Extraction of Eu(Ⅲ) and Am(Ⅲ) from Nitric Acid Solution with Bisdiglycolamides†

doi:10.7503/cjcu20140198

Abstract

Abstract:

Two bisdiglycolamides, N,N,N''',N'''-tetraoctyl-N',N″- ethanediyl bisdiglycolamide(TOE-BisDGA) and N,N,N''',N'''-tetraoctyl-N',N″-m-xylylene bisdiglycolamide(TOX-BisDGA), were synthesized by a mixed anhydrides method. Their extraction behaviors of Eu(Ⅲ) and Am(Ⅲ), as well as the extraction of nitric acid were investigated from nitric acid solution using kerosene/n-octanol(volume ratio 90∶10) as diluent. Nitric acid was extracted as the form of HNO₃·BisDGAs by BisDGAs at less than 1.0 mol/L HNO₃. The distribution ratios of Eu(Ⅲ) and Am(Ⅲ) increased with the increase of nitric acid concentration. TOE-BisDGA had a stronger extraction power for Eu(Ⅲ) and Am(Ⅲ) than TOX-BisDGA. Slope analyses showed that Eu(Ⅲ) and Am(Ⅲ) were extracted as di-solvated species by BisDGAs. The distribution ratios of Eu(Ⅲ) and Am(Ⅲ) decreased with temperature rise, which suggested that the extraction reaction of Eu(Ⅲ) and Am(Ⅲ) is exothermic. The two BisDGAs displayed a higher affinity toward Eu(Ⅲ) than Am(Ⅲ). In the mean time, the extraction mechanism was described and the apparent extraction equilibrium constant as well as Gibbs free energy change, enthalpy change and entropy change were presented. In addition, their Eu(Ⅲ) complexes were analyzed by IR and UV spectra.

Key words: Bisdiglycolamide, Americium, Europium, Extraction, Selectivity

CLC Number:

O615.11

TrendMD:

HUANG Song, DING Songdong, JIN Yongdong, MA Lijian, XIA Chuanqin, LI Shoujian, WU Yuxuan, HUANG Huang. Extraction of Eu(Ⅲ) and Am(Ⅲ) from Nitric Acid Solution with Bisdiglycolamides^†[J]. Chem. J. Chinese Universities, 2014, 35(7): 1369.

Figures/Tables 14

Scheme 1 Synthetic route for TOE-BisDGA and TOX-BisDGA

Table 1 Effect of diluents on the distribution ratios(D) of Eu(Ⅲ) and Am(Ⅲ)a

Extractant	D_Am				D_Eu
Extractant	Kerosene	Toluene	n-Octanol	Chloroform	Kerosene	Toluene	n-Octanol	Chloroform
TOE-BisDGA	1100^b	91	8.2	0.30	3459^b	406	37	1.1
TOX-BisDGA	411^b	98	16	0.22	592^b	273	112	1.4

Fig.1 Effect of extraction time on the distribution ratios of Eu(Ⅲ) and Am(Ⅲ) Organic phase: 0.1 mol/L TOE-BisDGA or TOX-BisDGA in kerosene/n-octanol(volume ratio 90∶10); aqueous phase: 3.0 mol/L HNO3; 1.3 mmol/L Eu(Ⅲ) or tracer amount of Am(Ⅲ).

Table 2 Extraction of nitric acid by 0.1 mol/L TOE-BisDGA or TOX-BisDGA in kerosene/n-octanol (volume ratio 90∶10) at different initial nitric acid concentration

c_ini(HNO₃)/(mol·L^-1)	TOX-BisDGA			TOE-BisDGA
c_ini(HNO₃)/(mol·L^-1)	[HNO₃]_org/(mol·L^-1)	D_H	[HNO₃]_org/(mol·L^-1)	D_H
0.5	1.37×10^-2	2.8×10^-2		2.06×10^-2	4.3×10^-2
1.0	3.66×10^-2	3.8×10^-2		4.58×10^-2	4.8×10^-2
2.0	9.16×10^-2	4.8×10^-2		1.05×10^-1	5.5×10^-2
3.0	1.60×10^-1	5.6×10^-2		1.69×10^-1	6.0×10^-2
4.0	2.29×10^-1	6.0×10^-2		2.34×10^-1	6.2×10^-2

Fig.2 Extraction of nitric acid by TOE-BisDGA or TOX-BisDGA in kerosene/n-octanol(volume ratio 90∶10) Aqueous phase: 0.5 or 1.0 mol/L HNO3. ■ 1.0 mol/L HNO3+TOX-BisDGA, slope=1.3, intercept=-0.19; ○ 1.0 mol/L HNO3+TOE-BisDGA, slope=1.1, intercept=-0.11; □ 0.5 mol/L HNO3+TOX-BisDGA, slope=1.0, intercept=-0.20; ● 0.5 mol/L HNO3+TOE-BisDGA, slope=1.0, intercept=-0.12.

Fig.3 Effect of initial nitric acid concentration on distribution ratios of Eu(Ⅲ) and Am(Ⅲ) Organic phase: 0.1 mol/L TOE-BisDGA or TOX-BisDGA in kerosene/n-octanol(volume ratio 90∶10); aqueous phase: 3.0 mol/L HNO3; 1.3 mmol/L Eu(Ⅲ) or tracer amount of Am(Ⅲ). ■ TOE-BisDGA-Eu; □ TOX-BisDGA-Eu; ● TOE-BisDGA-Am; ○ TOX-BisDGA-Am.

