Electrolysis fused electrolytes

Fluorine cannot be prepared directly by chemical methods. It is prepared in the laboratory and on an industrial scale by electrolysis. Two methods are employed (a) using fused potassium hydrogen-fluoride, KHFj, ill a cell heated electrically to 520-570 K or (b) using fused electrolyte, of composition KF HF = 1 2, in a cell at 340-370 K which can be electrically or steam heated. Moissan, who first isolated fluorine in 1886, used a method very similar to (b) and it is this process which is commonly used in the laboratory and on an industrial scale today. There have been many cell designs but the cell is usually made from steel, or a copper-nickel alloy ( Monel metal). Steel or copper cathodes and specially made amorphous carbon anodes (to minimise attack by fluorine) are used. Hydrogen is formed at the cathode and fluorine at the anode, and the hydrogen fluoride content of the fused electrolyte is maintained by passing in... 

Production. MetaUic strontium was first successfully produced by the electrolysis of fused strontium chloride. Although many attempts were made to develop this process, the deposited metal has a tendency to migrate into the fused electrolyte and the method was not satisfactory. A more effective early method was that described in Reference r5. Strontium oxide is reduced thermally with aluminum according to the following reaction ... 

Titanium metal also can be produced by electrolytic methods. In electrolysis, fused mixtures of titanium tetrachloride or lower chlorides with alkaline earth metal chlorides are electrolyzed to produce metal. Also, pure titanium can be prepared from electrolysis of titanium dioxide in a fused bath of calcium-, magnesium- or alkali metal fluorides. Other alkali or alkaline metal salts can be substituted for halides in these fused baths. Other titanium com-pouds that have been employed successfully in electrolytic titanium production include sodium fluotitanate and potassium fluotitanate. 

Faraday s law holds for solid electrolytic conductors as well as for fused electrolytes and solutions this is shown by the results of Tubandt and Eggert (1920) on the electrolysis of the cubic form of silver iodide quoted in Table III. The quantities of silver deposited in an ordinary... 

The composition of the solvent has a dramatic influence on the electrodeposition process of refractory metals in fused electrolytes [1]. Also, in contrast to other metals prepared by electrolysis at high temperatures such as alkali metals, magnesium or aluminium, all the refractory metals exist in a variety of oxidation states. The metal chlorides undergo disproportionation reactions leading to formation of seemingly colloidal metal in the melt. The... 

In 1854 Henri Etienne Sainte-Claire Deville prepared silicon by electrolysis in coimection with his pioneer work with aluminum. He used a fused electrolyte of impure sodium aluminum chloride. The aluminum metal, obtained at the cathode, contained 10% silicon. When dissolved in add, bright silicon laminae stayed undissolved. It is interesting to note that Deville expressed the opinion that the element silicon is not a real metal. 

Examples of the products of the electrolysis of molten or fused electrolytes are shown in Table 9.9. 

Fused-salt electrolysis of K2NbFy is not an economically feasible process because of the low current efficiency (31). However, electrowinning has been used to obtain niobium from molten alkaU haUde electrolytes (32). The oxide is dissolved in molten alkaU haUde and is deposited in a molten metal cathode, either cadmium or zinc. The reaction is carried out in a ceramic or glass container using a carbon anode the niobium alloys with the cathode metal, from which it is freed by vacuum distillation, and the niobium powder is left behind. 

Sir Humphry Davy first isolated metallic sodium ia 1807 by the electrolytic decomposition of sodium hydroxide. Later, the metal was produced experimentally by thermal reduction of the hydroxide with iron. In 1855, commercial production was started usiag the DeviUe process, ia which sodium carbonate was reduced with carbon at 1100°C. In 1886 a process for the thermal reduction of sodium hydroxide with carbon was developed. Later sodium was made on a commercial scale by the electrolysis of sodium hydroxide (1,2). The process for the electrolytic decomposition of fused sodium chloride, patented ia 1924 (2,3), has been the preferred process siace iastallation of the first electrolysis cells at Niagara Falls ia 1925. Sodium chloride decomposition is widely used throughout the world (see Sodium compounds). 

Electrolysis of Fused Sodium Hydroxide. The first successful electrolytic production of sodium was achieved with the Castner cell (2) ... 

Other commercial cells designed for the electrolysis of fused sodium chloride iaclude the Danneel-Lon2a cell and the Seward cell, both used before World War I. The former had no diaphragm and the sodium was confined to the cathode 2one by salt curtains (ceramic walls) the latter utili2ed the contact-electrode principle, where the cathode was immersed only a few millimeters ia the electrolyte. The Ciba cell was used over a longer period of time. 

Electrolytic Processes. The electrolytic procedures for both electrowinning and electrorefining beryUium have primarily involved electrolysis of the beryUium chloride [7787-47-5], BeCl2, in a variety of fused-salt baths. The chloride readUy hydrolyzes making the use of dry methods mandatory for its preparation (see Beryllium compounds). For both ecological and economic reasons there is no electrolyticaUy derived beryUium avaUable in the market-place. 

Anode Applications. Graphite has been used as the primary material for electrolysis of brine (aqueous) and fused-salt electrolytes, both as anode and cathode. Technological advances, however, have resulted in a dimensionally stable anode (DSA) consisting of precious metal oxides deposited on a titanium substrate that has replaced graphite as the primary anode (38—41) (see Alkali and chlorine products). 

Chemical Production. Electrolytic production of chemicals is conducted either by solution (water) electrolysis or fused-salt electrolysis. Fluorine, chlorine, chlorate, and manganese dioxide are Hberated from water solutions magnesium and sodium are generated from molten salt solutions. 

