Salts fused

Figure III-9u shows some data for fairly ideal solutions [81] where the solid lines 2, 3, and 6 show the attempt to fit the data with Eq. III-53 line 4 by taking ff as a purely empirical constant and line 5, by the use of the Hildebrand-Scott equation [81]. As a further example of solution behavior, Fig. III-9b shows some data on fused-salt mixtures [83] the dotted lines show the fit to Eq. III-SS.

The existence of the hydride ion is shown by electrolysis of the fused salt when hydrogen is evolved at the anode. If calcium hydride is dissolved in another fused salt as solvent, the amount of hydrogen evolved at the anode on electrolysis is 1 g for each Faraday of current (mole of electrons) passed, as required by the laws of electrolysis. 

The general characteristics of all these elements generally preclude their extraction by any method involving aqueous solution. For the lighter, less volatile metals (Li, Na, Be, Mg, Ca) electrolysis of a fused salt (usually the chloride), or of a mixture of salts, is used. The heavier, more volatile metals in each group can all be similarly obtained by electrolysis, but it is usually more convenient to take advantage of their volatility and obtain them from their oxides or chlorides by displacement, i.e. by general reactions such as... 

The tables in this section contain values of the enthalpy and Gibbs energy of formation, entropy, and heat capacity at 298.15 K (25°C). No values are given in these tables for metal alloys or other solid solutions, for fused salts, or for substances of undefined chemical composition. 

Chlorine from the Magnesium Process. Magnesium is produced by the fused salt electrolysis of MgCl2 (see Magnesium and magnesium... 

Significant vapor pressure of aluminum monofluoride [13595-82-9], AIF, has been observed when aluminum trifluoride [7784-18-1] is heated in the presence of reducing agents such as aluminum or magnesium metal, or is in contact with the cathode in the electrolysis of fused salt mixtures. AIF disproportionates into AIF. and aluminum at lower temperatures. The heat of formation at 25°C is —264 kJ/mol(—63.1 kcal/mol) and the free energy of formation is —290 kJ/mol(—69.3 kcal/mol) (1). Aluminum difluoride [13569-23-8] h.3.s been detected in the high temperature equihbrium between aluminum and its fluorides (2). 

Lithium hydride reacts vigorously with siUcates above 180°C. Therefore, glass, quart2, and porcelain containers cannot be used in preparative processes. That only traces dissolve in polar solvents such as ether reflects its significant (60—75%) covalent bond character. It is completely soluble in, and forms eutectic melting compositions with, a number of fused salts. 

Sodium hydride is insoluble in organic solvents but soluble in fused salt mixtures and fused hydroxides such as NaOH. It oxidizes in dry air and hydrolyzes rapidly in moist air. The pure material reacts violently with water ... 

Solutions of alkah metal and ammonium iodides in Hquid iodine are good conductors of electricity, comparable to fused salts and aqueous solutions of strong acids. The Hquid is therefore a polar solvent of considerable ionising power, whereas its own electrical conductivity suggests that it is appreciably ionized, probably into I" and I (triodide). Iodine resembles water in this respect. The metal iodides and polyiodides are bases, whereas the iodine haHdes are acids. 

Iron hahdes react with haHde salts to afford anionic haHde complexes. Because kon(III) is a hard acid, the complexes that it forms are most stable with F and decrease ki both coordination number and stabiHty with heavier haHdes. No stable F complexes are known. [FeF (H20)] is the predominant kon fluoride species ki aqueous solution. The [FeF ] ion can be prepared ki fused salts. Whereas six-coordinate [FeCy is known, four-coordinate complexes are favored for chloride. Salts of tetrahedral [FeCfy] can be isolated if large cations such as tetraphenfyarsonium or tetra alkylammonium are used. [FeBrJ is known but is thermally unstable and disproportionates to kon(II) and bromine. Complex anions of kon(II) hahdes are less common. [FeCfy] has been obtained from FeCfy by reaction with alkaH metal chlorides ki the melt or with tetraethyl ammonium chloride ki deoxygenated ethanol. 

The deposition of RE metals from aqueous solutions does not work because of the highly electropositive nature of the REE. Therefore, industrial production of RE metals is carried out by fused salt electrolysis or metaHothermic reduction. 

Fused Salt Electrolysis. Only light RE metals (La to Nd) can be produced by molten salt electrolysis because these have a relatively low melting point compared to those of medium and heavy RE metals. Deposition of an alloy with another metal, Zn for example, is an alternative. The feed is a mixture of anhydrous RE chlorides and fluorides. The materials from which the electrolysis cell is constmcted are of great importance because of the high reactivity of the rare-earth metals. Molybdenum, tungsten, tantalum, or alternatively iron with ceramic or graphite linings are used as cmcible materials. Carbon is frequently used as an anode material. 

