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本文研究稀土元素的水溶液在汞阴极上进行电沉积的条件及规律。各稀土元素的电沉积率随原子序数的变化在钆处发生明显转折。变价稀土钐、铕和镱的电沉积率最高,两相邻稀土间原子序数为奇数的电沉积率比偶数的高。在柠檬酸锂溶液体系中电解制得了钆、铽和镝汞齐。用季铵汞齐电极、锂汞齐电极在两种溶液体系中研究镧、镨、钕、钐、铕和镱的电沉积率随溶液pH的变化,结果表明:在四甲基铵汞齐电极上于柠檬酸溶液体系中,有可能自镧、镨、钕、钐和镱中分离铕;自镧、钐和镱中分离镨、钕;自钐、镱中分离镧。也可以考虑各稀土元素的分步电解分离。在四甲基铵汞齐电极上于磺基水杨酸溶液体系中,有可能自镧、镨、钕、钐和镱中分离铕;自镨、钕中分离钐和镱。在锂汞齐电极电极上于柠檬酸溶液体系中,有利于制备各稀土元素的汞齐或有可能进行轻、重稀土元素之间的分组分离。在锂汞齐电极上于磺基水杨酸溶液体系中,可以考虑镧、钐、铕和镱四元素与镨、钕的分离。在pH4的条件下(溶液组成为Ln~(3+)∶SSA~(3-)∶Li~+=1∶x∶6),有利于镨和钕的分离。
In this paper, the conditions and rules for the electrodeposition of rare earth elements in mercury cathodes were studied. Electrodeposition rate of rare earth elements with atomic number changes in the gadolinium at a significant turning point. The change rate of rare earth samarium, europium and ytterbium electrodepositing rate is highest, two adjacent rare earth atomic number odd number of electrodeposition rate higher than even number. Gadolinium, terbium and dysprosium amalgam electrolyzed in the solution of lithium citrate. Electrodeposition rate of lanthanum, praseodymium, neodymium, samarium, europium and ytterbium with solution pH was studied by quaternary ammonium amalgam electrode and lithium amalgam electrode in two solution systems. On the citric acid solution system, it is possible to separate europium from lanthanum, praseodymium, neodymium, samarium and ytterbium; to separate praseodymium and neodymium from lanthanum, samarium and ytterbium; to separate lanthanum from samarium and ytterbium. It is also possible to consider the stepwise electrolytic separation of the rare earth elements. On the tetramethylammonium amalgam electrode in the sulfosalicylic acid solution system, it is possible to separate europium from lanthanum, praseodymium, neodymium, samarium and ytterbium; to separate samarium and ytterbium from praseodymium and neodymium. In the lithium amalgam electrode electrode in the citric acid solution system, it is beneficial to prepare the amalgam of each rare earth element or it is possible to perform the segregation between light and heavy rare earth elements. The separation of lanthanum, samarium, europium and ytterbium tetrachloride from praseodymium and neodymium can be considered in the sulfosalicylic acid solution system at the lithium amalgam electrode. Under the condition of pH4 (solution composition Ln ~ (3+): SAA ~ (3-): Li ~ + = 1: x: 6), it is in favor of the separation of praseodymium and neodymium.