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Kinetics and optimisation of process parameters for electrochemical generation of uranous ions in nitric acid–hydrazine media

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Abstract

For the quantitative generation of uranous from uranyl ions in the presence of hydrazine in nitric acid medium, electrochemical reduction was carried out in divided and undivided cells. The influence of process conditions, viz. current density, concentration of nitric acid and hydrazine was studied for 50, 100 and 150 g/l of U(VI) solutions. The performance of the cathodes (titanium and platinum) was evaluated by calculating the conversion efficiencies in the reduction process using these electrodes for the reduction of 100 g/l U(VI) at 6 mA/cm2 as the cathodic current density. Batch mode experiments using Ti cathode revealed the reduction reaction of U(VI) to follow zero order kinetics and the simultaneous reduction of nitric acid to follow first order kinetics. From the temperature dependence, the activation energy for the reduction of U(VI) was determined to be 4.05 kJ/mol. The chemical stability of U(IV) in nitric acid–hydrazine medium, under ambient conditions of temperature and pressure was established from the amount of U(VI) produced from U(IV) by aerial oxidation over a period of 16 weeks.

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References

  1. Regnaut P, Faugeras P, Braut A, Helou R, Redon A (1958) Proceedings of the 2nd U.N. international conference on peaceful uses of atomic energy, vol 17, Geneva, pp 73–95

  2. Sreenivasa Rao K, Shyamlal R, Narayan CV, Jambunathan U, Ramanujam A, Kansra VP (2003) Report BARC/2003/E/009

  3. Abdunnabi HM, Ananyev AV, Krot NN (1994) J Radioanal Nucl Chem Lett 186:89

    Article  CAS  Google Scholar 

  4. Kumar S, Kumar R, Koganti SB (2005) Report IGC-273

  5. Reif DJ (1983) Report DP-1649

  6. Katz JJ, Seaborg GT (1986) Chemistry of the actinide elements, 2nd edn. Chapman and Hall, London, p 328

    Book  Google Scholar 

  7. Naylor A (1967) Pu–U separation techniques in TBP systems: use of ferrous sulphamate, U(IV) and aqueous soluble complexing agents. In: Advanced course in reprocessing of fuel from present and future power reactors. Netherlands-Norwegian Reactor School at Institute for Atomenergi, Norway, August–Sept, pp 172–200

  8. Crowder ML, Thomson MC (2002) Report WSRC-TR-2002-00389

  9. Schlea CS, Caverly MR, Henry HE, Jenkins WJ (1963) Report DP-808

  10. McKay HAC, Streeton RJW, Wain AG (1963) Report AERE–R-4381

  11. Streeton RJW, Jenkins WJ (1962) Report AERE-R-3938

  12. Kumar SV, Nadkarni MN, Ramanujam A, Venkatesan M, Gopalakrishnan V, Kazi JA (1976) Report BARC/I-381

  13. Pandey NK, Koganti SB (2004) Ind J Chem Technol 11:535

    CAS  Google Scholar 

  14. Gopinathan P, Siddiqui IA, Kumar SV (1991) Report BARC/1991/I/011

  15. Newton TW (1950) J Phys Chem 63:1493

    Article  Google Scholar 

  16. Biddle P, Miles JH, Waterman MJ (1966) J Inorg Nucl Chem 28:1736

    Article  CAS  Google Scholar 

  17. Ondrejcin RS (1961) Report DP-602

  18. Sreenivasa Rao K, Shyamlal R, Narayan CV, Patil AR, Jambunathan U, Ramanujam A, Kansra VP (2003) Report BARC/2003/E/010

