二(2-乙基己基)二硫代次膦酸对硝酸溶液中Am3+和Eu3+的萃取

doi:10.7503/cjcu20180133

摘要/Abstract

摘要：

以正十二烷作稀释剂, 研究了二(2-乙基己基)二硫代次膦酸(D2EHDTPA)对HNO₃溶液中Am³⁺和Eu³⁺的萃取行为. 考察了酸度、萃取剂及N $O 3 -$ 浓度和皂化度对萃取的影响. 在考察的pH范围(2.5~4.5)内, D2EHDTPA萃取Am³⁺和Eu³⁺的分配比(D)随pH值增大而增加; pH=3.65时, 分离因子(SF_Am/Eu)值达到最大(4000). 随D2EHDTPA浓度的增加, D_Am和D_Eu值均增加. 斜率分析表明, D2EHDTPA萃取Am³⁺和Eu³⁺主要形成3:1和2:1型的萃合物. N $O 3 -$ 未直接参与D2EHDTPA对Am³⁺和Eu³⁺的萃取反应. D2EHDTPA经NaOH皂化后, 萃取能力显著增强, SF_Am/Eu值提高到10⁴量级, 萃取容量约为理论值的60%. 此外, 使用高分辨质谱、红外光谱和等温微量热滴定方法研究了D2EHDTPA与Eu³⁺的配位化学行为, 得到了金属离子与配体的组成比、络合物稳定常数以及配位热力学参数ΔH, ΔS和ΔG值.

关键词: 二(2-乙基己基)二硫代次膦酸, Am³⁺, Eu³⁺, 萃取, 选择性

Abstract:

The extraction of Am³⁺ and Eu³⁺ from HNO₃ solution with di(2-ethylhexyl)dithiophosphinic acid(D2EHDTPA) were investigated using n-dodecane as diluent. Influences of acidity, ligand concentration, N $O 3 -$ concentration and saponification on the extraction of Am³⁺ and Eu³⁺ were evaluated. The distribution ratio values of both Am³⁺ and Eu³⁺ increased with increasing pH values from 2.5 to 4.5, and also with increasing the ligand concentration from 0.10 mol/L to 0.50 mol/L. The maximum value of separation factor(SF_Am/Eu) can reach 4000 at pH=3.65. Slope analyses indicated the main formation of 3:1 and 2:1 complexes of D2EHDTPA with Am³⁺ and Eu³⁺, respectively. The nitrate ion did not take part in the extraction reaction of D2EHDTPA with Am³⁺ or Eu³⁺. The extractability of D2EHDTPA was significantly enhanced through the saponification with NaOH solution. SF_Am/Eu values could be improved to the magnitude of 10⁴, and the extraction capacity was approximately 60% of the theoretical value. Furthermore, the complexation behaviors of D2EHDTPA with Eu³⁺ were also investigated by electrospray ionization mass spectrometry(ESI-MS), Fourier transform infrared(FTIR) and isothermal titration calorimetry(ITC). The composition and stability constants(lgβ) of the complex of D2EHDTPA with Eu³⁺, as well as the thermodynamic parameters(ΔH, ΔS and ΔG) were obtained.

Key words: Di(2-ethylhexyl)dithiophosphinic acid, Am³⁺, Eu³⁺, Extraction, Selectivity

中图分类号:

O615.11

TrendMD:

张利荣, 王志鹏, 刘莹, 徐超, 陈靖, 丁颂东. 二(2-乙基己基)二硫代次膦酸对硝酸溶液中Am³⁺和Eu³⁺的萃取. 高等学校化学学报, 2019, 40(1): 1.

ZHANG Lirong,WANG Zhipeng,LIU Ying,XU Chao,CHEN Jing,DING Songdong. Extraction of Trivalent Americium and Europiumfrom Nitric Acid Solution with Di(2-ethylhexyl)dithiophosphinic Acid^†. Chem. J. Chinese Universities, 2019, 40(1): 1.

图/表 13

Fig.1 Chemical structures of purified Cyanex 301 and D2EHDTPA

Fig.2 Influence of contact time on the distribution ratio of Am3+ and Eu3+Organic phase: 0.50 mol/L D2EHDTPA in n-dodecane; aqueous phase: trace amount of 241Am3+ or 152,154Eu3+ in 1.0 mol/L NaNO3 solution with pH of 3.35 and 4.05 for Am3+ and Eu3+, respectively.

Fig.3 Influence of pH on the distribution ratio of Am3+ and Eu3+Organic phase: 0.50 mol/L D2EHDTPA in n-dodecane; aqueous phase: trace amount of 241Am3+ or 152,154Eu3+ in 1.0 mol/L NaNO3 solution with various pH.

