Electrolyte molten

Molten sulphides are almost invariably semiconductors, and so their conductivities are typically larger than Arose of the average molten electrolyte. For example, the specific conductairce of molten AgaS can be described, as a function of temperature by the equation... 

The melt is heated by passing a large elecuical cunent between two electrodes, one of which is tire metal rod to be refined, and the otlrer is the liquid metal pool standing in a water-cooled copper hearth, which collects the metal drops as tlrey fall tluough the molten electrolyte. This pool tlrerefore freezes at the bottom, forming the ingot. Under optimum chcumstances tire product billet takes the form of a cylindrical solid separated from the molten salt by... 

On the negative side, the MCFC suffers from sealing and cathode corrosion problems induced by its high-temperature molten electrolyte. Thermal cycling is also limited because once the electrolyte solidifies it is prone to develop cracks during reheat-... 

The electrochemical behavior of niobium in different types of molten electrolytes and the influence of ligand substitution in niobium-containing complex ions on the reduction mechanism is comprehensively reviewed by Polyakov [555]. 

The properties of the molten electrolyte sodium aluminum chloride influence the performance and the behavior of the ZEBRA cell. 

The solubility of nickel chloride in the molten electrolyte is of interest because high solubilities of nickel chloride will cause capacity loss over the lifetime. Dissolved nickel chloride will not be contacted by the electronically conductive backbone nickel and cannot participate in the discharge reaction. Therefore it is essential that the nickel chloride is formed... 

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 ). 

The interfacial tension of an electrode surface being in contact with an electrolyte solution or molten electrolyte is related to the electrode potential and the charge on the electrode in a direct way ... 

If an electrode is brought into contact with an electrolyte solution or a molten electrolyte, the establishment of the electrochemical double layer will be accompanied by a transfer of electrical charge. In a suitable arrangement this charge can be measured as an external current. If the contact is made in a way which adjusts the electrode potential upon immersion exactly to the value of Epzc, the current will be nil. Various methods briefly described below have been devised to detect exactly this situation. 

Table 3.3. Electrode potentials of zero charge of metal electrodes in contact with molten electrolyte salts. )...

In electrocatalysis, the major subject are redox reactions occurring on inert, nonconsumable electrodes and involving substances dissolved in the electrolyte while there is no stoichiometric involvement of the electrode material. Electrocatalytic processes and phenomena are basically studied in aqueous solutions at temperatures not exceeding 120 to 150°C. Yet electrocatalytic problems sometimes emerge as well in high-temperature systems at interfaces with solid or molten electrolytes. 

As in the case of solutions, the specific conductance, K, the equivalent conductance, a, and the molar conductance, am, are also distinguished for molten electrolytes. These are defined in the same manner as done for the case of solutions of electrolytes. It may, however, be pointed out that molten salts generally have much higher conductivities than equivalent aqueous systems. 

Some chlorides exist, however, whose conductances are intermediate between those of good conductors and of insulators. This implies that even molten electrolytes can be categorized as strong, medium, and weak electrolytes. 

When a small amount of a strong molten electrolyte is dissolved in another strong molten electrolyte, the laws of ideal dilute solutions are obeyed until relatively high concentrations are attained, assuming occurrence of a virtually complete dissociation. 

One of the first scientists to place electrochemistry on a sound scientific basis was Michael Faraday (1791-1867). On the basis of a series of experimental results on electrolysis, in the year 1832 he summarized the phenomenon of electrolysis in what is known today as Faraday s laws of electrolysis, these being among the most exact laws of physical chemistry. Their validity is independent of the temperature, the pressure, the nature of the ionizing solvent, the physical dimensions of the containment or of the electrodes, and the voltage. There are three Faraday s laws of electrolysis, all of which are universally accepted. They are rigidly applicable to molten electrolytes as well as to both dilute and concentrated solutions of electrolytes. 

