Anodic Elimination

In anodic elimination reactions two substituents X, e.g., hydrogen or C02, are oxidatively split off from the substrate to yield double or triple bonds (Eq. (136) ) 

Anodic dehydrogenations, e.g., oxidations of alcohols to ketones, have been treated in Sect. 8.1 and formation of olefins by anodic elimination of C02 and H+ from carboxylic acids was covered in Sect. 9.1. Therefore this section is only concerned with anodic bisdecarboxylations of v/odicarboxylic acids to olefins. This method gives usually good results when its chemical equivalent, the lead tetraacetate decarboxylation, fails. Combination of bisdecarboxylation with the Diels-Alder reaction or [2.2] -photosensitized cycloadditions provides useful synthetic sequences, since in this way the equivalent of acetylene can be introduced in cycloadditions. 

Anodic bisdecarboxylation is normally conducted at a platinum anode in water-pyridine-triethylamine as electrolyte and with both carboxyl groups neutralized. Synthetic applications of this method are illustrated by the following examples (Eq. (139-145)). 

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Both properties contributed to reducing the energy consumption in operating the cells. With mercury cells, there is the added advantage that the dimensional stability of the new anode eliminated the continual adjustment of electrode spacing that is necessary with graphite electrodes. 

Spence and Cook (S21) described the commercial operation of th Thompson Refinery of International Nickel Company in Manitoba wher the nickel sulfide matte is melted and cast into anodes containing 76% Ni 20% S, and the balance made up mostly of copper, cobalt, and iron. Th direct casting of the sulfide matte into anodes eliminated two pyro... 

The International Nickel Company developed a method to refine impure nickel sulfide anodes directly to metal, using mixed sulfate-chloride electrolyte [45]. Nickel sulfide (cz-Nf ) anodes can be cast directly from low-copper converter matte or from melted nickel sulfide concentrate produced by the matte separation process. Controlled cooling is necessary to produce anodes with the required mechanical properties. The cooling of anodes can take up to 36 hours. Using nickel sulfide anodes eliminates the intermediate roasting of the sulfide... 

Anodic elimination (oxidative desul-fanylation-deprotonation) occms when a carbonyl or CN group (X) is attached... 

A viable electrocatalyst operating with minimal polarization for the direct electrochemical oxidation of methanol at low temperature would strongly enhance the competitive position of fuel ceU systems for transportation appHcations. Fuel ceUs that directiy oxidize CH OH would eliminate the need for an external reformer in fuel ceU systems resulting in a less complex, more lightweight system occupying less volume and having lower cost. Improvement in the performance of PFFCs for transportation appHcations, which operate close to ambient temperatures and utilize steam-reformed CH OH, would be a more CO-tolerant anode electrocatalyst. Such an electrocatalyst would reduce the need to pretreat the steam-reformed CH OH to lower the CO content in the anode fuel gas. Platinum—mthenium alloys show encouraging performance for the direct oxidation of methanol. 

In electrogalvanizing, copper foil, and other oxygen-evolving appHcations, the greatest environmental contribution has been the elimination of lead-contaminated waste streams through replacement of the lead anode. In addition, the dimensionally stable characteristic of the metal anode iatroduces greater consistency and simplification of the process, thus creating a measure of predictabiUty, and a resultant iacreased level of safety. 

Pyrometa.llurgica.1 Processes. Nickel oxide ores are processed by pyrometaHurgical or hydrometaHurgical methods. In the former, oxide ores are smelted with a sulfiding material, eg, gypsum, to produce an iron—nickel matte that can be treated similarly to the matte obtained from sulfide ores. The iron—nickel matte may be processed in a converter to eliminate iron. The nickel matte then can be cast into anodes and refined electrolyticaHy. 

Other methods of preparing tertiary bismuthines have been used only to a limited extent. These methods iaclude the electrolysis of organometaUic compounds at a sacrificial bismuth anode (54), the reaction between a sodium—bismuth or potassium—bismuth alloy and an alkyl or aryl haUde (55), the thermal elimination of sulfur dioxide from tris(arenesulfiaato)bismuthines (56), and the iateraction of ketene and a ttis(dialkylainino)bismuthine (57). 

Oxidation and reduction reactions can be carried out usiag reformer hydrogen and oxygen from the air. To decide when electroorganic synthesis is likely to be a viable option for a desired product, some opportunity factors are use of cheaper feedstock elimination of process step(s) or a difficult reaction avoidance of waste disposal, toxic materials, and/or abiUty to recycle reagent and abiUty to obtain products from anode and cathode. 

There have been a number of cell designs tested for this reaction. Undivided cells using sodium bromide electrolyte have been tried (see, for example. Ref. 29). These have had electrode shapes for in-ceU propylene absorption into the electrolyte. The chief advantages of the electrochemical route to propylene oxide are elimination of the need for chlorine and lime, as well as avoidance of calcium chloride disposal (see Calcium compounds, calcium CHLORIDE Lime and limestone). An indirect electrochemical approach meeting these same objectives employs the chlorine produced at the anode of a membrane cell for preparing the propylene chlorohydrin external to the electrolysis system. The caustic made at the cathode is used to convert the chlorohydrin to propylene oxide, reforming a NaCl solution which is recycled. Attractive economics are claimed for this combined chlor-alkali electrolysis and propylene oxide manufacture (135). 

Cathodic protection using sacrificial anodes or applied current can retard or eliminate tuberculation. However, costs can be high and technical installation can be very difficult. Costs are markedly reduced if surfaces are coated (see Material substitution below). 

The heat exchanger is brought into the cathodic protection circuit with a correctly rated balancing resistor, thus eliminating the anodic danger according to... 

The electrochemical effects of slowly and erratically thickening oxide films on iron cathodes are, of course, eliminated when the film is destroyed by reductive dissolution and the iron is maintained in the film-free condition. Such conditions are obtained when iron is coupled to uncontrolled magnesium anodes in high-conductivity electrolytes and when iron is coupled to aluminium in high-conductivity solutions of pH less than 4-0 or more than 12 0 . In these cases, the primary cathodic reaction (after reduction of the oxide film) is the evolution of hydrogen. 

The fundamental requirements of a sacrificial anode are to impart sufficient cathodic protection to a structure economically and predictably over a defined period, and to eliminate, or reduce to an acceptable level, corrosion that would otherwise take place. 

The effect of the backfill is to lower the circuit resistance and thus reduce potential loss due to the environment. The additive resistances of the anode/backfill and backfill/soil are lower than the single anode/soil resistance. Backfills attract soil moisture and reduce the resistivity in the area immediately round the anode. Dry backfill expands on wetting, and the package expands to fill the hole in the soil and eliminate voids. 

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