  19. Duerksen WK (1993) Report Y/DZ-1019

  20. Toth LM, Felker LK (1986) Report ORNL/TM-9

  21. Orebaugh EG, Propst RC (1980) Report DP-1549

  22. Bell JT, Billings MR (1975) J Inorg Nucl Chem 37:2529

    Article  CAS  Google Scholar 

  23. Sidhu MS, Kohli KB, Bhatia PVK, Sandhu SS (1994) J Radioanal Nucl Chem Lett 187:375

    Article  CAS  Google Scholar 

  24. Sidhu MS, Schnabel W (1996) J Radioanal Nucl Chem 21:375

    Article  Google Scholar 

  25. Sini K, Satyabrata M, Mallika C, Pandey NK, Falix L, Mudali UK, Natarajan R (2012) J Radioanal Nucl Chem. Published online. doi:10.1007/s10967-012-1940-6

  26. Segawa T, Itoh I (1975) Japanese Patent 1975-35029

  27. Nogami M, Hirose Y, Arai T, Wei YZ, Kumagai M (2008) J Alloys Compds 451:358

    Article  CAS  Google Scholar 

  28. Baumgartner F, Schmieder H (1978) Radiochim Acta 25:191

    Google Scholar 

  29. Nichols GS (1966) Report DP-1065

  30. Miller FC, Hildebrandt BW, Cassidy RM (1983) Report AECL-8256

  31. Hsiang CC, Chang CT (1975) J Inorg Nucl Chem 37:1949

    Article  CAS  Google Scholar 

  32. Schmieder H, Baumgartner F, Goldacker H, Hausberger H (1974) Report KFK-2082

  33. Sini K, Satyabrata M, Falix L, Srinivasan R, Mallika C, Kamachi Mudali U (2010) Generation of U(IV) by electrochemical reduction of uranyl ions. Fifteenth National Convention of Electrochemists (NCE-15), SAEST, Vellore, India

  34. Baxter W, Naylor A (1965) Solvent extraction chemistry of metals. Macmillan Press, London, p 117

    Google Scholar 

  35. Patric G, Galla U, Golkacker H, Heilgeist M, Kluth M, Schlenker R, Schmieder H, Ebert K (1984) Comparison of experiment and simulation for purex B-type electro reduction pulsed columns. In: I. Chem. E. symposium series, No. 88, pp 267–278

  36. Davies W, Gray W (1964) Talanta 11:1203

    Article  CAS  Google Scholar 

  37. Wei YZ, Fang B, Arai T, Kumagai M (2004) J Radioanal Nucl Chem 262:409

    Article  CAS  Google Scholar 

  38. Ghandour MA, Abo-Doma RA, Gomma EA (1982) Electrochim Acta 27:159

    Article  CAS  Google Scholar 

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Acknowledgments

The authors are indebted to Dr. S. B. Koganti, former Head, Reprocessing R&D Division and Shri S. C. Chetal, Director, IGCAR for their interest and constant encouragement during the course of this work. They are grateful to Shri Falix Lawrence, Scientific Officer and Shri U. Veeramani, Foreman, Reprocessing R&D Division for their help in the experimental work. One of the authors, Ms. Sini K. expresses her gratitude to Department of Atomic Energy for the award of Research Fellowship. This work forms a part of the thesis to be submitted to the University of Madras for the award of Ph.D. degree in Chemistry to Ms. Sini K.

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  1. Reprocessing Group, Indira Gandhi Centre for Atomic Research, Kalpakkam, 603102, Tamil Nadu, India

    K. Sini, Satyabrata Mishra, C. Mallika, N. K. Pandey, R. Srinivasan, U. Kamachi Mudali & R. Natarajan

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  1. K. Sini
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  2. Satyabrata Mishra
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  4. N. K. Pandey
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Correspondence to C. Mallika.

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Sini, K., Mishra, S., Mallika, C. et al. Kinetics and optimisation of process parameters for electrochemical generation of uranous ions in nitric acid–hydrazine media. J Radioanal Nucl Chem 298, 301–309 (2013). https://doi.org/10.1007/s10967-013-2470-6

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  • DOI: https://doi.org/10.1007/s10967-013-2470-6

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