Molten electrical conductivity

The composition to the melting point is estimated to be 65% Na AlF, 14% NaF, and 21% NaAlF [1382-15-3], The ions Na" and F ate the principal current carrying species in molten cryoHte whereas the AIF is less mobile. The stmctural evidences are provided by electrical conductivity, density, thermodynamic data, cryoscopic behavior, and the presence of NaAlF in the equiUbtium vapor (19,20). 

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. 

Bismuth Trichloride. Bismuth(III) chloride is a colodess, crystalline, dehquescent soHd made up of pyramidal molecules (19). The nearest intermolecular Bi—Cl distances are 0.3216 nm and 0.3450 nm. The density of the soHd is 4.75 g/mL and that of the Hquid at 254°C is 3.851 g/mL. The vapor density corresponds to that of the monomeric species. The compound is monomeric in dilute ether solutions, but association occurs at concentrations greater than 0.1 Af. The electrical conductivity of molten BiCl is of the same order of magnitude as that found for ionic substances. 

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. 

This polymer may be prepared by stirring the molten w-aminoundecanoic acid at about 220°C. The reaction may be followed by measurements of the electrical conductivity of the melt and the intrinsic viscosity of solutions in w-cresol. During condensation 0.4-0.6% of a 12-membered ring lactam may be formed by intramolecular condensation but this is not normally removed since its presence has little effect on the properties of the polymer. 

Molten I2CI6 has been much less studied as an ionizing solvent because of the high dissociation pressure of CI2 above the melt. The appreciable electrical conductivity may well indicate an ionic self-dissociation equilibrium such as... 

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. 

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. 

Molten lithium fluoride and sodium chloride have easily measured electrical conductivities. Nevertheless, these conductivities are lower than metallic conductivities by several factors of ten. Molten sodium chloride at 750°C has a conductivity about IQ-5 times that of copper metal at room temperature. It is unlikely that the electric charge moves by the same mechanism in molten NaCl as in metallic copper. Experiments show that the charge is carried in molten NaCl by Na+ and Cl- ions. This electrical conductivity of the liquid is one of the most characteristic... 

Beryllium is obtained by electrolytic reduction of molten beryllium chloride. The element s low density makes it useful for the construction of missiles and satellites. Beryllium is also used as windows for x-ray tubes because Be atoms have so few electrons, thin sheets of the metal are transparent to x-rays and allow the rays to escape. Beryllium is added in small amounts to copper the small Be atoms pin the Cu atoms together in an interstitial alloy that is more rigid than pure copper but still conducts electricity well. These hard, electrically conducting alloys are formed into nonsparking tools for use in oil refineries and grain elevators, where there is a risk of explosion. Beryllium-copper alloys are also used in the electronics industry to form tiny nonmagnetic parts and contacts that resist deformation and corrosion. 

Aluminum metal is produced from aluminum oxide by electrolysis using the Hall-Heroult process, whose story is detailed in our Chemical Milestones Box. The melting point of AI2 O3 is too high (2015 °C) and its electrical conductivity too low to make direct electrolysis commercially viable. Instead, AI2 O3 is mixed with cryolite (Na3 AlFfi) containing about 10% CaF2. This mixture has a melting point of 1000 °C, still a high temperature but not prohibitively so. Aluminum forms several complex ions with fluoride and oxide, so the molten mixture... 

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. "... 

Interpretation of this effect was considered to be a crucial key to a better understanding of the mechanism of electric conductance of molten... 

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. 

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. 

In an individual molten carbamide, the electrode processes are feebly marked at melt decomposition potentials (Fig. 1) because of its low electrical conductivity. Both electrode processes are accompanied by gas evolution. 

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