Mercury cathode reactions

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. 

Neta.1 Ama.lga.ms. Alkali metal amalgams function in a manner similar to a mercury cathode in an electrochemical reaction (63). However, it is more difficult to control the reducing power of an amalgam. In the reduction of nitro compounds with an NH4(Hg) amalgam, a variety of products are possible. Aliphatic nitro compounds are reduced to the hydroxylamines, whereas aromatic nitro compounds can give amino, hydra2o, a2o, or a2oxy compounds. 

The cathode reaction involves reduction of silver oxide to metallic silver [7440-22-4J. The reaction is a two-phase, heterogeneous reaction producing a substantially constant voltage during discharge. Some manganese dioxide may be added to the cathode, as in the case of mercury oxide cells. 

Here, the relative stability of the anion radical confers to the cleavage process a special character. Thus, at a mercury cathode and in organic solvents in the presence of tetraalkylammonium salts, the mechanism is expected16 to be an ECE one in protic media or in the presence of an efficient proton donor, but of EEC type in aprotic solvents. In such a case, simple electron-transfer reactions 9 and 10 have to be associated chemical reactions and other electron transfers (at the level of the first step). Those reactions are shown below in detail ... 

The principles outlined above are, of course, important in electro-synthetic reactions. The pH of the electrolysis medium, however, also affects the occurrence and rate of proton transfers which follow the primary electron transfer and hence determine the stability of electrode intermediates to chemical reactions of further oxidation or reduction. These factors are well illustrated by the reduction at a mercury cathode of aryl alkyl ketones (Zuman et al., 1968). In acidic solution the ketone is protonated and reduces readily to a radical which may be reduced further only at more negative potentials. 

The subsequent steps involve, among several proposed reactions, arylation of the mercury cathode, and release of lead, but most importantly they indicate [ArPbH] as evidence for polymer formation by the proposed route ... 

Kariv-Miller and Vajtner have successfully carried out selective defluorination of 1,3-difluorobenzene to fluorobenzene by cathodic reduction at a mercury cathode in diglyme containing Bu4NBF4 and a small amount of dimethylpyrrolidinium (DMP+) salt [6]. In this reaction, DMP+ is first reduced to form an amalgam, which reduces difluorobenzene catalytically as shown in Scheme 2.1. 

Figure 8-7 shows the anodic and cathodic polarization curves observed for a redox couple of hydrated titanium ions Ti /Ti on an electrode of mercury in a sulfuric add solution the Tafel relationship is evident in both anodic and cathodic reactions. FYom the slope of the Tafel plot, we obtain the symmetry factor P nearly equal to 0.5 (p 0.5). 

For further example, the decomposition of hydrogen peroxide, 2H202, , - 02. j + 2H20, which hardly occurs in aqueous basic solutions, catalytically proceeds on mercury electrodes as a mixed electrode process of anodic and cathodic reactions shown in Eqn. 11-3 ... 

Pyridinium salts tethered to ketones also undergo cathodic cyclization [1]. The reaction provides a convenient diastereoselective route to quinolizidine and indolizidine derivatives such as 203, 204 and 206, 208, and 209, and appears to hold significant promise as a route to alkaloids. Examples are portrayed and the optimal conditions are listed below the equations. A mercury cathode is preferred, as passivation occurs when lead is used, and the reaction does not occur... 

The intramolecular reaction of activated alkenes of the type 8 leads to the formation of 5- or 6-membered rings [26] and has been carried out only at a mercury cathode in a divided cell. In these processes, the activated alkene radical-anion is formed at a less negative potential than that required for cleavage of the carbon-bromine bond. Cyclization then occurs by nucleophilic substitution. 

Mesityl oxide at a mercury cathode in acetate buffer affords a mixture of tail-to-tail and head-to-tail hydrodimers. The initally formed reduction products undergo further reactions so that 32 and 33 are isolated [106, 107, 108]. A low yield of the head-to-head glycol has been isolated from some reactions [109, 110, 111]. The structures of these products were confirmed in 1955 [112], Methyl vinyl ketone yields a mixture of tail-to-tail and head-to-head hydrodimers [113],... 

Radical intermediates are also trapped by intramolecular reaction with an alkene or alkyne bond. At a mercury cathode this process competes with formation of the dialkylmercury [51], At a reticulated vitreous carbon cathode, this intramolecular cyclization of radicals generated by reduction of iodo compounds is an important process. Reduction of l-iododec-5-yne 5 at vitreous carbon gives the cyclopentane... 

Di(dibromomethyl)benzene is reduced at a mercury cathode to yield the poly(p-phenylenevinylene) 41. The reaction proceeds through a brominated poly-... 

The Kolbe reaction is earned out in an undivided cell with closely spaced platinum electrodes. Early examples used a concentrated, up to 50 %, aqueous solution of an alkali metal salt of the carboxylic acid and the solution became strongly alkaline due to hydrogen evolution at the cathode. Ingenious cells were devised with a renewing mercury cathode, which allowed removal of alkali metal amalgam. These experimental conditions have been replaced by the use of a solution of the carboxylic acid in methanol partially neutralised by sodium methoxide or trieth-... 

Attempts to prepare a bicyclobutane by reductive cydization of cyclobutane-1,3-diones have been unsuccessful [114]. a,o)-Dibenzoylalkanes are reduced at a mercury cathode to cycloalkanediols only when a ring size of 5 or 6 results. These reactions have been achieved using either aqueous ethanolic sodium hydroxide [115] or acetonitrile containing tetramethylammonium tetrafluoroborate [113] as electrolyte. Attempts to extend the process to formation of 7-membered rings lead only to oligomeric materials. 

The metal ion-water exchange process must be important in areas other than those of simple metal complex formation. For example, the discharge of nickel ion at a mercury cathode is probably controlled, not by diffusion, but by rearrangement of the water coordination shell. The estimated rates and heat of activation for this agree with the idea that this, in turn, is related to the water exchange process (66). Then too, the dimerization rate of metal hydroxy species may be controlled by water exchange. The reaction... 

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 variation of the overpotential with the current density for the reaction of hydrogen evolution on a mercury cathode in diluted sulfuric add at 25 °C is ... 

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