Thermodynamic calculation and reference electrode calibration for high temperature molten salts

Molten salts are important reaction media for chemical and electrochemical processing and have recently attracted attention for their potential in reprocessing and partitioning spent nuclear fuels. Electrochemical measurements are a convenient tool for exploring thermodynamic and kinetic properties of molten salts, but inconsistency in acquired data may arise from the use of inaccurate reference electrodes and differences in thermodynamic calculations. A thermodynamic approach to the calculation of half cell potentials for reactions in molten salts is proposed. As examples, chlorine/chloride and lithium ion/lithium half cell potentials in LiCl–KCl eutectic are thermodynamically analysed. The Ag/AgCl reference electrode is discussed as an example of a high temperature reference electrode. A technique involving in situ transient reduction of constitutive metal ions for the calibration of high temperature reference electrodes is developed which may enable the consistency of acquired data using different reference electrodes in a variety of molten salts. The thermodynamic approach and calibration technique may be extended to ionic liquid and other media at high and low temperatures.