Skip to main content
SpringerLink
Log in

Speciation of nitric acid third phase in a 30%TBP/n-dodecane solvent

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

Abstract

Third phase formation during nuclear solvent extraction has the delirious effect on operation of extractor cascade and may result in the criticality due to unsafe accumulation of the actinides. In this study, the nitric acid third phase was generated with 30%TBP-dodecane/nitric acid system and characterization studies were performed. The earlier model of author and coworker for U(IV) and Pu(IV) third phase could be extended to cover the current study. Experimental results indicated a presence of chain-linked nitric acid dimer to a single molecule of TBP in the generated nitric acid third phase whereas speciation in the light phase was similar to unpartitioned organic phase.

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
Fig. 3
Fig. 4
Fig. 5

Similar content being viewed by others

References

  1. Clark AE (2019) Amphiphile- based complex fluids: the self assembly ensemble as protagonist. ACS Cen Sci 6:10–12

    Article  Google Scholar 

  2. Servis MJ, Wu DT, Shafer JC, Clark AE. Preprint archive https://chemrxiv.org/engage/api-gateway/chemrxiv/assets/orp/resource/item/60c745954c8919daabad2a01/original/reimagining-third-phase-formation-as-the-miscibility-gap-of-a-molecular-solution.pdf. Accessed 12 May 2023

  3. Servis MJ, Stephenson, Mesostructuring in liquid-liquid extraction. Organic phase originating from critical points. https://www.osti.gov/servlets/purl/1831745. Accessed 12 May 2023

  4. Kumari I, Kumar BVR, Khanna A (2020) A review on UREX processes for nuclear spent fuel reprocessing. Nucl Eng Des 358:110410. https://doi.org/10.1016/j/nucengdes.2019.110410

    Article  CAS  Google Scholar 

  5. Taylor R, Carrot M, Galan H, Geist A, Heres X, Maher C, Mason C, Malmbeck R, Miguirditchian M, Modolo G, Rhodes C, Sarsfield M, Wilden A (2016) The EURO-GANEX process: current status of flowsheet development and process safety studies. Proc Chem 21:524–529

    Article  Google Scholar 

  6. Authen TL, Wilden A, Schneider D, Kreft F, Modolo G, Foreman MRS, Ekberg C (2021) Batch flowsheet test for a GANEX-type process: the CHALMEX FS-13 Process. Solv Extr Ion Exch. https://doi.org/10.1080/07366299.2021.1890372

    Article  Google Scholar 

  7. Burger LL, Slansky CM (1949) Density and viscosity of solutions in the tributyl phosphate process for uranium recovery. Technical Report HW-15233, Hanford Work USA

  8. Alcock K, Grimley SS, Healy TV, Kennedy J, McKay HAC (1956) The extraction of nitrates by tri-n-butyl phosphate (TBP), Part 1—the system TBP+diluent+H2O+HNO3. Trans Faraday Soc 52:39–47

    Article  CAS  Google Scholar 

  9. Healy TV, McKay HAC (1956) The extraction of nitrates by tri-n-butyl phosphate (TBP), Part 2—the nature of TBP phase. Trans Faraday Soc 52:633–642

    Article  CAS  Google Scholar 

  10. Mills AL, Logan WR (1967) In: Solvent extraction chemistry, Proc Intl Conf Gothenburg, Sweden. Dyrssen D, Liljenjin JO, Rydberg I (Eds.) North Holland, Amsterdam

  11. Horner DE (1971) Formation of third phases and the effect of temperature on the distribution of plutonium and uranium in extractions by tri-n-butyl phosphate. Technical Report ORNL-4724, Oak Ridge National Laboratory, USA

  12. Kolarik Z (1979) The formation of a third phase in the extraction of Pu(IV), U(IV) and Th(IV) nitrates with tributyl phosphate in alkane diluents. Proc Int Solv Extr Conf (ISEC-1977) CIM Spec 21:178–182

    CAS  Google Scholar 

  13. Gonda K, Oka K (1984) Accumulation process of plutonium third phase in mixer-settlers. Nucl Technol 64:14–18

    Article  CAS  Google Scholar 

  14. Tachimori S, Suzuki S, Ami N (1993) Study of the third phase in U(IV)-HNO3 and tri-n-butyl phosphate-dodecane extraction system, Proc Int Solv Extr Conf (ISEC-93), York. Logsdail DH, Slater MJ (Eds) SCI & Elsevier: London, pp 1546–1553