The development of electrical power made possible the electrochemical industry. Electrolysis of sodium chloride produces chlorine and either sodium hydroxide (from NaCl in solution) or metallic sodium (from NaCl fused). Sodium hydroxide has applications similar to sodium carbonate. The ad vantage of the electrolytic process is the production of chlorine which has many uses such as production of polyvinyl chloride. PVC, for plumbing, is produced in the largest quantity of any plastic. 

In 1808, Sir Humphry Davy reported the production of Mg in the form of an amalgam by electrolytic reduction of its oxide using a Hg cathode. In 1828, the Fr scientist A. Bussy fused Mg chloride with metallic K and became the first to produce free metallic Mg. Michael Faraday, in 1833, was the first to produce free metallic Mg by electrolysis, using Mg chloride. For many years, however, the metal remained a laboratory curiosity. In 1886, manuf of Mg was undertaken on a production scale in Ger, using electrolysis of fused Mg chloride. Until 1915, Ger remained the sole producer of Mg. However, when a scarcity of Mg arose in the USA as a result of the Brit blockade of Ger in 1915, and the price of Mg soared from 1.65 to 5.00 per lb, three producers initiated operations and thus started a Mg industry in the USA. Subsequently, additional companies attempted production of Mg, but by 1920 only two producers remained — The Dow Chemical Co (one of the original three producers) and. the American Magnesium Corn. In 1927. the latter ceased production, and Dow continued to be the sole domestic producer until 1941. The source of Mg chloride was brine pumped from deep wells. In 1941, Dow put a plant into operation at Freeport, Texas, obtaining Mg chloride from sea-... 

It has been shown that the electrodeposition of molybdenum chalcogenides from high-temperature molten salts can give large, well-defined crystals of these compounds. The preparation of M0S2 as well as WS2 by electrolytic reduction of fused salts was first reported by Weiss [145], who produced small hexagonal blue-gray platelets under drastic conditions of electrolysis. Schneemeyer and Cohen... 

The first production of aluminum was by the chemical reduction of aluminum chloride with sodium. The electrolytic process, based on the fused salt electrolysis of alumina dissolved in cryolite, was independently developed in 1886 by C. M. Hall in America and P. L. Heroult in France. Soon afterwards a chemical process for producing pure alumina from bauxite, the commercial source of aluminum, was developed by Bayer and this led to the commercial production of aluminum by a combination of the Bayer and the Hall-Heroult processes. At present this is the main method which supplies all the world s needs in primary aluminum. However, a few other processes also have been developed for the production of the metal. On account of problems still waiting to be solved none of these alternative methods has seen commercial exploitation. 

Sodium chloride, 22 797-822. See also Salt analytical methods for, 22 811-812 applications of, 22 814-820 from brine, 5 800-801 corrosive effect on iron, 7 806 deposits of, 22 798, 799, 805 described, 22 797 in detergent formulations, 3 418 economic aspects of, 22 810-811 electrolysis of, 22 760 electrolysis of fused, 22 769-772 electrolytic decomposition, 6 175-177 environmental impact of, 22 813-814, 817... 

Electrolytic reduction and thermal decomposition have not yet been apphed in large scale commercial methods. Electrolysis of alkali or alkaline earth borates produces boron in low purity. Electrolytic reduction of fused melts of boron trioxide or potassium tetrafluroborate in potassium chloride yield boron in high purity. Also, boron tribromide or boron hydrides may be thermally dissociated hy heating at elevated temperatures. 

Lithium metal is produced commercially by electrolysis of a fused eutectic mixture of hthium chloride-potassium chloride (45% LiCl) at 400 to 450°C. The eutectic mixture melts at 352°C in comparison to the pure LiCl melting at 606°C. Also, the eutectic melt is a superior electrolyte to LiCl melt. (Landolt, P.E. and C. A. Hampel. 1968. Lithium. In Encyclopedia of Chemical Elements.C. A. Hampel, Ed. Reinhold Book Corp. New York.) Electrolysis is carried out using graphite anodes and steel cathodes. Any sodium impurity in hthium chloride may be removed by vaporizing sodium under vacuum at elevated temperatures. All commercial processes nowadays are based on electrolytic recovery of the metal. Chemical reduction processes do not yield high purity-grade metal. Lithium can be stored indefinitely under airtight conditions. It usually is stored under mineral oil in metal drums. 

Manganese also is produced by electrolysis of fused salt. In one such process, the reduced MnO is blended to molten calcium fluoride and lime. The latter is used to neutralize silica in the ore. The fused composition of these salts is electrolyzed at 1,300°C in an electrolytic cell made up of high temperature ceramic material, using a carbon anode and a cathode consisting of iron bars internally cooled by water. 

There are two electrolytic methods that are of major importance. One involves the electrolysis of fused sodium chloride using the Downs cell. This method currently is most prevalent. The Downs cell consists of a steel cell with brick lining containing the fused bath. The multiple electrode arrangement consists of four cylindrical graphite anodes that project upward from the hase of the cell. Each anode is surrounded hy a diaphragm of iron gauge and a steel cathode. 

Another electrolysis process involves electrodeposition of dense, high-puri-ty tantalum metal. In this electrolysis, electrolyte consists of potassium fluotantalate and potassium fluoride and the anode is made of tantalum upon which electrodeposition from the fused salt occurs. 

In the electrolytic process, a fused bath of yttrium fluoride and lithium fluoride is heated to nearly 1,700°C and electrolyzed. The electrolysis is done in a graphite crucible using molybdenum cathodes at which yttrium is produced as molten metal. 

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