Fig.4 Influence of D2EHDTPA concentration on the extraction of Am3+ and Eu3+Organic phase: various concentration of D2EHDTPA in n-dodecane; aqueous phase: trace amount of 241Am3+ or 152,154Eu3+ in 1.0 mol/L NaNO3 solution with pH of 3.24 and 4.40 for Am3+ and Eu3+, respectively.

Fig.5 Influence of NO3- concentration on the extraction of Am3+ and Eu3+Organic phase: 0.10(A), 0.30(B) or 0.50(C) mol/L D2EHDTPA in n-dodecane; aqueous phase: trace amount of 241Am3+ or 152,154Eu3+ in various concentration NaNO3 solutions with pH of 3.24 and 4.40 for Am3+ and Eu3+, respectively.

Table 1 Apparent extraction equilibrium constants for Am3+ and Eu3+ by D2EHDTPA at 25 ℃

c_L /(mol·L^-1)	lg $K ex, Am a$	lg $K ex, Eu b$	c_L /(mol·L^-1)	lg $K ex, Am a$	lg $K ex, Eu b$
0.10	-7.22	-9.00	0.35	-7.21	-9.16
0.15	-7.17	-9.11	0.40	-7.19	-9.19
0.20	-7.22	-9.19	0.45	-7.20	-9.18
0.25	-7.21	-9.15	0.50	-7.20	-9.09
0.30	-7.24	-9.15	Average value	-7.21	-9.14

Table 1 Apparent extraction equilibrium constants for Am3+ and Eu3+ by D2EHDTPA at 25 ℃

c_L /(mol·L^-1)	lg $K ex, Am a$	lg $K ex, Eu b$	c_L /(mol·L^-1)	lg $K ex, Am a$	lg $K ex, Eu b$
0.10	-7.22	-9.00	0.35	-7.21	-9.16
0.15	-7.17	-9.11	0.40	-7.19	-9.19
0.20	-7.22	-9.19	0.45	-7.20	-9.18
0.25	-7.21	-9.15	0.50	-7.20	-9.09
0.30	-7.24	-9.15	Average value	-7.21	-9.14

Fig.6 Influence of the saponification degree of D2EHDTPA on the distribution ratio of Am3+ and Eu3+

Table 2 Influence of the saponification degree of D2EHDTPA on the separation factor*

Saponification degree(%)	0	1	3	5	10	15	20
SF_Am/Eu	5.55	5.05	1.34×10⁴	2.51×10⁴	1.34×10⁴	4.86×10³	5.07×10³

Table 3 Eu3+ concentration in organic phase after extraction by D2EHDTPAa

$c Eu i b$ /(mol·L^-1)	0.1	0.2	0.3	0.4	0.5
$c Eu o c$ /(mol·L^-1)	0.022	0.022	0.022	0.023	0.022

Table 3 Eu3+ concentration in organic phase after extraction by D2EHDTPAa

$c Eu i b$ /(mol·L^-1)	0.1	0.2	0.3	0.4	0.5
$c Eu o c$ /(mol·L^-1)	0.022	0.022	0.022	0.023	0.022

Fig.7 HRESI(+)-MS spectra of the organic phase loaded with Eu3+

Fig.8 FTIR spectra of D2EHDTPA(a) and the organic phase loaded with Eu3+(b)

Fig.9 Microcalorimentric titration of Eu(ClO4)3 with D2EHDTPA in EtOH-H2O(volume ratio 99:1)(A) and the observed and fitted cumulative heat and the speciation of Eu3+ along the titration(B)Initial conditions: [Eu3+]=1.0×10-3 mol/L, volume=1.40 mL; Titration conditions: [D2EHDTPA]=1.0×10-2 mol/L, 30 additions of 0.01 mL each.

Table 4 Thermodynamic parameters for the complexation of Eu3+ with D2EHDTPA at 25 ℃

Reaction	lgβ	ΔH/(kJ·mol^-1)	ΔS/(J·mol^-1·K^-1)	ΔG/(kJ·mol^-1)
Eu³⁺+L^-=EuL²⁺	3.56	12.7	72.3	-8.85
Eu³⁺+2L^-=Eu $L 2 +$	6.57	16.6	113	-17.2
Eu³⁺+3L^-=EuL₃	9.52	18.5	162	-29.8

Table 4 Thermodynamic parameters for the complexation of Eu3+ with D2EHDTPA at 25 ℃

Reaction	lgβ	ΔH/(kJ·mol^-1)	ΔS/(J·mol^-1·K^-1)	ΔG/(kJ·mol^-1)
Eu³⁺+L^-=EuL²⁺	3.56	12.7	72.3	-8.85
Eu³⁺+2L^-=Eu $L 2 +$	6.57	16.6	113	-17.2
Eu³⁺+3L^-=EuL₃	9.52	18.5	162	-29.8