  15. Boukis N, Kanellakopulos B (1983) Extractive phase distribution of uranium nitrate with tri-n-butyl phosphate. Technical Report KfK-3352, Kernforschungszentrum, Karlsruhe

  16. Kumar S, Koganti SB (1996) Empirical modeling of Pu(IV) third phase formation in 30%TBP/n-dodecane system. J Nucl Sci Technol 33:1003–1005

    Article  CAS  Google Scholar 

  17. Kumar S, Koganti SB (2003) Speciation studies in third phase formation: U(IV), Pu(IV) and Th(IV) third phases in TBP systems. Solv Extr Ion Exch 21:547–558

    Article  CAS  Google Scholar 

  18. Chiarizia R, Jensen MP, Borkowski M, Ferraro JR, Thiagarajan P, Littrell KC (2003) Third phase formation revisited: the U(VI), HNO3-TBP, n-dodecane system. Solv Extr Ion Exch 19:981–992

    Google Scholar 

  19. Plaue J, Gelis A, Czerwinski K, Thiagarajan P, Chiarizia R (2006) Small-angle neutron scattering study of plutonium third phase formation in 30%TBP/HNO3/alkane diluent system. Solv Extr Ion Exch 24:283–298

    Article  CAS  Google Scholar 

  20. Plaue J, Gelis A, Czerwinski K (2006) Actinide third phase formation in 1.1M TBP/nitric acid/alkane diluent system. Sep Sci Technol 41:2065–2074

    Article  CAS  Google Scholar 

  21. Ivanov P, Mu J, Leay L, Chang SY, Sharrad CA, Masters AJ, Schroeder SLM (2017) Organic and third phase in HNO3/TBP/n-dodecane system: no reverse Micelles. Solv Extr Ion Exch 34:251–265

    Article  Google Scholar 

  22. Mu J (2017) Computer simulation study of third phase formation in a nuclear extraction process. PhD Thesis, University of Manchester UK

  23. ASTM Standard D4052-11 (2011) Standard test method for density, relative density, and API gravity of liquids by digital density meter. ASTM International, West Conshohocken, PA, DOI: https://doi.org/10.1520/D4052-11

  24. Siddall TH III, Parker SG, Prout WE (1957) Equilibrium Distribution data for PUREX and similar extraction processes. Technical Report DP-53, E I du Pont de Nemours & Co USA

  25. Burger LL (1984) In: Chapter 3 of Science and Technology of Tributyl Phosphate, Vol I, Schulz WW, Navratil JD, Talbot AE (Eds.), CRC Press, Boca Raton, USA, p 25

  26. Schaekers JM (1986) Estimation of equilibrium constants for the extraction of nitric acid by TBP/kerosene mixtures. Proc Int Solv Extr Conf (ISEC-1986), Munich, pp 185–192

  27. Ferraro JR, Borkowski M, Chiarazia R, McAlister DR (2001) FT-IR spectroscopy of nitric acid in TBP/octane solution. Solv Extr Ion Exch 19:981–992

    Article  CAS  Google Scholar 

  28. Ami N, Suzuki S, Abe H, Tachimori S (1993) Formation characteristics and its numerical models of the third phase in the U(IV)-HNO3-TBP-n-Dodecane System. Technical Report JAERI-M 93-014, JAERI, Tokai-Mura Japan

Download references

Author information

Authors and Affiliations

  1. FRPPCG, RpG, Indira Gandhi Centre for Atomic Research, Kalpakkam, 603102, India

    Shekhar Kumar

Authors
  1. Shekhar Kumar
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Shekhar Kumar.

Ethics declarations

Conflict of interests

Author declares no conflict of interests.

Additional information

Publisher's Note

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

Rights and permissions

Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Kumar, S. Speciation of nitric acid third phase in a 30%TBP/n-dodecane solvent. J Radioanal Nucl Chem 332, 4541–4548 (2023). https://doi.org/10.1007/s10967-023-09155-1

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10967-023-09155-1

Keywords

Search

Navigation