Mercury cathode

Sodium hydroxide is manufactured by electrolysis of concentrated aqueous sodium chloride the other product of the electrolysis, chlorine, is equally important and hence separation of anode and cathode products is necessary. This is achieved either by a diaphragm (for example in the Hooker electrolytic cell) or by using a mercury cathode which takes up the sodium formed at the cathode as an amalgam (the Kellner-Solvay ceW). The amalgam, after removal from the electrolyte cell, is treated with water to give sodium hydroxide and mercury. The mercury cell is more costly to operate but gives a purer product. 

L. radius, ray) Radium was discovered in 1898 by Mme. Curie in the pitchblende or uraninite of North Bohemia, where it occurs. There is about 1 g of radium in 7 tons of pitchblende. The element was isolated in 1911 by Mme. Curie and Debierne by the electrolysis of a solution of pure radium chloride, employing a mercury cathode on distillation in an atmosphere of hydrogen this amalgam yielded the pure metal. 

The conventional electrochemical reduction of carbon dioxide tends to give formic acid as the major product, which can be obtained with a 90% current efficiency using, for example, indium, tin, or mercury cathodes. Being able to convert CO2 initially to formates or formaldehyde is in itself significant. In our direct oxidation liquid feed fuel cell, varied oxygenates such as formaldehyde, formic acid and methyl formate, dimethoxymethane, trimethoxymethane, trioxane, and dimethyl carbonate are all useful fuels. At the same time, they can also be readily reduced further to methyl alcohol by varied chemical or enzymatic processes. 

Fig. 7. Mercury cathode electroly2er and decomposer (11) 1, brine level 2, metal anodes 3, mercury cathode, flowing along baseplate 4, mercury pump 5, vertical decomposer 6, water feed to decomposer 7, graphite packing, promoting decomposition of sodium amalgam 8, caustic Hquor exit 9, denuded mercury 10, brine feed 11, brine exit 12, hydrogen exit from decomposer 13, chlorine gas space 14, chlorine exit 15, wash water.

Electrolysis. GalHum can be extracted by direct electrolysis of the aluminate solution at a strongly agitated mercury cathode. The recovery from a sodium gallate solution resulting from the carbonation process is another possibiHty. This process is probably no longer operative because of the environmental problems associated with the mercury. 

Electrolytic Preparation of Chlorine and Caustic Soda. The preparation of chlorine [7782-50-5] and caustic soda [1310-73-2] is an important use for mercury metal. Since 1989, chlor—alkali production has been responsible for the largest use for mercury in the United States. In this process, mercury is used as a flowing cathode in an electrolytic cell into which a sodium chloride [7647-14-5] solution (brine) is introduced. This brine is then subjected to an electric current, and the aqueous solution of sodium chloride flows between the anode and the mercury, releasing chlorine gas at the anode. The sodium ions form an amalgam with the mercury cathode. Water is added to the amalgam to remove the sodium [7440-23-5] forming hydrogen [1333-74-0] and sodium hydroxide and relatively pure mercury metal, which is recycled into the cell (see Alkali and chlorine products). 

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 word calcium is derived from calx, the Latin word for lime. The Romans used large quantities of calcium oxide or lime as mortar in constmction (see Lime and limestone). Because calcium compounds are very stable, elemental calcium was not produced until 1808 when a mercury amalgam resulted from electrolysis of calcium chloride in the presence of a mercury cathode. However, attempts to isolate the pure metal by distilling the mercury were only marginally successful. 

H. Y. Castner (US/UK) and C. Kellner (Vienna) independently developed commercial mercury-cathode cell for chlor-alkali production... 

According to U.S. Patent 2,966,493, the 2,3-bis-(3-pyridyl)-2,3-butanedlol used as the starting material may be prepared as follows. A solution of 1,430 g of 3-acetyl-pyridine in 7,042 ml of a 1 N aqueous solution of potassium hydroxide is placed into a cathode chamber containing a mercury cathode with a surface of 353 cm and is separated from an anode chamber by an Alundum membrane. As anode a platinum wire is used and the anolyte consists of a 1 N solution of aqueous potassium hydroxide which Is replenished from time to time. 

A mercury cathode finds widespread application for separations by constant current electrolysis. The most important use is the separation of the alkali and alkaline-earth metals, Al, Be, Mg, Ta, V, Zr, W, U, and the lanthanides from such elements as Fe, Cr, Ni, Co, Zn, Mo, Cd, Cu, Sn, Bi, Ag, Ge, Pd, Pt, Au, Rh, Ir, and Tl, which can, under suitable conditions, be deposited on a mercury cathode. The method is therefore of particular value for the determination of Al, etc., in steels and alloys it is also applied in the separation of iron from such elements as titanium, vanadium, and uranium. In an uncontrolled constant-current electrolysis in an acid medium the cathode potential is limited by the potential at which hydrogen ion is reduced the overpotential of hydrogen on mercury is high (about 0.8 volt), and consequently more metals are deposited from an acid solution at a mercury cathode than with a platinum cathode.10... 

Controlled-potential separation of many metals can be effected with the aid of the mercury cathode. This is because the optimum control potential and the most favourable solution conditions for a given separation can be deduced from polarograms recorded with the dropping mercury electrode see Chapter 16. 

An important use of a mercury cathode is in the purification of electrolyte solutions, for example the removal of traces of heavy metals from potassium chloride solutions.-All such impurities have much more positive deposition... 

The evolution of nitrogen aids in removing dissolved air. A salt bridge (4 mm tube) attached to the saturated calomel electrode is filled with 3 per cent agar gel saturated with potassium chloride and its tip is placed within 1 mm of the mercury cathode when the mercury is not being stirred this ensures that the tip trails in the mercury surface when the latter is stirred. It is essential that the mercury-solution interface (not merely the solution) be vigorously stirred, and for this purpose the propeller blades of the glass stirrer are partially immersed in the mercury. 

Table 14.1 Deposition of metals at controlled potential of the mercury cathode...

Details have been collected for the determination of some 50 elements by this technique21,22 and it is possible to effect many difficult separations, such as Cu and Bi, Cd and Zn, Ni and Co it has been widely used in the nuclear energy industry. A number of organic compounds can also be determined by this procedure, e.g. trichloroacetic acid and 2,4,6-trinitrophenol are reduced at a mercury cathode in accordance with the equations... 

Notes 1, Gold anode 2, silver anode 3, mercury anode 4, mercury cathode for reagent see footnote J 5, trace of mercury(II) acetate dissolved in acetic acid/methanol mixture added as catalyst, t A, amperometric I, indicator P, potentiometric. 

It is necessary to consider the factors which affect the limiting current with a dropping mercury cathode. 

Polarographic maxima. Current-voltage curves obtained with the dropping mercury cathode frequently exhibit pronounced maxima, which are reproducible and which can be usually eliminated by the addition of certain appropriate maximum suppressors . These maxima vary in shape from sharp peaks to rounded humps, which gradually decrease to the normal diffusion-current curve as the applied voltage is increased. A typical example is shown in Fig. 16.3. Curve A is that for copper ions in 0.1 M potassium hydrogencitrate solution, and curve B is the same polarogram in the presence of 0.005 per cent acid fuchsine solution. 

The reductant differs from the oxidant merely by n electrons, and together they form an oxidation-reduction system. Consider the reversible reduction of an oxidant to a reductant at a dropping mercury cathode. The electrode potential is given by ... 

Electrolysis with a mercury cathode or with controlled cathode potential. (g) Application of physical methods utilising selective absorption, chromatographic separations, and ion exchange separations. 

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