The cell for this process is unlike the cell for the electrolysis of aluminum which is made of carbon and also acts as the cathode. The cell for the fused-salt electrolysis is made of high temperature refractory oxide material because molten manganese readily dissolves carbon. The anode, like that for aluminum, is made of carbon. Cathode contact is made by water-cooled iron bars that are buried in the wall near the hearth of the refractory oxide cell. 

The most common fused salt baths are complex mixtures of alkah chlorides, rigorously purified and dried. Fused salt plating must be done under an inert atmosphere. Often argon is used because nitrogen can react with some metals. Inert anodes, eg, Pt-coated titanium or graphite, are used and the plating metal is suppHed by additions of an appropriate metal salt. 

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. 

A fused-salt electrolysis process has been demonstrated (30). Carbon dioxide is introduced to the cathode area of a melt of 60 wt % LiCl—40 wt % Li2C02 at 550°C. The carbon dioxide reacts with hthium oxide which is produced by electrolysis. Oxygen is released at the anode and carbon plates onto the cathode. The reaction requites a potential of 4.5 V. The reactions ate as follows ... 

Silver nitrate forms colorless, rhombic crystals. It is dimorphic and changes to the hexagonal rhombohedral form at 159.8°C. It melts at 212°C to a yellowish Hquid which solidifies to a white, crystalline mass on cooling. An alchemical name, lunar caustic, is stiU appHed to this fused salt. In the presence of a trace of nitric acid, silver nitrate is stable to 350°C. It decomposes at 440°C to metallic silver, nitrogen, and nitrogen oxides. Solutions of silver nitrate are usually acidic, having a pH of 3.6—4.6. Silver nitrate is soluble in ethanol and acetone. 

It was an adaptation of the Castner cell to sodium chloride for fused caustic electrolysis. A mixture of sodium chloride and other chlorides, molten at 620°C, was electroly2ed ia rectangular or oval cells heated only by the current. Several cells have been patented for the electrolysis of fused salt ia cells with molten lead cathodes (65). However, it is difficult to separate the lead from the sodium (see Electrochemical processing). 

Table 6. Tekkosha Fused-Salt Electrolysis Cells ...

Electroplating. When ionicaHy bonded molecules are dissolved in a solvent, some of the molecules dissociate into ions, whether the solvent is water, organic solvent, or a fused salt. A simple example is that of sulfuric acid or copper sulfate in water, giving... 

Refining of Vanadium. In addition to the purification methods described above, vanadium can be purified by any of three methods iodide refining (van Arkel-deBoer process), electrolytic refining in a fused salt, and electrotransport. 

Electron-beam melting of zirconium has been used to remove the more volatile impurities such as iron, but the relatively high volatiUty of zirconium precludes effective purification. Electrorefining is fused-salt baths (77,78) and purification by d-c electrotransport (79) have been demonstrated but are not in commercial use. 

Uthium-FeS 2 LiAl + FeS Li,S + 2 A1 + Fe 1.33 90 95 circulating electrolyte low cost, high temperature fused salt, second step possible... 

BeryUium reacts with fused alkaU haUdes releasing the alkaU metal until an equUibrium is estabUshed. It does not react with fused haUdes of the alkaline-earth metals to release the alkaline-earth metal. Water-insoluble fluoroberyUates, however, are formed in a fused-salt system whenever barium or calcium fluoride is present. BeryUium reduces haUdes of aluminum and heavier elements. Alkaline-earth metals can be used effectively to reduce beryUium from its haUdes, but the use of alkaline-earths other than magnesium [7439-95-4] is economically unattractive because of the formation of water-insoluble fluoroberyUates. Formation of these fluorides precludes efficient recovery of the unreduced beryUium from the reaction products in subsequent processing operations. 

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. 

BeryUium chloride [7787-47-5], BeCl2, is prepared by heating a mixture of beryUium oxide and carbon in chloride at 600—800°C. At pressures of 2.7—6.7 Pa (0.02—0.05 mm Hg) beryllium chloride sublimes at 350—380°C. It is easily hydrolyzed by water vapor or in aqueous solutions. BeryUium chloride hydrate [14871-75-1] has been obtained by concentrating a saturated aqueous solution of the chloride in a stream of hydrogen chloride. ChloroberyUate compounds have not been isolated from aqueous solutions, but they have been isolated from anhydrous fused salt mixtures. 

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. 

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