Sodium amalgams

Sodium amalgams may be made by adding small pieces of sodium to mercury, by electrolysis of sodium salts using a mercury cathode, or by adding mercury to molten sodium beneath an inert liquid such as paraffin oil. The following procedure, suggested by Vanstone,1 has advantages in both speed and simplicity. 

A sample of the material, dissolved in a little dilute sodium carbonate solution, should not decolorise a drop of permanganate solution. 

Cinnamic acid may also be hydrogenated catalytically (p. 377). If the sodium amalgam method is chosen, the catalytic method should be practised with phenol. 

Sodium Amalgam.—Mercury and sodium react with violence, sparks and flames being produced the amalgam must therefore be made inside a fume chamber and goggles must be worn. In a mortar of moderate size 300 g. of mercury are warmed to 30°—40° and the sodium (6 5 g. in all), cut into small cubes, is introduced on the point of a glass rod about 30 cm. long the pieces are pushed under the surface of the liquid in rapid succession. A porous plate is used as a cover for the mortar in order to provide protection against spurt- 

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Usually prepared by the action of NaCN on benzaldehyde in dilute alcohol. It is oxidized by nitric acid to benzil, and reduced by sodium amalgam to hydrobenzoin PhCHOHCHOHPh by tin amalgam and hydrochloric acid to des-oxybenzoin, PhCH2COPh and by zinc amalgam to stilbene PhCH = CHPh. It gives an oxime, phenylhydrazone and ethanoyl derivative. The a-oxime is used under the name cupron for the estimation of copper and molybdenum. 

Colourless crystals m.p. 122 C. It is prepared by reducing an alcoholic solution of xanthone with sodium amalgam. 

Originally, general methods of separation were based on small differences in the solubilities of their salts, for examples the nitrates, and a laborious series of fractional crystallisations had to be carried out to obtain the pure salts. In a few cases, individual lanthanides could be separated because they yielded oxidation states other than three. Thus the commonest lanthanide, cerium, exhibits oxidation states of h-3 and -t-4 hence oxidation of a mixture of lanthanide salts in alkaline solution with chlorine yields the soluble chlorates(I) of all the -1-3 lanthanides (which are not oxidised) but gives a precipitate of cerium(IV) hydroxide, Ce(OH)4, since this is too weak a base to form a chlorate(I). In some cases also, preferential reduction to the metal by sodium amalgam could be used to separate out individual lanthanides. 

Sodium amalgam. The amalgam which is generally employed for reductions contains from 1 to 3 per cent, of sodium. Amalgams with a greater sodium content than 1 2 per cent, are solid at the ordinary temperature and can be powdered in a mortar the 1 2 per cent, amalgam is semi-solid at room temperature but is completely fluid at 50°. Two methods of preparation are available. 

Commercial xanthhydrol may be used, but the pure white product, m.p. 120-121°, obtained by the reduction of xanthone with sodium amalgam (Section VII,16) gives better results. 

If pure triphenylchloromethane and freshly prepared sodium amalgam are used, the yield of sodium triphenyl-methide should be almost quantitative but is usually 0 15 mol per htre (1). The reagent should be used as soon as possible after its preparation. 

The best results are obtained with freshly prepared xanthhydrol (reduction of xanthone with sodium amalgam. Section VII,16). Dissolve 0 -25 g. of xanthhydrol and 0 -25g. of the primary sulphonamide in 10 ml. of glacial acetic acid. Shake for 2-3 minutes at the laboratory temperature and allow to stand for 60-90 minutes. Filter oflf the derivative, recrystallise it from dioxan-water (3 1), and dry at room temperature under water pump suction for 30 minutes. 

Hydrocinnamic acid may also be prepared by the reduction of cinnamic acid with sodium and alcohol or with sodium amalgam or with hydrogen in the presence of Adams platinum oxide catalyst (Section 111,150) ... 

Phenyl salicylate upon heating alone yields xanthone the latter is reduced by sodium amalgam to xanthhydrol ... 

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. 

