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${it In-situ}$ measurement of UO$$_{2}$$$$^{2+}$$ concentration in molten NaCl-2CsCl by differential pulse voltammetry

Nagai, Takayuki  ; Uehara, Akihiro*; Fujii, Toshiyuki*; Shirai, Osamu*; Yamana, Hajimu*

In order to assess the applicability of Differential Pulse Voltammetry technique to the ${it In-situ}$ measurement of UO$$_{2}$$$$^{2+}$$ concentration in the oxide electro-winning process, DPV measurements for UO$$_{2}$$Cl$$_{2}$$ in molten NaCl-2CsCl were studied. DPV measurement of UO$$_{2}$$$$^{2+}$$ in NaCl-2CsCl at 923 K, with a set of optimized parameters (potential sweep rate -0.1 V/s, pulse cycle 0.1 s, pulse width 10 ms, and pulse potential height 50 mV), showed a clear current peak at -0.9 V vs. Cl$$_{2}$$/Cl$$^{-}$$, and it was attributed to the reduction of UO$$_{2}$$$$^{2+}$$ to UO$$_{2}$$$$^{+}$$. The relation between the current peak height and the analytical concentration of the UO$$_{2}$$$$^{2+}$$ showed good proportionality in the concentration region up to 0.06 mol/${it l}$, and the applicability of UO$$_{2}$$$$^{2+}$$ concentration measurement by DPV was confirmed up to 0.4 mol/${it l}$. In order to assess the interference by the coexisting fission product elements to the measurement of UO$$_{2}$$$$^{2+}$$ concentration, DPV measurements of UO$$_{2}$$$$^{2+}$$ concentration in molten NaCl-2CsCl containing PdCl$$_{2}$$, NdCl$$_{3}$$, SmCl$$_{3}$$, and CeCl$$_{3}$$ were performed also. Even before removing Pd, the current peak at -0.9 V vs. Cl$$_{2}$$/Cl$$^{-}$$ by the reduction of UO$$_{2}$$$$^{2+}$$ to UO$$_{2}$$$$^{+}$$ was found to be distinguishable from the reduction currents of Pd$$^{2+}$$ to Pd at -0.7 V vs. Cl$$_{2}$$/Cl$$^{-}$$. As a result, the applicability of DPV measurement technique to the ${it In-situ}$ monitoring of UO$$_{2}$$$$^{2+}$$ concentration in oxide electro-winning method is proposed.

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