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Journal Articles

Electrochemical behaviors of PuN and (U, Pu)N in LiCl-KCl eutectic melts

Shirai, Osamu; Kato, Tetsuya*; Iwai, Takashi; Arai, Yasuo; Yamashita, Toshiyuki

Journal of Physics and Chemistry of Solids, 66(2-4), p.456 - 460, 2005/02

https://doi.org/10.1016/j.jpcs.2004.06.040
 Times Cited Count：8 Percentile：36.29(Chemistry, Multidisciplinary)

Electrochemical behaviors of PuN and (U, Pu)N in the LiCl-KCl eutectic melt containing UCl$$_{3}$$ and PuCl$$_{3}$$ at 773 K were investigated by cyclic voltammetry. The electrochemical dissolution of PuN and (U, Pu)N began nearly at -1.0 V vs. the Ag/AgCl reference electrode. The rest potentials of PuN and (U, Pu)N were observed at about 0.15 V more negative potential than that of UN since the equilibrium potential of UN is about 0.15 V more positive than that of PuN. In the cyclic voltammogram measured by using (U, Pu)N as the working electrode, a steep rise of the positive current was observed at more positive potential than -0.4 V in analogy with the cyclic voltammogram measured by using UN as the working electrode. In addition, there were two anodic current waves in the voltammogram with (U, Pu)N, though the wave form was not clear. This indicates that UN and PuN would be dissolved independently irrespective of formation of the solid solution, (U, Pu)N.

Journal Articles

Electrode reaction of the Np$$^{3+}$$/Np couple at liquid Cd and Bi electrodes in LiCl-KCl eutectic melts

Shirai, Osamu; Uozumi, Koichi*; Iwai, Takashi; Arai, Yasuo

Journal of Applied Electrochemistry, 34(3), p.323 - 330, 2004/03

https://doi.org/10.1023/B:JACH.0000015615.17281.51
 Times Cited Count：29 Percentile：53.05(Electrochemistry)

The electrode reactions of the Np$$^{3+}$$/Np couple at liquid Cd and Bi electrodes were investigated by cyclic voltammetry at 723, 773 and 823 K in LiCl-KCl eutectic melt. It was found that the diffusion of Np$$^{3+}$$ in the salt phase was a rate-determining step in the cathodic reaction when the concentration of NpCl$$_{3}$$ was less than about 1 wt.% and the liquid Cd or Bi phase was not saturated with Np. The redox potentials of the Np$$^{3+}$$/Np couple at liquid Cd electrode at 723, 773 and 823 K were observed more positively than those at Mo electrode by 0.158, 0.140 and 0.126 V, respectively. The potential shift would result from a lowering of activity of Np in Cd phase according to the alloy formation of NpCd$$_{11}$$ at 723 K and NpCd$$_{6}$$ at 773 and 823 K. The redox potentials of the Np$$^{3+}$$/Np couple at liquid Bi electrode at 723, 773 and 823 K were more positive than those at Mo electrode by 0.427, 0.419 and 0.410 V, respectively, which would be attributable to a lowering of activity of Np in Bi phase according to the formation of NpBi$$_{2}$$.

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