Molten salts electrical

Janz, G.J., Dampier, F.W., Lakshiminarayanan, G.R. et al. (1968) Molten Salts Electrical Conducance, Density and Viscosity Data, Vol. 24, National Bureau of Standards, Washington, DC. 

Each type of metallic coating process has some sort of hazard, whether it is thermal energy, the reactivity of molten salt or metal baths, particulates in the air from spray processes, poisonous gases from pack cementation and diffusion, or electrical hazards associated with arc spray or ion implantation. 

Maintenance of isothermal conditions requires special care. Temperature differences should be minimised and heat-transfer coefficients and surface areas maximized. Electric heaters, steam jackets, or molten salt baths are often used for such purposes. Separate heating or cooling circuits and controls are used with inlet and oudet lines to minimize end effects. Pressure or thermal transients can result in longer Hved transients in the individual catalyst pellets, because concentration and temperature gradients within catalyst pores adjust slowly. 

Based on the results of the Solar One plant. Southern California Edison formed a consortium that included DOE and EPRI to constmct a Solar Two Project. Solar Two will convert the idle Solar One central receiver plant from a water/steam system to a molten salt system, thereby improving efficiency and operating performance. With the molten salt technology, solar energy can be collected during the day and stored in the salt to produce electricity when needed. The three-year demonstration is scheduled to begin in late 1996. 

Bismuthides. Many intermetaUic compounds of bismuth with alkafl metals and alkaline earth metals have the expected formulas M Bi and M Bi, respectively. These compounds ate not saltlike but have high coordination numbers, interatomic distances similar to those found in metals, and metallic electrical conductivities. They dissolve to some extent in molten salts (eg, NaCl—Nal) to form solutions that have been interpreted from cryoscopic data as containing some Bi . Both the alkafl and alkaline earth metals form another series of alloylike bismuth compounds that become superconducting at low temperatures (Table 1). The MBi compounds are particularly noteworthy as having extremely short bond distances between the alkafl metal atoms. 

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. 

A reactor was cooled by a molten salt. At startup the salt was heated to reaction temperature by an electric heater. During one startup the temperature of the salt rose at only half the usual rate. Obviously one of the heaters was faulty, but no fault could be found. The problem was finally traced to a nitrogen valve, which had been left open. The flow of nitrogen through the reactor was taking away half the heat. 

The poor efficiencies of coal-fired power plants in 1896 (2.6 percent on average compared with over forty percent one hundred years later) prompted W. W. Jacques to invent the high temperature (500°C to 600°C [900°F to 1100°F]) fuel cell, and then build a lOO-cell battery to produce electricity from coal combustion. The battery operated intermittently for six months, but with diminishing performance, the carbon dioxide generated and present in the air reacted with and consumed its molten potassium hydroxide electrolyte. In 1910, E. Bauer substituted molten salts (e.g., carbonates, silicates, and borates) and used molten silver as the oxygen electrode. Numerous molten salt batteiy systems have since evolved to handle peak loads in electric power plants, and for electric vehicle propulsion. Of particular note is the sodium and nickel chloride couple in a molten chloroalumi-nate salt electrolyte for electric vehicle propulsion. One special feature is the use of a semi-permeable aluminum oxide ceramic separator to prevent lithium ions from diffusing to the sodium electrode, but still allow the opposing flow of sodium ions. 

Electrochemically, the system metal/molten salt is somewhat similar to the system metal/aqueous solution, although there are important differences, arising largely from differences in temperature and in electrical conductivity. Most fused salts are predominantly ionic, but contain a proportion of molecular constituents, while pure water is predominantly molecular, containing very low activities of hydrogen and hydroxyl ions. Since the aqueous system has been extensively studied, it may be instructive to point out some analogues in fused-salt systems. 

Electrolyte a substance, liquid or solid, which conducts electrical current by movement of ions (not of electrons). In corrosion science, an electrolyte is usually a liquid solution of salts dissolved in a solvent, or a molten salt. The term also applies to polymers and ceramics which are ionically conductive. 

