Salts, molten

A survey of recent developments in molten salts covers structures, physical properties, uses, and their reactions. Spectroscopic techniques for detecting and identifying complex ions in molten salts are also reviewed, together with the effects of complex ions on the activity, heats of mixing, and other physical properties. The information that can be obtained from Raman and i.r. spectroscopy is emphasized in a further review of molten salts covering types of reaction, ion solvation, and interionic vibrations in nitrates, halides, 

Nakamura, Muroran Kogyo Daigaku Kenkyu Hokoku, 1971, 7, 443. 

Structural studies in fused salts by means of careful and thorough high-temperature measurements of electrical conductivity, density, viscosity, and laser- Raman spectroscopy have been reviewed. Four problem areas are discussed (1) melting mechanisms of ionic compounds with large polyatomic cations, (2) salts as ultra-concentrated electrolyte solutions, (3) structural aspects and Raman spectroscopy, and (4) electrolysis of molten carbonates. The results in these areas are summarized and significant contributions to new experimental techniques for molten-salt studies are discussed.275 The physical properties and structure of molten salts have also been reviewed in terms of operational (hole, free volume, partly disordered crystal) and a priori (intermolecular potential) models.276 Electrochemistry 

In contrast to aqueous solutions, tungsten can be deposited from melts as metal at the cathode. 

TABLE 3.4. Position of Thngsten in the Electromotive Series of Metals in Different Molten Salts 

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Figure 13.5 shows a flowsheet for the manufacture of phthalic anhydride by the oxidation of o-xylene. Air and o-xylene are heated and mixed in a Venturi, where the o-xylene vaporizes. The reaction mixture enters a tubular catalytic reactor. The heat of reaction is removed from the reactor by recirculation of molten salt. The temperature control in the reactor would be diflficult to maintain by methods other than molten salt. 

The reactor is highly exothermic, and the data have been extracted as the molten salt being a hot stream. The basis of this is that it is assumed that the molten salt circuit is an essential feature of the reactor design. Thereafter, there is freedom within reason to choose how the molten salt is cooled. 

Steam is by far the most widely used medium, useful up to about 475 K. Up to about 700 K organic liquids such as the dowtherms and mineral oil may be used. Mercury and molten salts, such as the eutectic mixture of sodium nitrite, sodium nitrate and potassium nitrate may be used up to 875 K, while above this temperature air and flue gases must be used. 

It is accurate for simple low valence electrolytes in aqueous solution at 25 °C and for molten salts away from the critical point. The solutions are obtained numerically. A related approximation is the following. 

Levy H A and Danford M D 1964 Molten Salt Chemistry ed M Blander (New York Interscience)... 

Bredig M A 1969 Molten Salts ed G M Mamantov (New York Dekker)... 

Since, generally, any base stronger than OH will react with water to produce OH we must use another solvent to observe very strong bases. The high base strengths of the hydride ion and the oxide ion can best be observed in molten salts as solvents, since hydrides and ionic oxides are either insoluble in ordinary solvents or attack them. 

Thus, ihe strongly basic oxide ion attacks the weakly acidic SiOj in a molten salt as solvent (p. 187 ... 

The most direct effect of defects on tire properties of a material usually derive from altered ionic conductivity and diffusion properties. So-called superionic conductors materials which have an ionic conductivity comparable to that of molten salts. This h conductivity is due to the presence of defects, which can be introduced thermally or the presence of impurities. Diffusion affects important processes such as corrosion z catalysis. The specific heat capacity is also affected near the melting temperature the h capacity of a defective material is higher than for the equivalent ideal crystal. This refle the fact that the creation of defects is enthalpically unfavourable but is more than comp sated for by the increase in entropy, so leading to an overall decrease in the free energy... 

Iridium is not attacked by any of the acids nor by aqua regia, but is attacked by molten salts, such as NaCl and NaCN. The specific gravity of iridium is only very slightly lower than osmium, which is generally credited as the heaviest known element. Calculations of the densities of iridium and osmium from the space lattices give values of 22.65 and 22.61 g/cm 3, respectively. These values may be more reliable than actual physical measurements. At present, therefore, we know that either iridium or osmium is the densest known element, but the data do not yet allow selection between the two. 

The metal is a source of nuclear power. There is probably more energy available for use from thorium in the minerals of the earth s crust than from both uranium and fossil fuels. Any sizable demand from thorium as a nuclear fuel is still several years in the future. Work has been done in developing thorium cycle converter-reactor systems. Several prototypes, including the HTGR (high-temperature gas-cooled reactor) and MSRE (molten salt converter reactor experiment), have operated. While the HTGR reactors are efficient, they are not expected to become important commercially for many years because of certain operating difficulties. 

The catalytic vapor-phase oxidation of propylene is generally carried out in a fixed-bed multitube reactor at near atmospheric pressures and elevated temperatures (ca 350°C) molten salt is used for temperature control. Air is commonly used as the oxygen source and steam is added to suppress the formation of flammable gas mixtures. Operation can be single pass or a recycle stream may be employed. Recent interest has focused on improving process efficiency and minimizing process wastes by defining process improvements that use recycle of process gas streams and/or use of new reaction diluents (20-24). 

