Skip to main content
SpringerLink
Log in

Extraction mechanism of Tc(IV) by Di-(2-ethylhexyl)phosphoric acid (HDEHP)

  • Published:
Journal of Radioanalytical and Nuclear Chemistry Aims and scope Submit manuscript

Abstract

Di-(2-ethylhexyl)phosphoric acid, HDEHP, is a well-known extractant used for metal ion extraction in an industrial scale and for research work. Understanding metal extraction mechanisms is crucial for accurate interpretation of data obtained from solvent extraction experiments. The extraction mechanism of many metals by HDEHP has been determined. However, the mechanism for Tc(IV) extraction by HDEHP has not been specifically described in the literature and various assumptions have been made on the identity of the extracted Tc(IV) complex, without convincing demonstration. This work reports that TcO(OH)(DEHP)(HDEHP) is the Tc(IV) complex extracted by HDEHP into dodecane from an aqueous solution of 3 M NaClO4 at pH 2, with one HDEHP dimer participating in the extraction and one proton undergoing transfer from the HDEHP into the aqueous phase. The proposed mechanism agrees with other established metal hydroxide mechanisms and follow overall extraction trends for tetravalent metals with HDEHP.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2

Adapted from the literature [33]

Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9

Similar content being viewed by others

References

  1. El-Sweify FH, Kamel MW (1996) Studies on the extraction behavior of Zr(IV), Ce(III), Th(IV) and U(VI) from aqueous solutions of Arzenazo-I with HDEHP, HTTA, TDA and TCMA. J Radioanal Nucl Chem 207:369–382

    Article  CAS  Google Scholar 

  2. Lohithakshan KV, Patil P, Aggarwal SK (2014) Solvent extraction studies of plutonium(IV) and americium(III) in room temperature ionic liquid (RTIL) by di-2-ethyl hexyl phosphoric acid (HDEHP) as extractant. J Radioanal Nucl Chem 301:153–157. https://doi.org/10.1007/s10967-014-3119-9

    Article  CAS  Google Scholar 

  3. Reddy L, Reddy B, Harikrishna K, Venugopal Chetty K (1994) Solvent extraction of Hf(IV) from mixed electrolyte solutions into di-2-ethylhexylphosphoric acid (HDEHP). J Radioanal Nucl Chem 178:173–178

    Article  CAS  Google Scholar 

  4. Shakir K (1992) Extraction of certain actinide and lanthinide elements from different acid media by polyurethane foams loaded with di-2-ethylhexylphosphoric acid (HDEHP). J Radioanal Nucl Chem 162:371–380

    Article  CAS  Google Scholar 

  5. Islam F, Biswas RK (1980) Kinetics of solvent extraction of metal ions with HDEHP - II Kinetics and mechanism of solvent extraction of V(IV) from acid aqueous solutions with bis-(2-ethylhexyl) phosphoric acid in benzene. Journal of ionrganic and nuclear chemistry 42:421–429

    Article  CAS  Google Scholar 

  6. Rydberg Michael; Musikas, Claude; Choppin, Gregory R. J cox, (2004) Solvent Extraction Principles and Practice. Marcel Dekker, New York

    Google Scholar 

  7. Peppard DF, Mason GW, McCarty S (1960) Extraction of thorium(IV) by di-esters of orthophosphoric acid, (GO)2PO(OH). J Inorg Nucl Chem 1:138–150

    Article  Google Scholar 

  8. Cecilie M, Hiscox B, Nash KL (2012) Characterization of HDEHP-lanthanide complexes formed in a non-polar organic phase using 31 P NMR and ESI-MS. Dalton Trans 41:1054–1064. https://doi.org/10.1039/c1dt11534k

    Article  CAS  Google Scholar 

  9. Lieser KH (1993) Technetium in the nuclear fuel cycle, in medicine and in the environment. Radiochim Acta 63:5–8

    Article  CAS  Google Scholar 

  10. Hess NJ, Xia Y, Rai D, Conradson SD (2004) Thermodynamic model for the solubility of TcO2·xH2O(am) in the aqueous Tc(IV) - Na+- Cl– H+- OH– H2O system. J Solution Chem 33:199–226. https://doi.org/10.1023/B:JOSL.0000030285.11512.1f

    Article  CAS  Google Scholar 

  11. Guillaumont R, Fanghanel T, Neck V et al (2003) Update on the chemical thermodynamics of uranium, neptunium, plutonium, americium and technetium. Chemical Thermodynamics 5:919

    Google Scholar 

  12. Yalçintaş E, Gaona X, Altmaier M et al (2016) Thermodynamic description of Tc(IV) solubility and hydrolysis in dilute to concentrated NaCl, MgCl2and CaCl2solutions. Dalton Trans 45:8916–8936. https://doi.org/10.1039/c6dt00973e

