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Journal of Radioanalytical and Nuclear Chemistry

, Volume 298, Issue 1, pp 301–309 | Cite as

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

  • K. Sini
  • Satyabrata Mishra
  • C. Mallika
  • N. K. Pandey
  • R. Srinivasan
  • U. Kamachi Mudali
  • R. Natarajan
Article

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.

Keywords

Electro-reduction of U(VI) Performance of cathodes Optimization of current density Kinetics of reduction Effect of temperature Aerial oxidation of U(IV) 

Notes

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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Copyright information

© Akadémiai Kiadó, Budapest, Hungary 2013

Authors and Affiliations

  • K. Sini
    • 1
  • Satyabrata Mishra
    • 1
  • C. Mallika
    • 1
  • N. K. Pandey
    • 1
  • R. Srinivasan
    • 1
  • U. Kamachi Mudali
    • 1
  • R. Natarajan
    • 1
  1. 1.Reprocessing Group, Indira Gandhi Centre for Atomic ResearchKalpakkamIndia

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