Skip to main content
Log in

Electrode processes of plutonium ions in phosphate media

  • Original Papers
  • Anorganic Analysis
  • Published:
Fresenius' Journal of Analytical Chemistry Aims and scope Submit manuscript

Summary

The electrolytic behaviour of plutonium ions in a mixture of phosphate and nitrate solutions was studied by flow-coulometry with column electrodes of glassy carbon(GC)-fibers and voltammetry with a GC disc electrode, and compared with that in phosphate-free media. The redox processes, PuO 2+2 /PuO +2 and Pu4+/Pu3+, were demonstrated to be reversible even in the phosphate media and their half wave potentials shifted more negatively due to the formation of PuO2(H2PO4)+ and Pu(HPO4)2. The rate of the irreversible reduction of PuO +2 to Pu3+ increased in the presence of phosphoric acid and the quantitative reduction was attained with the column electrode even at +0.35 V vs. saturated KCl-Ag/AgCl. The reduction process of PuO +2 was elucidated considering an intermediate Pu(IV)-species, PuO2+, which decomposed into Pu4+ by a post-chemical reaction. Analytical advantages of the use of phosphate media are discussed.

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

Access this article

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

Instant access to the full article PDF.

Similar content being viewed by others

References

  1. Jackson DD, Hollen RM, Roensch FR, Rein JE (1980) Anal Chim Acta 117:205–215

    Google Scholar 

  2. Silver GL (1982) Talanta 29:959–960

    Google Scholar 

  3. Davies W, Townsend M (1974) UKAEA Report TRG-2463 (D)

  4. Cleveland JM (1970) The chemistry of plutonium. Gordon and Breach, New York, pp 92–140

    Google Scholar 

  5. Keller C (1971) The chemistry of the transuranium elements. Verlag Chemie, Weinheim, pp 409–419

    Google Scholar 

  6. Denotkina RG, Moskvin AI, Shevchenko VB (1960) Russ J Inorg Chem (Engl Transl) 5:387–389 and 731–734

    Google Scholar 

  7. Denotkina RG, Shevchenko VB (1967) Russ J Inorg Chem (Engl Transl) 12:1237

    Google Scholar 

  8. Riglet C, Robouch P, Vitorge P (1989) Radiochim Acta 46:85–94

    Google Scholar 

  9. Schwabe K, Nebel D (1962) Z Phys Chem 220:339–354

    Google Scholar 

  10. Howland JJ, Jr, Hindman JC, Kraus KA (1949) In: Seaborg GT, Katz JJ, Manning WM (eds) The transuranium elements. McGraw Hill, New York, p 133

    Google Scholar 

  11. Kraus KA, Moore GE (1949) In: Seaborg GT, Katz JJ, Manning WM (eds) The transuranium elements. McGraw Hill, New York, p 550

    Google Scholar 

  12. Connick RE, McVey WH (1951) J Am Chem Soc 73:1798–1804

    Google Scholar 

  13. Rabideau SW, Lemons JF (1951) J Am Chem Soc 73:2895–2899

    Google Scholar 

  14. Rabideau SW (1956) J Am Chem Soc 78:2705–2707

    Google Scholar 

  15. Aoyagi H, Yoshida Z, Kihara S (1987) Anal Chem 59:400–405

    Google Scholar 

  16. Fujinaga T, Kihara S (1977) CRC Critical reviews in analytical chemistry, vol 6. CRC Press, Cleveland, pp 223–254

    Google Scholar 

  17. Milyukova MS, Gusev NI, Sentyurin IG, Sklyarenko IS (1967) Analytical chemistry of plutonium. Israel Program for Scientific Translations, pp 280–290

  18. Katz JJ, Seaborg GT, Morss LR (ed) (1986) The chemistry of the actinide elements, 2nd edn, vols 1 and 2. Chapman and Hall, London, pp 828–839

    Google Scholar 

  19. Phillips G, Crossley D (1977) UKAEA Report AERA-R8794

  20. Kihara S (1973) J Electroanal Chem 45:31–44 and 45–58

    Google Scholar 

  21. Hindman JC (1954) In: Seaborg GT, Katz JJ (eds) The actinide elements. McGraw-Hill, New York, pp 301–370

    Google Scholar 

  22. Wick OJ (ed) (1967) Plutonium Handbook, a guide to the technology, vol 1. Gordon and Breach, New York, pp 444–453

    Google Scholar 

  23. Sillen LG, Martell AE (1964) Stability constants of metal-ion complexes, 2nd edn. The Chemical Society London, pp 180–182

  24. Harned HS, Owen BB (1958) The physical chemistry of electrolytic solutions, 3rd edn. Reinhold, New York, p 595

    Google Scholar 

  25. Katz JJ, Seaborg GT, Morss LR (ed) (1986) The chemistry of the actinide elements, 2nd edn, vols 1 and 2. Chapman and Hall, London, pp 1532–1538

    Google Scholar 

  26. Bard AJ, Faulkner LR (1980) Electrochemical methods, fundamentals and applications. Wiley, New York, pp 283–292

    Google Scholar 

  27. Lemire RJ, Tremaine PRJ (1980) Chem Eng Data 25:361–370

    Google Scholar 

Download references

Author information

Authors and Affiliations

Authors

Rights and permissions

Reprints and permissions

About this article

Cite this article

Yoshida, Z., Aoyagi, H. & Kihara, S. Electrode processes of plutonium ions in phosphate media. Fresenius J Anal Chem 340, 403–409 (1991). https://doi.org/10.1007/BF00322411

Download citation

  • Received:

  • Revised:

  • Issue Date:

  • DOI: https://doi.org/10.1007/BF00322411

Keywords

Navigation