    Article  PubMed  Google Scholar 

  13. Omoto T, Wall NA (2017) Evaluation of vanadium(IV) as a non-radioactive surrogate for technetium(IV) by comparison of stability constants for polyamino polycarboxylate ligand complexation. J Solution Chem 46:1981–1994. https://doi.org/10.1007/s10953-017-0680-1

    Article  CAS  Google Scholar 

  14. Wall NA, Karunathilake N, Dong W (2013) Interactions of Tc(IV) with citrate in NaCl media. Radiochim Acta. https://doi.org/10.1524/ract.2013.2001

    Article  Google Scholar 

  15. Wall NA, Mathews SA (2005) Sustainability of humic acids in the presence of magnesium oxide. Appl Geochem. https://doi.org/10.1016/j.apgeochem.2005.04.004

    Article  Google Scholar 

  16. Boggs MA, Islam M, Dong W, Wall NA (2013) Complexation of Tc(IV) with EDTA at varying ionic strength of NaCl. Radiochim Acta. https://doi.org/10.1524/ract.2013.2000

    Article  Google Scholar 

  17. Xia Y, Hess NJ, Felmy AR (2006) Stability constants of technetium(IV) oxalate complexes as a function of ionic strength. Radiochim Acta 94:137–141. https://doi.org/10.1524/ract.2006.94.3.137

    Article  CAS  Google Scholar 

  18. Parker TG, Omoto T, Dickens SM et al (2018) Complexation of Tc(IV) with SO42- in NaCl Medium. J Solution Chem 47:1192–1201. https://doi.org/10.1007/s10953-018-0785-1

    Article  CAS  Google Scholar 

  19. Shannon BYRD, H M, Baur NH, et al (1976) Revised effective ionic radii and systematic studies of interatomie distances in halides and chaleogenides

  20. Hu G, Chen D, Wang L et al (2014) Extraction of vanadium from chloride solution with high concentration of iron by solvent extraction using D2EHPA. Separ Purif Technol 125:59–65. https://doi.org/10.1016/j.seppur.2014.01.031

    Article  CAS  Google Scholar 

  21. Xing-bin LI, Chang WEI, Jun WU et al (2012) Thermodynamics and mechanism of vanadium (IV) extraction from sulphate medium with D2EHPA, EHEHPA and CYANEX 272 in kerosene. Trans Nonferr Met Soc China 22:461–466. https://doi.org/10.1016/S1003-6326(11)61199-0

    Article  CAS  Google Scholar 

  22. Zhang Y, Zhang T, Lv G et al (2016) Synergistic extraction of vanadium ( IV ) in sulfuric acid media using a mixture of D2EHPA and EHEHPA. Hydrometallurgy 166:87–93. https://doi.org/10.1016/j.hydromet.2016.09.003

    Article  CAS  Google Scholar 

  23. Biswas RK, Begum DA (1998) Solvent extraction of tetravalent titanium from chloride solution by di-2-ethylhexyl phosphoric acid in kerosene. Hydrometallurgy 1:263–274

    Article  Google Scholar 

  24. Liem DH, Sinegribova O (1971) Synergistic and antagonistic effects in th extraction of Hf(IV) by dibutylphosphate (HDBP) and di(2-ethyl-hexyl)phosphate (HDEHP) in the presence of trioctylphosphineoxide (TOPO) or trioctylamine (TOA) in hexane and toluene. Acta Chem Scand 25:301–322

    Article  CAS  Google Scholar 

  25. Vermaak V, Krieg HM, De Beer L, Van der Westhuizen D (2018) Mechanistic study of hafnium and zirconium extraction with organophosphorous extractants. Solvent Extr Ion Exch 36:150–161. https://doi.org/10.1080/07366299.2018.1431078

  26. Abdel-Fattah AA, Ali SM, El-Sweify FH (2002) Thermodynamics of the solvent extraction of Zr ( IV ) by Amberlite LA-2, TBP and HDEHP from different aqueous media. J Radioanal Nucl Chem 253:465–475

  27. Koladkar DV, Dhadke PM (2002) Extraction and separation of Th (IV) and U (VI) from nitric acid media using PIA-8 and HDEHP. J Radioanal Nucl Chem 253:297–302

    Article  CAS  Google Scholar 

  28. Peppard DF, Mason GW (1963) Some mechanisms of extraction of M(II), (III), (IV), and (VI) metals by acidic organophosphorous extractants. Nucl Sci Eng 16:382–399

    Article  CAS  Google Scholar 

  29. Ali SM (2008) Extraction thermodynamics of Th (IV) in various aqueous organic systems. J Chem Thermodyn 40:798–805. https://doi.org/10.1016/j.jct.2008.01.013

    Article  CAS  Google Scholar 

  30. Joseph Steigman WCE (1992) The Chemistry of Technetium in Medicine

  31. Tang J, C.M. W, (1986) Solvent extraction of lanthanides with a crown ether carboxylic acid. J Anal Chem 58:3233–3235. https://doi.org/10.1021/ac00127a068

