Molten salts melting point

Molten cryohte dissolves many salts and oxides, forming solutions of melting point lower than the components. Figure 1 combines the melting point diagrams for cryolite—A1F. and for cryohte—NaF. Cryohte systems ate of great importance in the HaH-Heroult electrolysis process for the manufacture of aluminum (see Aluminumand ALUMINUM alloys). Table 5 Hsts the additional examples of cryohte as a component in minimum melting compositions. 

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. 

Lithium Chloride. Lithium chloride [7447- 1-8], LiCl, is produced from the reaction of Hthium carbonate or hydroxide with hydrochloric acid. The salt melts at 608°C and bods at 1382°C. The 41-mol % LiCl—59-mol % KCl eutectic (melting point, 352°C) is employed as the electrolyte in the molten salt electrolysis production of Hthium metal. It is also used, often with other alkaH haHdes, in brazing flux eutectics and other molten salt appHcations such as electrolytes for high temperature Hthium batteries. 

Calcium metal was produced in 1855 by electrolysis of a mixture of calcium, strontium, and ammonium chlorides, but the product was highly contaminated with chlorides (1). By 1904 fairly large quantities of calcium were obtained by the electrolysis of molten calcium chloride held at a temperature above the melting point of the salt but below the melting point of calcium metal. An iron cathode just touched the surface of the bath and was raised slowly as the relatively chloride-free calcium solidified on the end. This process became the basis for commercial production of calcium metal until World War II. 

The mobilities of ions in molten salts, as reflected in their electrical conductivities, are an order of magnitude larger than Arose in Are conesponding solids. A typical value for diffusion coefficient of cations in molten salts is about 5 X lO cm s which is about one hundred times higher Aran in the solid near the melting point. The diffusion coefficients of cation and anion appear to be about the same in Are alkali halides, wiAr the cation being about 30% higher tlrair Are anion in the carbonates and nitrates. 

What constitutes an ionic liquid, as distinct from a molten salt It is generally accepted that ionic liquids have relatively low melting points, ideally below ambient temperature [1, 2]. The distinction is arbitrarily based on the salt exhibiting liquidity at or below a given temperature, often conveniently taken to be 100 °C. However, it is clear from observation that the principle distinction between the materials of interest today as ionic liquids (and more as specifically room-temperature ionic liquids) and conventional molten salts is that ionic liquids contain organic cations rather than inorganic ones. This allows a convenient differentiation without concern that some molten salts may have lower melting points than some ionic liquids . 

The presence of several anions in these ionic liquids has the effect of significantly decreasing the melting point. Considering that the formation of eutectic mixtures of molten salts is widely used to obtain lower melting points, it is surprising that little effort has been put into identifying the effects of mixtures of cations or anions on the physical properties of other ionic liquids [17]. 

The first examples of alkylation reactions in molten salts were reported in the 1950 s. Baddeley and Williamson performed a number of intramolecular cycliza-tion reactions [76] (Scheme 5.1-46), carried out in mixtures of sodium chloride and aluminium chloride. The reactions were run at below the melting point of the pure salt, and it is presumed that the mixture of reagents acts to lower the melting point. 

Molten salts promote rapid corrosion of many constmctional materials at relatively low temperatures. Low-melting-point salts include sodium salts from saline atmospheres, fireside ash, silicate insulation, contaminants in the feed, etc. Corrosion rates of several mm/year can be observed at temperatures as low as 520°C. High chromium- and nickel-containing alloys up to 50% Cr/50% Ni are employed. 

Consideration will also be given to attack arising from contact with solids such as refractories, and with molten materials such as salts, glasses, and lower-melting-point metals and alloys. On a fundamental basis, the distinction between some of these latter reactions and normal-temperature aqueous corrosion is not always clear, since galvanic effects may be of significance in both cases, but for practical purposes a distinction can be made on the basis of the temperature involved. 

Reactions of contaminants in the fuel or air in the combustion zone can result in the formation of compounds which can condense as molten salts onto cooler components in the system. This type of process can occur when fuels containing sulphur or vanadium are burnt. In the case of sulphur contaminants, alkali sulphates form by reactions with sodium which may also be present in the fuel or in the combustion air, and for vanadium-containing fuels low-melting-point sodium vanadates or vanadium pentoxide are produced, particularly when burning residual oils high in vanadium. Attack by molten salts has many features in common which will be illustrated for the alkali-sulphate-induced attack, but which will be subsequently shown to be relevant to the case of vanadate attack. 