参考文献 49

[1]	Bhattacharyya A., Ghanty T. K., Mohapatra P. K., Manchanda V. K., Inorg.Chem.,2011, 50, 3913—3921
[2]	Xue W. J., Zhang A. Y., Chai Z. F., China Science Paper.,2012, 7(9), 657—665
	(薛文静, 张安运, 柴之芳. 中国科技论文, 2012, 7(9), 657—665)
[3]	Mathur J. N., Murali M. S., Nash K. L., Solvent Extr. IonExch.,2001, 19(3), 357—390
[4]	Nash K. L., Solvent Extr. Ion Exch., 1993, 11(4), 729—768
[5]	Mincher B. J., Modolo G., Mezyk S. P., Solvent Extr. Ion Exch.,2010, 28(4), 415—436
[6]	Chen J., Wang F., He X. H., Pan D. F., Prog.Chem.,2011, 23(7), 1338—1344
	(陈靖, 王芳, 何喜红, 盘登芳. 化学进展, 2011, 23(7), 1338—1344)
[7]	Dam H. H., Reinhoudt D. N., Verboom W., Chem. Soc.Rev.,2007, 36, 367—377
[8]	Jensen M. P., Bond A. H., J. Am. Chem.Soc.,2002, 124, 9870—9877
[9]	Kolarik Z., Müllich U., Gassner F., Solvent Extr. Ion Exch.,1999, 17(1), 23—32
[10]	Trumm S., Geist A., Panak P. J., Fanghänel T., Solvent Extr. Ion Exch., 2011, 29(4), 213—229
[11]	Foreman M. R. S., Hudson M. J., Geist A., Madic C., Weigl M., Solvent Extr. Ion Exch., 2005, 23, 645—662
[12]	Retegan T., Ekberg C., Dubois I., Fermvik A., Wass T. J., Skarnemark G., Solvent Extr. Ion Exch., 2007, 25(4), 417—431
[13]	Galletta M., Scaravaggi S., Macerata E., Famulari A., Mele A., Panzeri W., Sansone F., Casnati A., Mariani M., Dalton Trans.,2013, 42, 16930—16938
[14]	Edwards A. C., Wagner C., Geist A., Burton N. A., Sharrad C. A., Adams R. W., Pritchard R. G., Panak P. J., Whitehead R. C., Harwood L. M., Dalton Trans.,2016, 45, 18102—18112
[15]	Bremer A., Ruff C. M., Girnt D., Müllich U., Rothe J., Roesky P. W., Panak P. J., Karpov A., Müllich T. J. J., Denecke M. A., Geist A., Inorg.Chem., 2012, 51, 5199—5207
[16]	Wang J. R., Su D. P., Wang D. Q., Ding S. D., Huang C., Huang H., Hu X. Y., Wang Z. P., Li S. M., Inorg.Chem., 2015, 54, 10648—10655
[17]	Su D.P., Liu Y., Li S. M., Ding S. D., Jin Y. D., Wang Z. P., Hu X. Y., Zhang L. R.,Eur. J. Inorg. Chem., 2017, 651—658
[18]	Hu X. Y., Su D. P., Li S. M., Wang Z. P., Zhang L. R., Liu Y., Song L. J., Chen Z. L., Ding S. D., Chem. J. Chinese Universities.,2017, 38(8), 1324—1333
	(胡晓阳, 苏冬萍, 李诗萌, 王志鹏, 张利荣, 刘莹, 宋莲君, 陈志力, 丁颂东. 高等学校化学学报. , 2017, 38(8), 1324—1333)
[19]	Geist A., Hill C., Modold G., Foreman M. R. St. J., Weigl M., Gompper K., Hudson M. J., Solvent Extr. Ion Exch., 2007, 24, 463—483
[20]	Zhu Y. J., Chen J., Jiao R. Z., Solvent Extr. IonExch., 1996, 14(1), 61—68
[21]	Wang X. H., Zhu Y. J., Jiao R. Z., J. Radioanal. Nucl. Chem.,., 2002, 251 487—492
[22]	Bhattacharyya A., Mohapatra P. K., Manchanda V. K., Solvent Extr. Ion Exch.,2006, 24(1), 1—17
[23]	Bhattacharyya A., Mohapatra P. K., Manchanda V. K., Solvent Extr. Ion Exch.,2007, 25(1), 27—39
[24]	Ionova G., Rabbe C., Hill C., Madic C., Guillaumont R., Krupa C., Solvent Extr. Ion Exch., 2001, 19(3), 391—414
[25]	Cao X. Y., Heidelberg D., Ciupka J., Dolg M., Inorg.Chem.,2010, 49(22), 10307—10315
