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.
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References
Jackson DD, Hollen RM, Roensch FR, Rein JE (1980) Anal Chim Acta 117:205–215
Silver GL (1982) Talanta 29:959–960
Davies W, Townsend M (1974) UKAEA Report TRG-2463 (D)
Cleveland JM (1970) The chemistry of plutonium. Gordon and Breach, New York, pp 92–140
Keller C (1971) The chemistry of the transuranium elements. Verlag Chemie, Weinheim, pp 409–419
Denotkina RG, Moskvin AI, Shevchenko VB (1960) Russ J Inorg Chem (Engl Transl) 5:387–389 and 731–734
Denotkina RG, Shevchenko VB (1967) Russ J Inorg Chem (Engl Transl) 12:1237
Riglet C, Robouch P, Vitorge P (1989) Radiochim Acta 46:85–94
Schwabe K, Nebel D (1962) Z Phys Chem 220:339–354
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
Kraus KA, Moore GE (1949) In: Seaborg GT, Katz JJ, Manning WM (eds) The transuranium elements. McGraw Hill, New York, p 550
Connick RE, McVey WH (1951) J Am Chem Soc 73:1798–1804
Rabideau SW, Lemons JF (1951) J Am Chem Soc 73:2895–2899
Rabideau SW (1956) J Am Chem Soc 78:2705–2707
Aoyagi H, Yoshida Z, Kihara S (1987) Anal Chem 59:400–405
Fujinaga T, Kihara S (1977) CRC Critical reviews in analytical chemistry, vol 6. CRC Press, Cleveland, pp 223–254
Milyukova MS, Gusev NI, Sentyurin IG, Sklyarenko IS (1967) Analytical chemistry of plutonium. Israel Program for Scientific Translations, pp 280–290
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
Phillips G, Crossley D (1977) UKAEA Report AERA-R8794
Kihara S (1973) J Electroanal Chem 45:31–44 and 45–58
Hindman JC (1954) In: Seaborg GT, Katz JJ (eds) The actinide elements. McGraw-Hill, New York, pp 301–370
Wick OJ (ed) (1967) Plutonium Handbook, a guide to the technology, vol 1. Gordon and Breach, New York, pp 444–453
Sillen LG, Martell AE (1964) Stability constants of metal-ion complexes, 2nd edn. The Chemical Society London, pp 180–182
Harned HS, Owen BB (1958) The physical chemistry of electrolytic solutions, 3rd edn. Reinhold, New York, p 595
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
Bard AJ, Faulkner LR (1980) Electrochemical methods, fundamentals and applications. Wiley, New York, pp 283–292
Lemire RJ, Tremaine PRJ (1980) Chem Eng Data 25:361–370
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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
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DOI: https://doi.org/10.1007/BF00322411