Mercury hydrogen evolution

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. 

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 14.6 Influence of surface-active ions [N(C4H9)4]+ (curve 2) and I (curve 3) on the polarization curve for hydrogen evolution at a mercury electrode in acidic solutions (curve 1 is for the base electrolyte). 

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). 

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)...

In the presence of iodide ions, the overpotential at a mercury electrode decreases, although the adsorption of iodide is minimal in the potential region corresponding to hydrogen evolution. The adsorption of iodide... 

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 effect of the condensed adsorption layer on hydrogen evolution at mercury electrode has been studied by Ponomarev et al. [45]. 

The Co(II) -phenylthiourea-borax buffer system has been studied applying CSV at HMDE [69]. An irreversible peak observed at —1.5 V was attributed to the catalytic hydrogen evolution. The first reduction step, combined with the adsorptive accumulation of herbicide metribuzin at mercury electrode, has been used for its determination by adsorptive stripping voltammetry [70]. 

Fig. 7.73 The reaction order of the hydrogen-evolution reaction (on mercury) in respect to a hydrogen ion is equal to 1, as seen from the slope of the straight line.

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 importance of double layer structure on electrode kinetics was first shown by Frumkin for the hydrogen evolution reaction on mercury [44]. As a result of the structure of the electrochemical interface, the pre-electrode plane, i.e. the plane where the reactant undergoes electron transfer to become product, is such that the concentration of the reactant ion is different from that in the bulk solution and the corresponding potential difference with respect to the solution, (less than the applied electrode—solution potential difference ([Pg.34]

The first quantum mechanical treatment for the radiationless electron transfer was developed by Gurney [68] for hydrogen evolution on mercury. In his model, Gurney assumed that the intermediate H " is not... 

One of the most important reasons for the application of mercury to the construction of working electrodes is the very high overpotential for hydrogen evolution on such electrodes. Relative to a platinum electrode, the overpotential of hydrogen evolution under comparable conditions on mercury will be -0.8 to -1.0 V. It is therefore possible in neutral or (better) alkaline aqueous solutions... 

Also, the hydrogen evolution overpotential may be decreased when using this type of MFE. The mercury film thickness can be easily regulated by electrolytic deposition with a coulometric control. When the film is relatively thick, its thickness along the MFE surface may not be uniform. MFEs are not stable in time when the mercury film thickness is very low, due to the diffusion of mercury into the metallic support. 

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