[26]	Tian G. X., Zhu Y. J., Xu J. M., Hu T. D., Xie Y. N., J. Alloys Compd.,2002, 334(1/2), 86—91
[27]	Tian G. X., Zhu Y. J., Xu J. M., Zhang P., Hu T. D., Xie Y. N., Zhang J., Inorg.Chem. ,2003, 42, 735—741
[28]	Tian G. X., Kimura T., Yoshida Z., Zhu Y. J., Rao L. F., Radiochim .Acta.,2004, 92(8), 495—499
[29]	Sole K. C., Hiskey J. B., Ferguson T. L., Solvent Extr. IonExch.,1993, 11(5), 783—796
[30]	Chen J., The Separation of Amerieium from Lanthanides by Bis(2,4,4-trimethylpentyl)dithiophosphinic Acid Extraction, Tsinghua University, Beijing, 1996
	(陈靖. 二(2,4,4-三甲基戊基)二硫代膦酸萃取分离镅与镧系元素, 北京: 清华大学, 1996)
[31]	Chen J., Wang S. W., Xu C., Wang X. H., Feng X. G., Procedia Chemistry.,2012, 7, 172—177
[32]	Sole K. C., Hiskey J. B., Hydrometallurgy.,1995, 37, 129—147
[33]	Tian G. X., Zhu Y. J., Xu J. M., Solvent Extr. Ion Exch., 2001, 19(6), 993—1005
[34]	Xu Q. C., Wu J. F., Chang Y. Z., Zhang L. X., Yang Y. S., Radiochim.Acta.,2008, 96, 771—779
[35]	Xu C., Rao L. F., Chem. Eur.J.,2014, 20, 14807—14815
[36]	Xu G.X., Wang W. Q., Wu J. G., Gao H. C., Shi N., Extraction Chemistry Principle., Shanghai Science and Technology Press, Shanghai, 1985, 87—91
	(徐光宪, 王文清, 吴瑾光, 高宏成, 施鼐. 萃取化学原理., 上海: 上海科学技术出版社, 1985, 87—91)
[37]	Peterman D. R., Greenhalgh M. R., Tillotson R. D., Klaehn J. R., Harrup M. K., Luther T. A., Law J. D., Sep. Sci.Technol.,2010, 45, 1711—1717
[38]	Jensen M. P., Chiarizia R., Urban V., Solvent Extr. Ion Exch., 2001, 19(5), 865—884
[39]	Pattee D., Musikas C.,Faure A., Chachaty C., J. Less-Common Metals.,1986, 122, 295—302
[40]	Horwitz E. P., Muscatello A. L., Kalina D. G., Kaplan L., Sep. Sci.Technol.,1981, 16(4), 417—437
[41]	Chen J., Zhu Y. J., Jiao R. Z., Solvent Extr. Ion Exch., 1996, 31(19), 2723—2731
[42]	Chen H. H., Zhao X., Luan X. H., Yu G. L., Chem. J. Chinese Universities.,2015, 36(1), 1—8
	(陈欢欢, 赵峡, 栾晓红, 于广利. 高等学校化学学报., 2015, 36(1), 1—8)
[43]	Zhang L., Li H. F., Chen P., Sun W. B., Yan P. F., Chem. Res. Chinese Universities.,2016, 32(4), 534—538
[44]	Ferraro J. R., J. Inorg. Nucl.Chem., 1959, 10, 319—324
[45]	Bernardo P. D., Melchior A., Tolazzi M., Zanonato P. L., Coord. Chem.Rev., 2012, 256, 328—351
[46]	Xu C., Sun T. X., Rao L. F., Inorg.Chem.,2017, 56, 2556—2565
[47]	Wang L. F., He D. Q., Chen W., Yu H. Q., Water Research.,2015, 81, 325—332
[48]	Shi X. L., Zhang T., Li X. W., Feng Y., Tan X., Jin Y. R., Chem. Res. Chinese Universities.,2016, 32(4), 556—560
[49]	Wang L.F., Interactions Between Natural Organic MatterNOM) and Metal Ions/Nanoparticles and Their Effects in Membrane Fouling Process, University of Science and Technology of China,Hefei, 2016
	(王龙飞. 天然有机脂与金属离子/纳米颗粒的相互作用及其对膜污染过程的影响, 合肥: 中国科学技术大学, 2016)

二(2-乙基己基)二硫代次膦酸对硝酸溶液中Am³⁺和Eu³⁺的萃取

Extraction of Trivalent Americium and Europiumfrom Nitric Acid Solution with Di(2-ethylhexyl)dithiophosphinic Acid^†

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