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利用计时电位法研究了Ce~(3+)在LiC1-KC1共晶熔体和Sm~(3+)在等摩尔KCl-NaCl熔体中固体阴极上的电化学反应。在LiCl-KCl熔体中,Ce~(3+)的电化学反应为:Ce~(3+)+3e→Ce°;在KCl-NaCl熔体中,Sm~(3+)为Sm_(3+)+e→Sm~(2+)。在600℃下Ce~(3+)的扩散系数Dc_e~(3+)=2.08·10~(-5)cm~2/s;Sm~(3+)的扩散系数与温度的关系式为:lgDs_m~(3+)=-2.802-250/T。实验结果表明,Ce~(3+)可完全放电变为Ce°;而Sm~(3+)在比其它稀土离子更正的析出电位下还原为Sm~(2+),在氧化还原条件下Sm~(2+)的电化学反应为;Sm~(3+)+eSm~(2+)。
The electrochemical reaction of Ce ~ (3+) on solid cathodes of LiC1-KC1 eutectic melt and Sm ~ (3+) in equimolar KCl-NaCl melt was studied by chronopotentiometry. In LiCl-KCl melt, the electrochemical reaction of Ce ~ (3+) is: Ce ~ (3 +) + 3e → Ce °. In the melt of KCl-NaCl, Sm 3+ is Sm 3 +) + e → Sm ~ (2+). The diffusion coefficient of Ce ~ (3+) at 600 ℃ is Dc_e ~ (3 +) = 2.08 · 10 ~ (-5) cm ~ 2 / s and the diffusion coefficient of Sm ~ (3+) lgDs_m ~ (3 +) = -2.802-250 / T. The experimental results show that Ce 3+ can be completely discharged to Ce °, and Sm 3+ can be reduced to Sm 2+ at the deposition potential more correct than other rare earth ions. Under the redox condition, Sm The electrochemical reaction of ~ (2+) is Sm ~ (3 +) + eSm ~ (2+).