Abstract
Electrochemical studies of the redox couple Sm(III)/Sm(II) were carried out in NaCl-KCl-SmCl3 and NaCl-KCl-SmCl3 melts in a temperature range of 973-1173 K by cyclic voltammetry.Diffusion coefficients (D) of Sm(III) in these melts were determined using Randels–Shevchik equation. It was found that D in the NaCl-KCl-SmF3 melt are less than D in the NaCl-KCl-SmCl3 melt. At the same time activation energies for diffusion (ΔU) of Sm(III) in the NaCl-KCl-SmF3 melt are higher than ΔU in the NaCl-KCl-SmCl3 melt that is related to the increased strength of the complexes in transition from SmCl3 to SmF3 molten system. The standard rate constants of charge transfer (k s) for the Sm(III)/Sm(II) redox couple were determined by cyclic voltammetry both in NaCl-KCl-SmCl3 and NaCl-KCl-SmF3 molten salts using the Nicholson’s equation. The higher values of k s were obtained in chloride melt than in chloride-fluoride molten system.
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