When an ionic solid like sodium chloride is melted, the molten salt conducts electric current. The conductivity is like that of an aqueous salt solution Na+ and Cl- ions are present. The extremely high melting temperature (808°C) shows that a large amount of energy is needed to tfear apart the regular NaCl crystalline arrangement to free the ions so they can move. 

The National Institute of Standards and Technology (NIST) molten salts database has been designed to provide engineers and scientists with rapid access to critically evaluated data for inorganic salts in the molten state. Properties include density, viscosity, electrical conductance, and surface tension. Properties for approximately 320 single salts and 4000 multicomponent systems are included, the latter being primarily binary. Data have been abstracted from the literature over the period 1890-1990. The primary data sources are the National Bureau of Standards-National... 

The molten salt standard program was initiated at Rensselaer Polytechnic Institute (RPI) in 1973 because of difficulties being encountered with accuracy estimates in the NBS-NSRDS molten salt series. The density, surface tension, electrical conductivity, and viscosity of KNO3 and NaCl were measured by seven laboratories over the world using samples distributed by RPI. The data from these round-robin measurements of raw properties were submitted to RPI for evaluation. Their recommendations are summarized in Table 2. 

Some 30 years ago, transport properties of molten salts were reviewed by Janz and Reeves, who described classical experimental techniques for measuring density, electrical conductance, viscosity, transport number, and self-diffusion coefficient. 

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. "... 

It is not as easy as it appears to know whieh are the eleetrieally conducting species in molten salts. It seems to be nearly impossible to determine the electrically conducting species by experiment alone. ... 

Data on high-temperature melts are still limited. Conventional methods are difficult to apply because of the high values of thermal conductivity. Other difficulties in measuring molten salts are their corrosiveness, high electrical conductivities, and the necessity of careful preparation. Special care should be taken to exclude convection errors, which are usually the most serious source of errors, even at room temperature. 

Kato et al. have used electric stepwise heating of a thin metal layer to measure thermal diffusivity of molten salts. The ratio of the temperatures with time and 2/i at distance x below tlie heating plate was evaluated as a function of the Fourier number ... 

Gustafsson et al. measured the thermal conductivity and thermal diffusivity of molten NaNOs KNO3. The approximate dimension of the foil used for NaNO, was platinum measuring 0.010 X 40 X 86 mm The foil was heated by a constant electric current and the measurements were completed within 10 s. Errors due to radiation were considered to be negligible. The accuracy was claimed to be +2.6% for thermal conductivity and 3% for thermal diffusivity, but the effect of current leak from the metallic foil to the molten salts was neglected. 

G. J. Janz, J. Phys. Chem. Ref Data 9 (1980) 791 Molten Salts Data as Reference Standards for Density, Surface Tension, viscosity and Electrical Conductance KN03 and NaCl, American Chemical Society-American Institute of Physics-National Bureau of Standards, Washington, DC, 1980. 

The composition of the electrolyte is quite important in controlling the electrolytic deposition of the pertinent metal, the chemical interaction of the deposit with the electrolyte, and the electrical conductivity of the electrolyte. In the case of molten salts, the solvent cations and the solvent anions influence the electrodeposition process through the formation of complexes. The stability of these complexes determines the extent of the reversibility of the overall electroreduction process and, hence, the type of the deposit formed. By selecting a suitable mixture of solvent cations to produce a chemically stable solution with strong solute cation-anion interactions, it is possible to optimize the stability of the complexes so as to obtain the best deposition kinetics. In the case of refractory and reactive metals, the presence of a reasonably stable complex is necessary in order to yield a coherent deposition rather than a dendritic type of deposition. 

Janz, G. J., Thermodynamic and Transport Properties for Molten Salts Correlation Equations for Critically Evaluated Density, Surface Tension, Electrical Conductance, and Viscosity Data. 1988, New York American Institute of Physics. 

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