二(2-乙基己基)二硫代次膦酸对硝酸溶液中Am~(3+)和Eu~(3+)的萃取
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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HNO_3溶液中Am~(3+)和Eu~(3+)的萃取行为.考察了酸度、萃取剂及NO-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Am~(3+)和Eu~(3+)的分配比(D)随pH值增大而增加; p H=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Am~(3+)和Eu~(3+)主要形成3∶1和2∶1型的萃合物. NO_3~-未直接参与D2EHDTPA对Am~(3+)和Eu~(3+)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Eu~(3+)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.
The extraction of Am~(3+)and Eu~(3+)from HNO_3 solution with di( 2-ethylhexyl) dithiophosphinic acid( D2EHDTPA) were investigated using n-dodecane as diluent. Influences of acidity,ligand concentration,NO_3~-concentration and saponification on the extraction of Am~(3+)and Eu~(3+)were evaluated. The distribution ratio values of both Am~(3+)and Eu~(3+)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 Am~(3+)and Eu~(3+),respectively. The nitrate ion did not take part in the extraction reaction of D2EHDTPA with Am~(3+)or Eu~(3+). The extractability of D2EHDTPA was significantly enhanced through the saponification with NaOH solution. SF_(Am/Eu)values could be improved to the magnitude of 10~4,and the extraction capacity was approximately 60% of the theoretical value. Furthermore,the complexation behaviors of D2EHDTPA with Eu~(3+)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 Eu~(3+),as well as the thermodynamic parameters( ΔH,ΔS and ΔG)were obtained.
The extraction of Am~(3+)and Eu~(3+)from HNO_3 solution with di( 2-ethylhexyl) dithiophosphinic acid( D2EHDTPA) were investigated using n-dodecane as diluent. Influences of acidity,ligand concentration,NO_3~-concentration and saponification on the extraction of Am~(3+)and Eu~(3+)were evaluated. The distribution ratio values of both Am~(3+)and Eu~(3+)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 Am~(3+)and Eu~(3+),respectively. The nitrate ion did not take part in the extraction reaction of D2EHDTPA with Am~(3+)or Eu~(3+). The extractability of D2EHDTPA was significantly enhanced through the saponification with NaOH solution. SF_(Am/Eu)values could be improved to the magnitude of 10~4,and the extraction capacity was approximately 60% of the theoretical value. Furthermore,the complexation behaviors of D2EHDTPA with Eu~(3+)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 Eu~(3+),as well as the thermodynamic parameters( ΔH,ΔS and ΔG)were obtained.
引文
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[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
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[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
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[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 Matter(NOM)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)
[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. Ion Exch.,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.,Fanghnel 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. Ion Exch.,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. Ion Exch.,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 Matter(NOM)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)