| PMBP与1,10菲绕啉对希土离子的协同萃取 |
| SYNERGIC EXTRACTION OF RARE EARTH JONS WITH PMBP AND 1,10-PHENANTHROLINE |
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| 摘要: 本文研究了1-苯基-3-甲基-4-苯甲酰基吡唑酮-5(PMBP,HA)及1,10-菲绕啉(B)从高氯酸及醋酸钠构成的缓冲溶液中(pH=4,μ=0.1),对全部希土离子(包括Y3+,不包括Pm3+)的协同萃取。此体系可表示为Ln3+(10-4M)/HClO4,NaAc(μ=0.1)/PMBP-Phen-CHCl3。用斜率法确定协萃合物组成为LnA3B,并求出各希土离子的协萃平衡常数logKs.e.o以logKs.e.o对原子序数Z作图,表现出四分组效应。相邻希土之间以及轻重希土之间的分离系数比单独用PMBP萃取时来得大。此体系有希望用于轻重希土分离。此外,还用萃取法制得了固体协萃合物,并对其红外光谱进行了分析讨论。 |
| 关键词: 协同萃取 吡唑酮 希土 1,10菲绕啉 |
| 基金项目: |
| Abstract: The solvent extraction studies of rare earth ions with l-phenyl-3-methyl- 4-benzoyl-pyrazolone- 5 (PMBP, HA) have been numerous. But only a few works investigate the solvent extraction behavior of all the 15 rare earth ions. Furthermore, the synergic extraction by PMBP and neutral extractant (such as TBP, TOPO, DPSO, DOSO...etc.) have been reported and the synergic extraction by another B-diketone (such as HTTA) and bidentate amines (such as 1,10-phenanthroline, simplified as phen and β) have been reported as well. But the synergic extraction behavior of all rare earth ions with PMBP and phen as extractants have not been reported yet. We have investigated the synergic extraction of the 15 rare earth ions (including yttrium but excepting promethium) by PMBP and phen from aqueous perchloric acid and sodium acetate buffer at pH equal to 4 and at 25℃. This system can be expressed as Ln3+ (104M)/HClO4, NaAc (H =0.1) /PMBP-phen-CHCl3.By slope analysis method the formulas of the synergic extracted complexes have been shown to be LnA3B and the synergic extraction constants have been calculated. The composition of the extracted complexes and the synergic extraction constants of all rare earth ions are shown in Table 3. In this table Ks.e is the extraction constant evaluated by Roy. The values of the equilibrium constant (log B3,1) for LnA3B show large synergic effect and increase with increase of atonic number. The mean separation factor calculated from logKs.e between the adjacent rare earth ions in this series is 2.3 and the separation factor between lanthanum" and lutetium is 3.4×104, which is about ten fold greater than the value obtained by both Roy and Chen by extracting with PMBP alone. This system can be used for the separation of lighter and heavier rare earth ions. A plot of, log Ks.e. values against atomic number Z show tetrad grouping (Fig. 1). The synergic extraction constant of yttrium located-its position between gadolinium and terbium. The results are in agreement with that of Roy and Chen. But log Ks.e of lutetium is greater than that of ytterbium.The complexes both in the organic phase and in the solid state were studied by IR spectroscopy. The spectrum of the CHCl3 solution of PMBP and phen after extraction compared with that before extraction has changed significiently in the 1400 to 1650 region, where the specified C = O and C = N vibration bands locate. In this spectrum, there are some new bands which may be assigned to the coupling vibrations of C = O and C = N vibrations while they both form chelate rings with the same rare earth ion. The pattern of IR spetrum of HoA3B in solid state and that of the complex in organic phase were very much alike. By IR spectroscopy the chelate bondings of the complexes both in solid state and in organic phase have been further comfirmed. |
| Keywords: synergic extraction pyrazolohe rare earth 1,10-pkenanthroline |
| 投稿时间：1985-03-13 |
| 摘要点击次数: 1246 |
| 全文下载次数: 1118 |
| 罗明润,程立,宋乐新,张定荣.PMBP与1,10菲绕啉对希土离子的协同萃取[J].无机化学学报,1986,2(2):39-48. |
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