Mercury, amalgam with sodium

A similar reaction can be carried out in which mercury is amalgamated with sodium ... 

The reduction of lactones of polyhydroxy carboxylic acids to the corresponding aldoses with sodium amalgam can be successfully achieved by electroreduction at a mercury cathode, provided that the catholyte contains salts of amalgam-forming metals. The electroreduction of the lactones of n-ribonic and n-arabinonic acids to n-ribose and n-arabinose, respectively, is performed at a mercury cathode, with sodium, potassium, or zinc sulfate (or their mixtures) as the catholyte, and platinum gauze as the anode, immersed in aqueous, 15% sulfuric acid. The electrolyzer compartments are separated by a diaphragm, and the electrolysis is performed with intensive stirring of the catholyte, which is maintained at a temperature of +5 to +12° and at a constant pH (adjusted by additions of dilute sulfuric acid). Yields of monosaccharide are increased by addition of boric acid to the reaction mixture. 

Production of CI2 and NaOH by electrolysis of NaCl is a huge industry with annual production capacity in excess of 50 million tons of NaOH per year. Membrane cells are the state-of-the-art technology, but mercury and diaphragm cells are still used because the capital cost for their replacement is substantial. The mercury cell technology is more than a century old and stiU accounts for nearly half of the world s production capacity. Chlorine evolves from a DSA (dimensionally stable anode) situated above a pool of mercury with NaCl brine in between. Mercury reacts with sodium to form sodium amalgam, which is removed and hydrolyzed in a separate reactor. 

Many metals are oxidised by water. At ordinary temperatures the more electropositive metals, for example, sodium, calcium (or their amalgams with mercury), react to give hydrogen, for example ... 

The metal is slowly oxidised by air at its boiling point, to give red mercury(II) oxide it is attacked by the halogens (which cannoi therefore be collected over mercury) and by nitric acid. (The reactivity of mercury towards acids is further considered on pp. 436, 438.) It forms amalgams—liquid or solid—with many other metals these find uses as reducing agents (for example with sodium, zinc) and as dental fillings (for example with silver, tin or copper). 

Rubidium can be liquid at room temperature. It is a soft, silvery-white metallic element of the alkali group and is the second most electropositive and alkaline element. It ignites spontaneously in air and reacts violently in water, setting fire to the liberated hydrogen. As with other alkali metals, it forms amalgams with mercury and it alloys with gold, cesium, sodium, and potassium. It colors a flame yellowish violet. Rubidium metal can be prepared by reducing rubidium chloride with calcium, and by a number of other methods. It must be kept under a dry mineral oil or in a vacuum or inert atmosphere. 

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). 

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. 

Recently it has been shown that the oxides of the platinum metals can have a higher corrosion resistance than the metals themselves , and have sufficient conductivity to be used as coatings for anodes, e.g. with titanium cores. Anodes with a coating of ruthenium dioxide are being developed for use in mercury cells for the electrolysis of brine to produce chlorine , since they are resistant to attack if in contact with the sodium-mercury amalgam. 

Mercury forms amalgams with numerous metals. Usually, this conversion is very exothermic, therefore it can present risks the reaction can become violent if a metai is added too quickly into mercury. Accidents have been described with caicium (at 390°C), aluminium, alkali metals (lithium, sodium, potassium, rubidium) and cerium. Some of these alloys are very inflammable, in particular the Hg-Zn amalgam. 

Interaction of sodium and mercury to form sodium amalgam is violently exothermic, and moderation of the reaction with an inert liquid, or by adding mercury slowly to the sodium is necessary. Even so, temperatures of 400°C may be attained. 

This process not only produces chlorine, it is also a way in which enormous quantities of sodium hydroxide are produced with hydrogen being the other product. Two types of cells are in use. The first and by far the most important employs a diaphragm to separate the anode and cathode compartments. A second type of cell utilizes a mercury cathode with which the sodium forms an amalgam. 

In many applications, such as the analysis of mercury in open ocean seawater, where the mercury concentrations can be as small as 10 ng/1 [468,472-476], a preconcentration stage is generally necessary. A preliminary concentration step may separate mercury from interfering substances, and the lowered detection limits attained are most desirable when sample quantity is limited. Concentration of mercury prior to measurement has been commonly achieved either by amalgamation on a noble-metal metal [460,467, 469,472], or by dithizone extraction [462,472,475] or extraction with sodium diethyldithiocarbamate [475]. Preconcentration and separation of mercury has also been accomplished using a cold trap at the temperature of liquid nitrogen. 

The final class of electrodes we encounter are amalgam electrodes, formed by dissolving a metal in elemental (liquid) mercury, generally to yield a solid. We denote an amalgam with brackets, so the amalgam of sodium in mercury is written as Na(Hg). The properties of such amalgams can be surprisingly different from their... 

Elemental sulfur is present in most soils and sediments (especially anaerobic), and is sufficiently soluble in most common organic solvents that the extract should be treated to remove it prior to analysis by ECD-GC or GC-MS. The most effective methods available are (1) reaction with mercury or a mercury amalgam [466] to form mercury sulfide (2) reaction with copper to form copper sulfide or (3) reaction with sodium sulfite in tetrabutyl ammonium hydroxide (Jensen s reagent) [490]. Removal of sulfur with mercury or copper requires the metal surface to be clean and reactive. For small amounts of sulfur, it is possible to include the metal in a clean-up column. However, if the metal surface becomes covered with sulfide, the reaction will cease and it needs to be cleaned with dilute nitric acid. For larger amounts of sulfur, it is more effective to shake the extract with Jensen s reagent [478]. 

Silver is usually extracted from high-grade ores by three common processes that have been known for many years. These are amalgamation, leaching, and cyanidation. In one amalgamation process, ore is crushed and mixed with sodium chloride, copper sulfate, sulfuric acid, and mercury, and roasted in cast iron pots. The amalgam is separated and washed. Silver is separated from its amalgam by distillation of mercury. 

Sodium forms alloys with a number of metals including lead, chromium, mercury, aluminum, silicon, and iron. With mercury, it forms sodium amalgam. Sodium-lead alloy is commercially used to produce tetraethyllead, which was used historically as an additive to gasoline ... 

Various processes separate rare earths from other metal salts. These processes also separate rare earths into specific subgroups. The methods are based on fractional precipitation, selective extraction by nonaqueous solvents, or selective ion exchange. Separation of individual rare earths is the most important step in recovery. Separation may be achieved by ion exchange and solvent extraction techniques. Also, ytterbium may be separated from a mixture of heavy rare earths by reduction with sodium amalgam. In this method, a buffered acidic solution of trivalent heavy rare earths is treated with molten sodium mercury alloy. Ybs+ is reduced and dissolved in the molten alloy. The alloy is treated with hydrochloric acid, after which ytterbium is extracted into the solution. The metal is precipitated as oxalate from solution. 

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