Electromotive force (emf) measurements made using a combination of solute- and solvent-based electrodes were used to determine the activity of NiF2 in molten FLiNaK eutectic at 823 K across a concentration range of x NiF2 = 5.2 × 10–4–1.0 × 10–2. The solute emf values were measured using electrodes consisting of Ni wires immersed in FLiNaK with dissolved NiF2 contained in graphite crucibles. The measured emf values were then converted to the FLiNaK Eutectic Potassium Electrode (FEKE) potential and used to quantify the activity of dissolved NiF2. This quantification was based upon comparative measurements of a reference solvent electrode consisting of a K-Bi alloy immersed in pure FLiNaK contained in a boron nitride crucible and a solute electrode. Short cell lives were characteristic of the measurements due to the corrosive nature of the fluoride salts. Quantifying the activity of NiF2 will improve the utility of Ni2+/Ni reference electrodes in molten fluoride salts, which are notoriously difficult electrolytes to work with because of their reactivity. This work demonstrates the general nature of the solute-solvent approach as a repeatable, easily employed method for measuring the activity values of electroactive species in a variety of molten salts to improve understanding of the electroactive species behavior in these systems.
Electromotive force (emf) measurements made using a combination of solute- and solvent-based electrodes were used to determine the activity of NiF2 in molten FLiNaK eutectic at 823 K across a concentration range of xNiF2 = 5.2 × 10-4–1.0 × 10-2. The solute emf values were measured using electrodes consisting of Ni wires immersed in FLiNaK with dissolved NiF2 contained in graphite crucibles. The measured emf values were then converted to the FLiNaK Eutectic Potassium Electrode (FEKE) potential and used to quantify the activity of dissolved NiF2. This quantification was based upon comparative measurements of a reference solvent electrode consisting of a K-Bi alloy immersed in pure FLiNaK contained in a boron nitride crucible and a solute electrode. Short cell lives were characteristic of the measurements due to the corrosive nature of the fluoride salts.Quantifying the activity of NiF2 will improve the utility of Ni2+/Ni reference electrodes in molten fluoride salts, which are notoriously difficult electrolytes to work with because of their reactivity. This work demonstrates the general nature of the solute-solvent approach as a repeatable, easily employed method for measuring the activity values of electroactive species in a variety of molten salts to improve understanding of the electroactive species behavior in these systems.
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