Mercury cathodes, hydrogen evolution

Adsorption of surface-active substances is attended by changes in EDL structure and in the value of the / -potential. Hence, the effects described in Section 14.2 will arise in addition. When surface-active cations [NR] are added to an acidic solution, the / -potential of the mercury electrode will move in the positive direction and cathodic hydrogen evolution at the mercury, according to Eq. (14.16), will slow down (Fig. 14.6, curve 2). When I ions are added, the reaction rate, to the contrary, will increase (curve 3), owing to the negative shift of / -potential. These effects disappear at potentiafs where the ions above become desorbed (at vafues of pofarization of less than 0.6 V in the case of [NR]4 and at values of polarization of over 0.9 V in the case of I ). 

FIGURE 15.3 pH dependence of potential (1) and polarization (2) in cathodic hydrogen evolution at a mercury electrode (lOmA/cm ), and the pH dependence of equilibrium potential of the hydrogen electrode (3). 

The second type of cell is a mercury pool type. A mercury cathode is particularly useful for separating easily reduced elements as a preliminary step in an analysis. l or example, copper, nickel, cobalt, silver, and cadmium are readily separated from ions such as aluminum, titanium, the alkali metals, and phosphates. The precipitated elements dissolve in the mercury little hydrogen evolution occurs even at high applied potentials because of large overvoltage effects. A coulomet-ric cell such as that shown in Figure 24-5b is also useful for coulometric determination of metal ions and certain types of organic compounds as well. 

Mercury Cells. The cathode material ia mercury cells, mercury [7439-97-6] Hg, has a high hydrogen overvoltage. Hydrogen evolution is suppressed and sodium ion reduction produces sodium amalgam [11110-32-4J, HgNa. 

For the cathodic reduction of organic substances, electrodes of two types are used the platinum and the mercury type. Those of the first type (platinum metals, and in alkaline solutions nickel) exfiibit low polarization in hydrogen evolution their potential can be pushed in the negative direction no further than to -0.3 V (RHE). Hydrogen readily adsorbs on these electrodes, which is favorable for reduction... 

Fig. 5.39 Tafel plot of hydrogen evolution at a mercury cathode in 0.15 m HC1, 3.2 m KI electrolyte at 25°C. (According to L. I. Krishtalik)...

Further evidence for surface effects upon the stereochemistry of electrochemical reduction of ketones comes from the discovery that the nature of the cathode material may effect stereochemistry. Reduction of 2-methylcyclo-hexanone affords pure trans-2-methylcyclohexanone at mercury or lead cathodes, a mixture of cis and trans alcohols (mostly trans) at nickel, and pure cis alcohol at copper 81 >. Reduction could not be effected at platinum presumably hydrogen evolution takes place before the potential necessary for reduction of the ketone can be reached. 

The stereochemistry of electrochemical reduction of acetylenes is highly dependent upon the experimental conditions under which the electrolysis is carried out. Campbell and Young found many years ago that reduction of acetylenes in alcoholic sulfuric acid at a spongy nickel cathode produces cis-olefins in good yields 126>. It is very likely that this reduction involves a mechanism akin to catalytic hydrogenation, since the reduction does not take place at all at cathode substances, such as mercury, which are known to be poor hydrogenation catalysts. The reduction also probably involves the adsorbed acetylene as an intermediate, since olefins are not reduced at all under these conditions and since hydrogen evolution does not occur at the cathode until reduction of the acetylene is complete. Acetylenes may also be reduced to cis olefins in acidic media at a silver-palladium alloy cathode, 27>. 

Mercury, lead, cadmium and graphite are commonly used cathode materials showing large overpotentials for hydrogen evolution in aqueous solution. Liquid mercury exhibits a clean surface and is very convenient for small-scale laboratory use. Sheet lead has to be degreased and the surface can be activated in an electrochemical oxidation, reduction cycle [3, 22], Cadmium surfaces are conveniently prepared by plating from aqueous cadmium(ii) solutions on a steel cathode. 

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-... 

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 ... 

The cross-section of a typical mercury button cell is shown in Fig. 3.24. The cathode and anode current collectors are the steel case and steel top, respectively. Attention is drawn to the sophisticated engineering design of this cell, which has provision for automatic venting of any pressure caused by hydrogen evolution, with any electrolyte displaced being absorbed in the safety sleeve between the inner and outer case. 

The advantages of the liquid surface and large overpotential for hydrogen evolution make mercury the material of choice for cathodic processes, unless the use of mercury is specifically contraindicated by some incompatibility with the system. Incompatibility can arise from strong specific absorption, as with some sulfur-containing compounds, or in high-temperature systems such as fused salts because of the low boiling point of mercury (356.6°C). 

We have just mentioned that one reason for a limited range of potentials in a particular SSE is the reactivity of the components of the SSE toward oxidation and reduction. It is also obvious that the limiting cathodic process in protic solvents, nos 1-9 in Table 4, must be reduction of protons or the equivalent, the proton donor. The unfavourable cathodic limit for reduction of protons can, however, be vastly improved by the use of mercury as the cathode material and a tetraalkylammonium salt as SSE (nos. 1 and 3). The reason for mercury being such a favourable material is its large overpotential (see Section 10) for the reduction of protons (hydrogen evolution reaction). We have already commented (p. 24) on the fact that the reduction of protons occurs many orders of magnitude faster on certain metals than on others, and this manifests itself by the overpotential, i.e., in order to make the reaction go at a measurable rate one has to increase the electrode potential from the equilibrium potential. Table 6 shows overpotentials for hydrogen evolution and... 

V versus SCE [64], The cathodic limiting reaction is hydrogen evolution, thus forming the acid anion as the coproduct. The apparent electrochemical window of acetic acid is about 4 V [63], whereas that of formic acid is around 1 V [49], For methanol and ethanol, there are reports on limiting cathodic potentials around -2 V versus mercury pool electrode [65], and their accessible electrochemical window is around 2 V. The cathodic limiting reactions are probably hydrogen evolution and an alkoxide formation. 

Zn(OH)2 is soluble in the alkaline solution as [Zn(OH)3]- until the solution is saturated with K[Zn(OH)3]. In addition Zn(OH)2 can be dehydrated to ZnO. An enhanced power density (when compared with the - Leclanche cell) is accomplished by using particulate zinc (flakes) soaked with the alkaline electrolyte solution. This anode cannot be used as a cell vessel like in the Leclanche cell. Instead it is mounted in the core of the cell surrounded by the separator the manganese dioxide cathode is pressed on the inside of the nickel-plated steel can used as battery container. In order to limit self-discharge by corrosion of zinc in early cells mercury was added, which coated the zinc effectively and suppressed hydrogen evolution because of the extremely low exchange current density... 

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