Sensors for EMF Measurements in Molten Salt Electrolysis

"The use of emf measurements to derive classical thermochemical data has been in use for many years. The reaction associated with electrochemical process is harnessed in a galvanic cell and energy involved measured in terms of electromotive force. The property requirements of sensor electrodes used differ for various aqueous, molten salt and solid electrolyte systems. The electrodes for molten salt electrolytes need special care for construction. This paper describes the studies carried out using an Ag/ AgCI reference electrode. This electrode was used to measure the solubility of compounds in molten salt electrolytes. The results obtained using this electrode are in excellent agreement with the values from chemical analysis method.I. IntroductionThe technique of obtaining a metal from its oxides by electrolysis is more than a century old process now. In these processes, it has been well established that for halide electrolytes, only the dissolved oxides are available for the dissociation at the electrode to release the metal during electrolysis. Therefore, the solubility of metallic oxides in the molten salt electrolytes is an important parameter which determines the economical and technical viability of these processes. The widely used molten salts systems in halides are fluorides and chlorides. The fluoride electrolyte system is used in our present study.The viability of obtaining aluminum alloys by in-situ electrochemical processing has been outlined in our earlier publications[1-8]. Studies on the solubility of various alloying element compounds is a part of our ongoing research efforts for the direct production of Al-Li alloys. As mentioned above, the solubility of lithium oxide and lithium carbonate compounds in molten fluoride electrolyte system have studied using EMF technique. The change in potential of the molten electrolyte was measured by a working electrode against the reference electrode with the addition of lithium compound."