dry cells. In neutral environments, where the cathodic... 

Zinc should give a potential of -1 - 05 V vs. CU/CUSO4 and should have a driving potential of about -0-25 V with respect to cathodically protected steel. Zinc is therefore sufficiently negative to act as a sacrificial anode, and its first use for such purposes was on the copper-sheathed hulls of warships more than a century ago. The first attempts to fit zinc anodes to steel hulls, however, were a complete failure, for the sole reason that it had not been realised that the purity of the zinc was of paramount importance. The presence of even small amounts of certain impurities leads to the formation of dense adherent films, which cause the anodes to become inactive. 

The reason for the use of zinc as a power-impressed rather than a sacrificial anode is that the high concrete resistivity limits the current output, and a higher driving voltage than that provided by the e.m.f. between zinc and steel in concrete is used to provide the necessary current output. No cementitious overlay is required, although it may be advisable to paint the top surface of the sprayed zinc to prevent atmospheric corrosion of the zinc anode. 

Where sacrificial anode technology is employed, typically zinc or magnesium anodes are provided, although zinc anodes cannot be employed at over 140°F because of a reversal of potential above that temperature. In the boiler waterside circuits, they preferentially corrode,... 

FIGURE 12.20 In the cathodic protection of a buried pipeline or other large metal construction, the artifact is connected to a number of buried blocks of metal, such as magnesium or zinc. The sacrificial anodes (the magnesium block in this illustration) supply electrons to the pipeline (the cathode of the cell), thereby preserving it from oxidation. 

Low-valent cobalt pyridine complexes, electrogenerated from CoCl2 in DMF containing pyridine and associated with a sacrificial zinc anode, are also able to activate aryl halides to form arylzinc halides.223 This electrocatalytic system has also been applied to the addition of aryl bromides containing an electron-withdrawing group onto activated alkenes224 and to the synthesis of 4-phenylquinoline derivatives from phenyl halides and 4-chloroquinoline.225 Since the use of iron as anode appeared necessary, the role of iron ions in the catalytic system remains to be elucidated. 

The reactions appear to be similar to organometallic synthesis, where the reduction is performed by the metal instead of electricity. However, these reactions have been shown to be essentially different from the corresponding organometallic reactions. This method has valuable advantages. As the anode reaction is controlled, an undivided cell can be used, the reaction occurs in one-step, the conditions are quite simple, and so on. Sibille and Perichon et al. have found that the sacrificial zinc anode is quite effective for trifluoromethylation of aldehydes to form trifluoromethylated alcohols in almost quantitative yields (Eq. 6) [19]. The reaction proceeds via the reduction of Zinc(II) salts, followed by a chemical reaction between the reduced metal, CF3Br, and aldehyde. 

Furthermore, 2,2-difluoro-3-hydroxyesters are readily obtained from ClCF2COOMe and carbonyl compounds by electrolysis in a one-compartment cell using a sacrificial zinc anode and a nickel-complex catalyst [26], The catalytic cycle is shown in Scheme 3.11 and nickel zinc exchange is a key step. 

The use of Fe, indium, and zinc as sacrificial anodes in the electrochemically assisted Reformatsky reaction of ethyl 2-bromoalkanoates with succinic anhydride is found to be effective, giving l-ethyl-3-oxohexanedioates in 49 80%... 

Cathodic protection is a common approach to reducing corrosion of metals in marine service. Virtually every steel ship in the U.S. Fleet is protected by the placement of zinc anodes which corrode sacrificially, thereby protecting the steel. The benefits of cathodic protection are enormous - steel hulls would be quite short lived without it. 

The formation of arylzinc reagents can also be accomplished by using electrochemical methods. With a sacrificial zinc anode and in the presence of nickel 2,2-bipyridyl, polyfunctional zinc reagents of type 36 can be prepared in excellent yields (Scheme 14) . An electrochemical conversion of aryl halides to arylzinc compounds can also be achieved by a cobalt catalysis in DMF/pyridine mixture . The mechanism of this reaction has been carefully studied . This method can also be applied to heterocyclic compounds such as 2- or 3-chloropyridine and 2- or 3-bromothiophenes . Zinc can also be elec-trochemically activated and a mixture of zinc metal and small amounts of zinc formed by electroreduction of zinc halides are very reactive toward a-bromoesters and allylic or benzylic bromides . ... 

The sacrificial zinc anode process has also been used to perform the electrochemical cyclopropanation of alkenes from dibromomethane or bromochloromethane in CH2C12/... 

The electrochemical reduction of bromotrifluoromethane (CF3Br) in DMF in a cell fitted with a sacrificial zinc anode and a stainless steel or nickel cathode is a typical case where the organometallic compound formation can be realized according to two different processes, and where a transient species having a different reactivity compared to usual organometallics can be produced. 

The gradual disappearance of the catalyst precursor by formation of species ( ) -2-1-, which become more and more difficult to reduce as x increases, is highly counterbalanced by the in situ generation of Zn2+ ions coming from the sacrificial zinc anode. It allows one to dehalogenate the cobalt(II) species and to restore the cobalt catalyst into its initial form Co2+. 

Electrosyntheses are conducted in a one-compartment cell already described2, fitted with a sacrificial zinc anode and either a nickel foam or a stainless steel cathode. The presence of a supporting electrolyte is unnecessary, the ionic conductivity of the medium... 

If sacrificial anodes are used in condenser water boxes, it is desirable to select a type that will last for several years. Pure zinc or specially formulated zinc anodes have regained favor in recent years with some operators. High-purity zinc is said to be self-regulating and does not require a resistance to control the current. In some cases, the tube sheet and tube ends also are coated to reduce the current drain on the anodes. 

The formation of arylzinc reagents can also be accomplished by using electrochemical methods. With a sacrificial zinc anode and in the presence of nickel 2,2-bipyridyl, polyfunctional zinc reagents of type 5 can be prepared in excellent yields (Equation (5)). An electrochemical conversion of aryl halides to arylzinc compounds can also... 

The sacrificial anode system consists of a galvanic cell system in which the anode is made of a more active metal than the structure. The anode is attached to the structure and the anode output current may be measured. Magnesium and zinc anodes are commonly use in underground operations, zinc and aluminum alloy anodes in salt water. 

Anode, sacrificial — a rather easily oxidizable metal, e.g., zinc, magnesium, aluminum, electrically connected with a metal construction to be protected from corrosion. Due to the formation of a -> galvanic cell the sacrificial anode is oxidized instead of the metal to be protected. Sacrificial anodes are the oldest and simplest means for electrochemical corrosion protection. 

The principle of cathodic or sacrificial protection is founded in the natural potential differentials between different metals. Zinc anodes are intentionally placed in electrical contact with steel structures so that, as they corrode, the steel is protected. In other systems, a current may be applied to the structure to be protected so as to cause the current to flow to an artificial anode. 

C-C double bonds are elTiciently cyclopropanated electrochemically in a one-compartment cell fitted with a sacrificial zinc anode which allowed the formation of organozinc species from geminal dihaloalkanes. Electrolysis of dibromomethane in dichloromethane/dimethyl-formamide as solvent mixture is recommended as the standard condition for electrolysis. The best chemical yields were obtained with allylic alcohols and unfunctionalized alkenes. For example electrolysis of allyl alcohol 23 gave cyclopropane 24 in 70% yield. 

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