Determination of Kinetic Properties of Ni(II) Ions in Molten LiF-NaF-KF via Voltammetry

Abstract

Kinetic properties of Ni(II) in eutectic LiF-NaF-KF (FLiNaK) molten salt were determined at T = 748–823 K using cyclic voltammetry (CV), square wave voltammetry (SWV), and chronoamperometry (CA) measurements using a glassy C working electrode, Ni(II)/Ni reference electrode, and Ni counter electrode. Reduction of Ni(II) to Ni(s) was determined to be a single step, two-electron transfer process. Diffusivity values were calculated using the Berzins and Delahay equation and semi-integral electroanalysis from the CV measurements as well as using the Cottrell equation from the CA measurements. Diffusivity of Ni(II) in molten FLiNaK at T = 748–823 K was determined to be 3.27 × 10 –7 –3.04 × 10 –6 cm 2 s –1 with an activation energy of 62–104 kJ mol –1 . The estimated kinetic properties varied appreciably among methodologies possibly due to inherent assumptions in theory regarding reversibility and unit activity during Ni metal deposition on the working electrode. Diffusivity of Ni(II) in FLiNaK determined electrochemically Valuable discussion of reversibility and employment of variety of approaches Calculated properties of Ni(II) in molten salt useful for corrosion prevention Berzins-Delahay, semi-integral convolution, and Cottrell techniques utilized Deficiencies and advantages of differing theoretical approaches addressed