One of the most important impurities, found particularly in the residual oils, is vanadium, occurring in the resultant ash as vanadium pentoxide. The fluxing action of the ash with which corrosion is normally associated and the marked difference in severity of attack at temperatures above and below the melting point of the ash again suggest molten salt induced attack. 

The experiment may also be repeated using a platinum (indicator) electrode and a tungsten wire reference electrode. If the tungsten electrode has been left idle for more than a few days, the surface must be cleaned by dipping into just molten sodium nitrate (CARE ). The salt should be only just at the melting point or the tungsten will be rapidly attacked it should remain in the melt for a few seconds only and is then thoroughly washed with distilled water. 

Attention has been given for some time to the use of lithium alloys as an alternative to elemental lithium. Groups working on batteries with molten salt electrolytes that operate at temperatures of 400-450 °C, well above the melting point of lithium, were especially interested in this possibility. Two major directions evolved. One involved the use of lithium-aluminium alloys [5, 6], whereas another was concerned with lithium-silicon alloys [7-9]. 

The electrolyte salt must be processed to recover the ionic plutonium orginally added to the cell. This can be done by aqueous chemistry, typically by dissolution in a dilute sodium hydroxide solution with recovery of the contained plutonium as Pu(OH)3, or by pyrochemical techniques. The usual pyrochemical method is to contact the molten electrolyte salt with molten calcium, thereby reducing any PUCI3 to plutonium metal which is immiscible in the salt phase. The extraction crucible is maintained above the melting point of the contained salts to permit any fine droplets of plutonium in the salt to coalesce with the pool of metal formed beneath the salt phase. If the original ER electrolyte salt was eutectic NaCl-KCl a third "black salt" phase will be formed between the stripped electrolyte salt and the solidified metal button. This dark-blue phase can contain 10 wt. % of the plutonium originally present in the electrolyte salt plutonium in this phase can be recovered by an additional calcium extraction stepO ). 

Obviously this method is limited to liquid metals like mercury and gallium and their amalgams respectively alloys. Modifications of this method have been reported [86FIor]. At elevated temperatures with molten salt electrolytes alloys with an appropriately low melting point can be investigated, too. 

Salt-inclusion solids described herein were synthesized at high temperature (>500°C) in the presence of reactive alkali and alkaline-earth metal halide salt media. For single crystal growth, an extra amount of molten salt is used, typically 3 5 times by weight of oxides. The reaction mixtures were placed in a carbon-coated silica ampoule, which was then sealed under vacuum. The reaction temperature was typically set at 100-150 °C above the melting point of employed salt. As shown in the schematic drawing in Fig. 16.2, the corresponding metal oxides were first dissolved conceivably via decomposition because of cor-... 

The electrolysis apparatus operates well above the melting point of aluminum (660 °C), and liquid aluminum has a higher density than the molten salt mixture, so pure liquid metal settles to the bottom of the reactor. The pure metal is drained through a plug and cast into ingots. 

Good electrical conductance is one of the characteristics of many though not all molten salts. This characteristic has often been employed industrially. Various models have been proposed for the mechanism of electrical conductance. Electrolytic conductivity is related to the structure, although structure and thermodynamic properties are not the main subjects of this chapter. Electrolytic conductivities of various metal chlorides at the melting points are given in Table 4 together with some other related properties. "... 

In general, the electrolysis of a molten salt at inert electrodes produces the metal at the cathode, e.g., calcium from calcium chloride (melting point 774 °C). The anion is often a halide ion which, on discharge, yields the halogen, e.g., chlorine from calcium chloride. 

The electrolyte is made by in situ chlorination of vanadium to vanadium dichloride in a molten salt bath. Higher valent chlorides are difficult to retain in the bath and thus are not preferred. The molten bath, which is formed by sodium chloride or an equimolar mixture of potassium chloride-sodium chloride or of potassium chloride-lithium chloride or of sodium chloride-calcium chloride, is contained in a graphite crucible. The crucible also serves as an anode. Electrolysis is conducted at a temperature about 50 °C above the melting point of the salt bath, using an iron or a molybdenum cathode and a cathode current density of 25 to 75 A dnT2. The overall electrochemical deposition reaction involves the formation and the discharge of the divalent ionic species, V2+ ... 

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