高等学校化学学报 ›› 2014, Vol. 35 ›› Issue (7): 1369.doi: 10.7503/cjcu20140198
黄松1, 丁颂东1(), 金永东1, 马利建1, 夏传琴1, 李首建1, 吴宇轩1,2, 黄璜1,2
收稿日期:
2014-03-11
出版日期:
2014-07-10
发布日期:
2014-05-19
作者简介:
联系人简介: 丁颂东, 男, 博士, 研究员, 主要从事核燃料循环与材料研究. E-mail: 基金资助:
HUANG Song1, DING Songdong1,*(), JIN Yongdong1, MA Lijian1, XIA Chuanqin1, LI Shoujian1, WU Yuxuan1,2, HUANG Huang1,2
Received:
2014-03-11
Online:
2014-07-10
Published:
2014-05-19
Contact:
DING Songdong
E-mail:dsd68@163.com
Supported by:
摘要:
采用混合酸酐法合成了两种双二苷酰胺(bisdiglycolamide, BisDGA)萃取剂: N,N,N''',N'''-四正辛基-N',N″-乙二基-双二苷酰胺(TOE-BisDGA)和N,N,N''',N'''-四正辛基-N',N″-间苯二甲基-双二苷酰胺(TOX-BisDGA). 以磺化煤油和正辛醇混合溶液(体积比 90∶10)作稀释剂, 研究了它们在硝酸溶液中对Eu(Ⅲ)和Am(Ⅲ), 以及自身对HNO3的萃取行为. 结果表明, 2种BisDGAs对HNO3均有一定萃取, 当酸度不超过1.0 mol/L时, 二者形成1∶1型的萃合物. 随HNO3浓度增加, Eu(Ⅲ)和Am(Ⅲ)的萃取分配比增加. 相同条件下, TOE-BisDGA对Eu(Ⅲ)和Am(Ⅲ)的萃取能力强于TOX-BisDGA. 斜率分析表明TOE-BisDGA和TOX-BisDGA与Eu(Ⅲ)和Am(Ⅲ)均形成2∶1型的萃合物. 温度升高, 萃取分配比下降, 萃取反应是放热反应. 2种BisDGAs对Eu(Ⅲ)的亲和力强于对Am(Ⅲ)的亲合力, 表明BisDGAs对Eu(Ⅲ)有一定的选择性. 同时, 研究了BisDGAs萃取Eu(Ⅲ)和Am(Ⅲ)的机理, 给出了表观萃取平衡常数和萃取反应热力学函数ΔH, ΔS和ΔG的值. 此外, 还对TOE-BisDGA和TOX-BisDGA与Eu(Ⅲ)形成的配合物进行了红外和紫外光谱分析.
中图分类号:
TrendMD:
黄松, 丁颂东, 金永东, 马利建, 夏传琴, 李首建, 吴宇轩, 黄璜. 双二苷酰胺从硝酸溶液中萃取Eu(Ⅲ)和Am(Ⅲ). 高等学校化学学报, 2014, 35(7): 1369.
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†. Chem. J. Chinese Universities, 2014, 35(7): 1369.
Extractant | DAm | DEu | |||||||
---|---|---|---|---|---|---|---|---|---|
Kerosene | Toluene | n-Octanol | Chloroform | Kerosene | Toluene | n-Octanol | Chloroform | ||
TOE-BisDGA | 1100b | 91 | 8.2 | 0.30 | 3459b | 406 | 37 | 1.1 | |
TOX-BisDGA | 411b | 98 | 16 | 0.22 | 592b | 273 | 112 | 1.4 |
Table 1 Effect of diluents on the distribution ratios(D) of Eu(Ⅲ) and Am(Ⅲ)a
Extractant | DAm | DEu | |||||||
---|---|---|---|---|---|---|---|---|---|
Kerosene | Toluene | n-Octanol | Chloroform | Kerosene | Toluene | n-Octanol | Chloroform | ||
TOE-BisDGA | 1100b | 91 | 8.2 | 0.30 | 3459b | 406 | 37 | 1.1 | |
TOX-BisDGA | 411b | 98 | 16 | 0.22 | 592b | 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).
cini(HNO3)/(mol·L-1) | TOX-BisDGA | TOE-BisDGA | ||||
---|---|---|---|---|---|---|
[HNO3]org/(mol·L-1) | DH | [HNO3]org/(mol·L-1) | DH | |||
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 |
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
cini(HNO3)/(mol·L-1) | TOX-BisDGA | TOE-BisDGA | ||||
---|---|---|---|---|---|---|
[HNO3]org/(mol·L-1) | DH | [HNO3]org/(mol·L-1) | DH | |||
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.
cini(HNO3)/(mol·L-1) | SFEu/Am | cini(HNO3)/(mol·L-1) | SFEu/Am | ||
---|---|---|---|---|---|
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 |
Table 3 Effect of initial nitric acid concentration on the separation factor SFEu/Am
cini(HNO3)/(mol·L-1) | SFEu/Am | cini(HNO3)/(mol·L-1) | SFEu/Am | ||
---|---|---|---|---|---|
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.
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 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 |
Strip stage | M | TOE-BisDGA | TOX-BisDGA | |||
---|---|---|---|---|---|---|
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 |
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 | |||
---|---|---|---|---|---|---|
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 |
Compound | c/(mol·L-1) | λmax/nm | εmax/(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 |
Table 6 Relevant data of UV spectra of free ligands and their Eu(Ⅲ) complexes
Compound | c/(mol·L-1) | λmax/nm | εmax/(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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