Table 3 Effect of initial nitric acid concentration on the separation factor SFEu/Am

c_ini(HNO₃)/(mol·L^-1)	SF_Eu/Am		c_ini(HNO₃)/(mol·L^-1)	SF_Eu/Am
c_ini(HNO₃)/(mol·L^-1)	TOE-BisDGA		TOX-BisDGA	TOE-BisDGA	TOX-BisDGA
0.5	3.1	10	3.0	9.0	17
1.0	4.7	13	4.0	9.8	12
2.0	8.2	22

Fig.4 Effect of extractant concentration on the distribution ratios of Eu(Ⅲ) and Am(Ⅲ) Organic phase:TOE-BisDGA or TOX-BisDGA in kerosene/n-octanol(volume ratio 90∶10); aqueous phase: 3.0 mol/L HNO3; 1.3 mmol/L Eu(Ⅲ) or tracer amount of Am(Ⅲ). △ TOE-BisDGA-Eu, slope=1.8; ■ TOX-BisDGA-Eu, slope=1.9; ▽ TOE-BisDGA-Am, slope=2.2; ● TOX-BisDGA-Am, slope=2.2.

Fig.5 Effect of temperature on the apparent extraction equilibrium constant lgKex Organic phase: 0.1 mol/L TOE-BisDGA or TOX-BisDGA in kerosene/n-octanol(volume ratio 90∶10); Aqueous phase: 3.0 mol/L HNO3; 1.3 mmol/L Eu(Ⅲ) or tracer amount of Am(Ⅲ). ○ TOE-BisDGA-Eu, slope=2.16, intercept=-2.78; ■ TOX-BisDGA-Eu, slope=2.81, intercept=-5.08; ● TOE-BisDGA-Am, slope=1.12, intercept=-0.09; □ TOX-BisDGA-Am, slope=2.18, inter-cept=-3.88.

Table 4 Thermodynamic parameters for the extraction of Eu(Ⅲ) and Am(Ⅲ) at 25 ℃*

Extraction system	ΔG/ (kJ·mol^-1)	ΔH/ (kJ·mol^-1)	ΔS/ (J·mol^-1·K^-1)
TOE-BisDGA-Eu	-26.8	-43.1	-54.6
TOE-BisDGA-Am	-21.6	-22.8	-4.0
TOX-BisDGA-Eu	-26.6	-56.3	-99.6
TOX-BisDGA-Am	-20.3	-42.7	-75.1

Table 5 Percentage of strippingextraction of Eu(Ⅲ) and Am(Ⅲ) from the loaded organic phase of 0.1 mol/L TOE-BisDGA or TOX-BisDGA in kerosene/n-octanol(volume ratio 90∶10) with deionized water or 0.01 mol/L HNO3 as the stripping agents

Strip stage	M	TOE-BisDGA		TOX-BisDGA
Strip stage	M	Deionized water	0.01 mol/L HNO₃	Deionized water	0.01 mol/L HNO₃
1	Eu	7	6	17	19
	Am	14	15	39	36
2	Eu	72	63	94	93
	Am	33	42	88	62
3	Eu	80	78	97	99
	Am	51	77	91	82
4	Eu	87	91	99	100
	Am	84	87	93	89
5	Eu	94	96	100	$*$
	Am	92	93	97	98
6	Eu	99	99	$*$	$*$
	Am	99	99	99	99

Strip stage	M	TOE-BisDGA		TOX-BisDGA
Strip stage	M	Deionized water	0.01 mol/L HNO₃	Deionized water	0.01 mol/L HNO₃
1	Eu	7	6	17	19
	Am	14	15	39	36
2	Eu	72	63	94	93
	Am	33	42	88	62
3	Eu	80	78	97	99
	Am	51	77	91	82
4	Eu	87	91	99	100
	Am	84	87	93	89
5	Eu	94	96	100	$*$
	Am	92	93	97	98
6	Eu	99	99	$*$	$*$
	Am	99	99	99	99

Fig.6 IR spectra of free ligands(a) and their Eu(Ⅲ) complexes(b) (A) TOE-BisDGA and TOE-BisDGA-Eu complex; (B) TOX-BisDGA and TOX-BisDGA-Eu complex.

Fig.7 UV spectra of free ligands and their Eu(Ⅲ) complexes a. TOX-BisDGA-Eu complex; b. TOE-BisDGA-Eu complex; c. TOX-BisDGA; d. TOE-BisDGA.

Table 6 Relevant data of UV spectra of free ligands and their Eu(Ⅲ) complexes

Compound	c/(mol·L^-1)	λ_max/nm	ε_max/(L·mol^-1·cm^-1)
TOX-BisDGA-Eu	1.0×10^-5	206	9.0×10⁴
TOX-BisDGA	1.0×10^-5	205	2.8×10⁴
TOE-BisDGA-Eu	1.0×10^-5	206	4.6×10⁴
TOE-BisDGA	1.0×10^-5	206	1.7×10⁴

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