    Article  CAS  Google Scholar 

  32. Friend MT, Eiroa-Lledo C, Lecrivain LM et al (2018) Thermodynamic parameters for the complexation of technetium(IV) with EDTA. Radiochim Acta 106:963–970. https://doi.org/10.1515/ract-2018-2992

    Article  CAS  Google Scholar 

  33. Stary J (1964) Composition and stability of metal chelates. In: The solvent extraction of metal chelates. pp 4–20

  34. Favre-Reguillon A, Fiaty K, Laurent P et al (2007) Solid/liquid extraction of zirconium and hafnium in hydrochloric acid aqueous solution with anion exchange resin s kinetic study and equilibrium analyses. Ind Eng Chem Res 46:1286–1291. https://doi.org/10.1021/ie060444p

  35. Rydberg J (1956) Studies on the formation of composite complexes by means of an extractive technique. J R Netherl Chem Soc 75:737–742

    CAS  Google Scholar 

  36. Rossotti F, Rossotti H (1961) The determination of stability constants

  37. Rydberg J (1954) Studies on the extraction of metal complexes. XII-A Arkic Kemi 8:101

    Google Scholar 

  38. Andersson C, Andersson SO, Liljenzin JO et al (1969) Solvvent extraction studies by the AKUFVE Method 1969.pdf. Acta Chem Scand 23:2781–2796

    Article  CAS  Google Scholar 

  39. There H (1976) Hydrolysis of Cu (II)

  40. Ronald N. S, Malcolm R. D (1978) The hydrolysis of metal ions. Part 1. Copper (II). JCS Daltion 232–235

  41. Hess NJ, Qafoku O, Xia Y, et al (2008) Thermodynamic Model for the Solubility of TcO 2 · x H 2 O in Aqueous Oxalate Systems. 1471–1487. https://doi.org/10.1007/s10953-008-9328-5

  42. Parker L, Lledo EC, Tabada DL, Wall DE, Wall NA, TGL (2019) Comparison of the solvent extraction behavior of ReO4- and TcO4-. Radiochim Acta. https://doi.org/10.1515/ract-2019-0006

    Article  Google Scholar 

  43. Partridge JA, Jensen RC (1969) Purification of di-(2-ethylhexyl)phosphoric acid by precipitation of copper(II) di-(2-ethylhexyl)phosphate. J Inorg Nucl Chem 31:2587–2589

    Article  Google Scholar 

  44. J⊘rgensen CK, Schwochau K, (1965) Comparative interpretation of absorption spectra of technetium (iv) and rhenium (iv) hexahalides. Zeitschrift fur Naturforschung - Section A J Phys Sci 20:65–75. https://doi.org/10.1515/zna-1965-0112

    Article  Google Scholar 

  45. Gu B, Dong W, Liang L, Wall NA (2011) Dissolution of Technetium ( IV ) Oxide by Natural and Synthetic Organic Ligands under both Reducing and Oxidizing Conditions. 4771–4777. https://doi.org/10.1021/es200110y

  46. Yalcintas E, Gaona X, Scheinost AC et al (2015) Redox chemistry of Tc(VII)/Tc(IV) in dilute to concentrated NaCl and MgCl2solutions. Radiochim Acta 103:57–72. https://doi.org/10.1515/ract-2014-2272

    Article  CAS  Google Scholar 

  47. Sillén LG (1956) On equilibria with polynuclear complexes. Recueil des travaux chimiques des Pays-Bas 75:705–710

  48. Banda R, Lee MS (2015) Solvent extraction for the separation of Zr and Hf from aqueous solutions. Separ Purif Rev 44:199–215. https://doi.org/10.1080/15422119.2014.920876

    Article  CAS  Google Scholar 

  49. Miralles N, Sastre A, Martinez M, Aguilar M (1992) The aggregation of organophosphorus acid compounds in toluene. Anal Sci 8:773–777

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This work was funded by the U.S. National Nuclear Security Administration, under the SSAA Grant DE-NA0002916.

Author information

Authors and Affiliations

  1. Department of Chemistry, Washington State University, Pullman, WA, 99164, USA

    Cecilia Eiroa-Lledo & Nathalie A. Wall

  2. Nuclear Science Center, Washington State University, Pullman, WA, 99164, USA

    Donald E. Wall

  3. Department of Materials Science and Engineering, Nuclear Engineering Program, University of Florida, Gainesville, FL, 32611, USA

    Donald E. Wall & Nathalie A. Wall

Authors
  1. Cecilia Eiroa-Lledo
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Donald E. Wall
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Nathalie A. Wall
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Nathalie A. Wall.

Additional information

Publisher's Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Eiroa-Lledo, C., Wall, D.E. & Wall, N.A. Extraction mechanism of Tc(IV) by Di-(2-ethylhexyl)phosphoric acid (HDEHP). J Radioanal Nucl Chem 331, 2751–2760 (2022). https://doi.org/10.1007/s10967-022-08303-3

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10967-022-08303-3

Keywords

Search

Navigation