Although the electrolysis of molten salts does not in principle differ from that of aqueous solutions, additional complications are encountered here owing to the problems related to the higher temperatures of operation, the resultant high reactivities of the components, the thermoelectric forces, and the stability of the deposited metals in the molten electrolyte. As a result of this, processes taking place in the melts and at the electrodes cannot be controlled to the same extent as in aqueous or other types of solutions. Considerations pertaining to Faraday s laws have indicated that it would be difficult to prove their applicability to the electrolysis of molten salts, since the current efficiencies obtained are generally too small in such cases. 

The standard emf series based on hydrogen is obviously not applicable to molten salt electrolysis systems. No emf series similar to that for aqueous systems has been established for molten electrolytes this is due to the nonavailability of accepted standard electrodes and the use of numerous molten electrolytes involving widely differing tamperers, consequent to the widely varying melting temperatures of the salts used. In spite of these, many emf series have been compiled, using a variety of molten salts with different stand-... 

A difference between electrolytes in solution and in the molten state is that the latter, in general, do not need solvents to dissociate. When an electrolyte exists in the molten state as the only component present and not as a solution of one electrolyte in another molten electrolyte, all phenomena associated with the ionic concentration during electrolysis, such as concentration polarization, cease to be relevant. 

Electrolysis in molten salts obeys Faraday s laws, although the demonstration of their validity is sometimes very difficult, as mentioned earlier. In fact, often during the electrolysis of molten electrolytes there are considerable and not readily avoidable losses in the current efficiency. Some of the causes of such losses are (i) evaporation or distillation of metal separated in the molten state (ii) secondary reactions between the separated molten metal and the materials with which it comes into contact and (iii) the solubility of the metal in the electrolyte. The latter cause appears to be the main one leading to a loss in current efficiency. 

The metallic impurities present in an impure metal can be broadly divided into two groups those nobler (less electronegative) and those less noble or baser (more electronegative) as compared to the metal to be purified. Purification with respect to these two classes of impurities occurs due to the chemical and the electrochemical reactions that take place at the anode and at the cathode. At the anode, the impurities which are baser than the metal to be purified would go into solution by chemical displacement and by electrochemical reactions whereas the nobler impurities would remain behind as sludges. At the cathode, the baser impurities would not get electrolytically deposited because of the unfavorable electrode potential and the concentration of these impurities would build up in the electrolyte. If, however, the baser impurities enter the cell via the electrolyte or from the construction materials of the cell, there would be no accumulation or build up because these would readily co-deposit at the cathode and contaminate the metal. It is for this reason that it is extremely important to select the electrolyte and the construction materials of the cell carefully. In actual practice, some of the baser impurities do get transferred to the cathode due to chemical reactions. As an example, let the case of the electrorefining of vanadium in a molten electrolyte composed of sodium chloride-potassium chloride-vanadium dichloride be considered. Aluminum and iron are typically considered as baser and nobler impurities in the metal. When the impure metal is brought into contact with the molten electrolyte, the following reaction occurs... 

The electroextraction process for molybdenum involves the use of its oxides, carbides or sulfides as soluble anodes in a potassium chloride-potassium hexachloromolybdate (K3MoCl6) molten electrolyte. An inert atmosphere electrolytic cell, with a provision for semicontinuous electrolysis, is used for this purpose. The process operation consists of the following steps. 

Strontium metal is not found in its elemental state in nature. Its salts and oxide compounds constitute only 0.025% of the Earths crust. Strontium is found in Mexico and Spain in the mineral ores of strontianite (SrCO ) and celestite (SrSO ). As these ores are treated with hydrochloric acid (HCl), they produce strontium chloride (SrCy that is then used, along with potassium chloride (KCl), to form a eutectic mixture to reduce the melting point of the SrCl, as a molten electrolyte in a graphite dish-shaped electrolysis apparatus. This process produces Sr cations collected at the cathode, where they acquire electrons to form strontium metal. At the same time, Cl anions give up electrons at the anode and are released as chlorine gas Cl T. 

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