The catholyte from diaphragm cells typically analyzes as 9—12% NaOH and 14—16% NaCl. This ceUHquor is concentrated to 50% NaOH in a series of steps primarily involving three or four evaporators. Membrane cells, on the other hand, produce 30—35% NaOH which is evaporated in a single stage to produce 50% NaOH. Seventy percent caustic containing very Httie salt is made directiy in mercury cell production by reaction of the sodium amalgam from the electrolytic cells with water in denuders. 

Overvoltages for various types of chlor—alkali cells are given in Table 8. A typical example of the overvoltage effect is in the operation of a mercury cell where Hg is used as the cathode material. The overpotential of the H2 evolution reaction on Hg is high hence it is possible to form sodium amalgam without H2 generation, thereby eliminating the need for a separator in the cell. 

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.

The mercury cell operates efficiently because of the higher overpotential of hydrogen on mercury to achieve the preferential formation of sodium amalgam. Certain trace elements, such as vanadium, can lower the hydrogen overpotential, however, resulting in the release of hydrogen in potentially dangerous amounts. 

Manufacture is either by reaction of molten sodium with methyl alcohol or by the reaction of methyl alcohol with sodium amalgam obtained from the electrolysis of brine in a Castner mercury cell (78). Both these methods produce a solution of sodium methylate in methanol and the product is offered in two forms a 30% solution in methanol, and a soHd, which is a dry, free-flowing white powder obtained by evaporating the methanol. The direct production of dry sodium methylate has been carried out by the introduction of methanol vapors to molten sodium in a heavy duty agitating reactor. The sohd is supphed in polyethylene bags contained in airtight dmms filled in a nitrogen atmosphere. 

Reduction of propylene oxide to propylene is accompHshed by use of metallocenes, such as Ti(AH5)2Cl2, and sodium amalgam (88). 

Sodium amalgam is employed ia the manufacture of sodium hydroxide sodium—potassium alloy, NaK, is used ia heat-transfer appHcations and sodium—lead alloy is used ia the manufacture of tetraethyllead and tetramethyUead, and methylcyclopentadienylmanganesetricarbonyl, a gasoline additive growing ia importance for improving refining efficiency and octane contribution. 

Xyhtol is synthesized by reduction of D-xylose catalyticahy (40), electrolyticahy (41), and by sodium amalgam (42). D-Xylose is obtained by hydrolysis of xylan and other hemiceUulosic substances obtained from such sources as wood, com cobs (43), almond shells, hazelnuts, or oHve waste (44). Isolation of xylose is not necessary xyhtol results from hydrogenation of the solution obtained by acid hydrolysis of cottonseed hulls (45). 

D,L-Mannitol has been obtained by sodium amalgam reduction of D,L-mannose. The identical hexitol is formed from the formaldehyde polymer, acrose, by conversion through its osazone and osone to D,L-fmctose (a-acrose) followed by reduction (83). 

Reduction of vanillin by means of platinum black in the presence of ferric chloride gives vanillin alcohol in excellent yields. In 1875, Tiemann reported the reduction of vanillin to vanillin alcohol by using sodium amalgam in water. The yields were poor, however, and there were a number of by-products. High yields of vanillin alcohol have been obtained by electrolytic reduction. 

Twenty-four years before its detection in nature PEA was first synthesized in 1876 (56) by reducing phenylacetaldehyde [122-78-1] with sodium amalgam. Then, in 1900, it was independently identified in otto of rose (57) and rose water (58). Subsequently, PEA has been identified in numerous flower oils such as ylang-ylang, narcissus, hyacinth, lily, neroH, and geranium as well as various other natural products like tea, tobacco, orange juice, beer, cigarette smoke, etc. 

Dithionites. Although the free-dithionous acid, H2S2O4, has never been isolated, the salts of the acid, in particular zinc [7779-86-4] and sodium dithionite [7775-14-6] have been prepared and are widely used as industrial reducing agents. The dithionite salts can be prepared by the reaction of sodium formate with sodium hydroxide and sulfur dioxide or by the reduction of sulfites, bisulfites, and sulfur dioxide with metallic substances such as zinc, iron, or zinc or sodium amalgams, or by electrolytic reduction (147). 

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