High Efficiency and Selective Extraction of Uranyl Ion by N,N'-Diethyl-N,N'-bis(propoxyphenyl)-2,6-dipicolinamide†

doi:10.7503/cjcu20150160

Abstract

Abstract:

To acquire a more efficent and selective dipicolinamide, the affinity of three novel diamide derivatives of dipicolinic acids N,N'-diethyl-N,N'-bis(propoxyphenyl)-2,6-dipicolinamide(1a—1c) for uranyl ion was investigated by liquid-liquid extraction method. In the absence of HNO₃ and in the presence of 6 mol/L HNO₃, the extractability of compound 1a for uranyl ion was 99% and 94%, respectively. At the same high acidity, selective separation of uranyl from lanthanides(La, Eu and Yb) was achieved using compound 1a as extractant [SF_{U(VI)/Ln(III)}>20]. In contrast, compounds 1b and 1c were able to separate uranyl ion from lighter lanthanides(La and Eu). Result of lg-lg plot experiments indicated the stoichiometric ratios of compounds 1a, 1b and 1c with uranyl were found to fall between 1 and 2, suggesting the presence of two kinds of extracted species in 2∶1 and 1∶1 ratios(extractant∶uranyl). ¹H NMR and FTIR spectra of the extracted complexes implicated the involvement of nitrogen atom in the pyridine ring and carbonyl group in coordinating uranyl ion. The results showed that compound 1a is the most promising extractant and probably can be used in the recycling of uranyl ion.

Key words: Dipicolinamide, Uranyl ion, Extraction, Selectivity

CLC Number:

O655
O615

TrendMD:

CHEN Long, LI Yan, WANG Zhenwen, PENG Zhiyong, YANG Zeming, YUAN Lihua, FENG Wen. High Efficiency and Selective Extraction of Uranyl Ion by N,N'-Diethyl-N,N'-bis(propoxyphenyl)-2,6-dipicolinamide^†[J]. Chem. J. Chinese Universities, 2015, 36(8): 1485.

Figures/Tables 8

Fig.1 Chemical structures of compounds 1a—1c and 2

Table 1 Extractabilities(%) of UO22+ for compounds 1a—1c and 2 at various concentrations of HNO3

Compd.	c(HNO₃)/(mol·L^-1))
Compd.	0	1	2	3	4	5	6
1a^a	99.0±0.2	7.2±0.9	46.5±0.7	79.1±0.2	91.4±0.3	93.5±0.5	94.3±0.0
1b^a	15.8±0.2	<1^b	7.8±0.6	26.4±1.2	59.7±0.3	78.4±0.6	84.4±0.3
1c^a	24.3±2.2	<1^b	15.8±0.8	45.7±0.8	73.5±0.8	85.1±0.2	88.8±0.2
2^a	26.9±0.2	<1^b	2.6±1.6	17.7±1.9	42.4±0.5	63.6±0.2	78.0±0.6

Fig.2 Plots of lgD vs. lg[NO3-] for the extraction of UO22+ with compounds 1a—1c(a—c)

Fig.3 Distribution ratio(D) of UO22+ for all extrac-tants at various concentrations of HNO3

Table 2 Distribution ratio of selective lanthanides and actinides(1×10-4 mol/L) for compounds 1a—1c and 2 from HNO3 aqueous solution(6 mol/L) into F-3

Compd.	D
Compd.	La³⁺	Eu³⁺	Yb³⁺	U
1a	<0.01^*	0.02	0.86	18.2
1b	<0.01^*	0.08	4.06	6.02
1c	<0.01^*	0.07	7.24	8.09
2	0.01	0.04	1.8	3.39

Fig.4 Separation factor of UO22+ to some lanthanides(La3+, Eu3+ and Yb3+) from HNO3 aqueous solution(6 mol/L) into F-3

Fig.5 Plots of lgD vs. lg[L] for the extraction of UO22+ with compounds 1a—1c(a—c)

Scheme 1 Selective extraction of UO22+ by compound 1a

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