Oxidation Step. A review of mechanistic studies of partial oxidation of propylene has appeared (58). The oxidation process flow sheet (Fig. 2) shows equipment and typical operating conditions. The reactors are of the fixed-bed shell-and-tube type (about 3—5 mlong and 2.5 cm in diameter) with a molten salt coolant on the shell side. The tubes are packed with catalyst, a small amount of inert material at the top serving as a preheater section for the feed gases. Vaporized propylene is mixed with steam and ak and fed to the first-stage reactor. The feed composition is typically 5—7% propylene, 10—30%... 

The preheated gases react exothermically over the first-stage catalyst with the peak temperature ia the range of 330—430°C, depending on conditions and catalyst selectivity. The conversion of propylene to waste gas (carbon dioxide and carbon monoxide) is more exothermic than its conversion to acroleia. At the end of the catalyst bed the temperature of the mixture drops toward that of the molten salt coolant. 

N. Watanabe, Proc. Int. Symp. Molten Salt Chem. Technol, Molten Salt Comm, of the Electrochem. Soc. ofJapan, 21 (1983). 

The principal use of AIF. is as a makeup ingredient in the molten cryoflte, Na.. AIF AI2O2, bath used in aluminum reduction cells in the HaH-Haroult process and in the electrolytic process for refining of aluminum metal in the Hoopes cell. A typical composition of the molten salt bath is 80—85%... 

The molten salts quickly dissolve the metal oxides at high temperatures to form a clean metal surface. Other uses are as catalysts and in fire-retardant formulations (see Flame retardants). 

Other applications of zirconium tetrafluoride are in molten salt reactor experiments as a catalyst for the fluorination of chloroacetone to chlorofluoroacetone (17,18) as a catalyst for olefin polymerization (19) as a catalyst for the conversion of a mixture of formaldehyde, acetaldehyde, and ammonia (in the ratio of 1 1 3 3) to pyridine (20) as an inhibitor for the combustion of NH CIO (21) in rechargeable electrochemical cells (22) and in dental applications (23) (see Dentalmaterials). 

The direct, one-step production of DMF from carbon monoxide, hydrogen, and ammonia has also been reported. A mthenium carbonyl catalyst is used, either ia a polar organic solvent (20) or ia a phosphonium molten salt medium (21). 

Molten Carbonate Fuel Cell. The electrolyte ia the MCFC is usually a combiaation of alkah (Li, Na, K) carbonates retaiaed ia a ceramic matrix of LiA102 particles. The fuel cell operates at 600 to 700°C where the alkah carbonates form a highly conductive molten salt and carbonate ions provide ionic conduction. At the operating temperatures ia MCFCs, Ni-based materials containing chromium (anode) and nickel oxide (cathode) can function as electrode materials, and noble metals are not required. 

Gold and gold-based alloys ate used for corrosion-resistant equipment. Gold—platinum alloys, 75 Au-25 Pt or 84 Au-15 Pt-1 Rh, ate used as cmcible material for many molten salts (98). Spinnerets for rayon manufacture ate based on the Au—Pt system which exhibits a broad miscibility gap in the soHd state so that the alloys can be age-hardened. Spinneret alloys contain 30—40% or mote platinum modified by small additions of usually rhodium (99). Either gold or gold—platinum alloys ate used in mpture disks for service with corrosive gases (100). 

Molten Salt Distillation. Hafnium tetrachloride is slightly more volatile than zirconium tetrachloride, but a separation process based on this volatility difference is impractical at atmospheric pressures because only soHd and vapor phases exist. The triple point for these systems is at about 2.7 MPa (400 psia) and 400°C so that separation of the Hquids by distillation would necessarily require a massive pressurized system (13). 

Although Hitec is nonflammable, it is a strong oxidizer and supports the combustion of other materials. Consequendy, combustible materials must be excluded from contact with the molten salt. Hitec is compatible with carbon steel at temperatures up to 450°C. At higher temperatures, low alloy or austenitic stainless steel is recommended. Adding water to Hitec does not appreciably alter its corrosion behavior. 

Hydrotherm Molten Salt Heat Transfer System, American Hydrotherm Corp., New York. 

Hot Corrosion. Hot corrosion is an accelerated form of oxidation that arises from the presence not only of an oxidizing gas, but also of a molten salt on the component surface. The molten salt interacts with the protective oxide so as to render the oxide nonprotective. Most commonly, hot corrosion is associated with the condensation of a thin molten film of sodium sulfate [7757-82-6], Na2S04, on superaHoys commonly used in components for gas turbines, particularly first-stage turbine blades and vanes. Other examples of hot corrosion have been identified in energy conversion systems, particularly coal gasifiers and direct coal combustors. In these cases the salt originates from alkali impurities in the coal which condense on the internal... 

For most alloys, the corrosion rate displays a maximum at 850—900°C, and decreases very rapidly at temperatures up to 1000°C (28), again strongly suggesting that a molten salt is necessary in order to initiate hot corrosion. 

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. 

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