Redox behavior of Ce(IV)/Ce(III) in the presence of nitrilotriacetic acid: A surrogate study for An(I\T)/AD(III) redox behavior
Using cyclic voltammetry, we investigated the redox behavior of Ce(IV)/Ce(III), which is a surrogate for An(IV)/An(III) (An=actinides), in a solution of nitrilotriacetic acid (NTA) at 25 C. The cyclic voltammogram of Ce in a 0.1 M NTA solution at pH 6 showed a reversible one-electron redox reaction for Ce(IV)/Ce(III) at 0.51 V vs. Ag/AgCl. This redox potential was much lower than that obtained in 1 M nitric acid, indicating that Ce(IV) was preferentially stabilized by complexation with NTA. The redox potential in the NTA solution was independent of the Ce concentration from 2 to 20 mM, NTA concentration from 5 to 200 mM and pH between 3 and 7. These results indicated that no polymerization and no additional coordination of NTA and OH{sup -} to the Ce(III)-NTA complex took place during the redox reaction. As the speciation calculation of Ce(III) in the NTA solution showed that the predominant species was Ce{sup III}(nta){sub 2}{sup 3-} (H{sub 3}nta = NTA), the redox reaction of the Ce-NTA complex was expressed by the following: Ce{sup IV}(nta){sub 2}{sup 2-} +e{sup -} Ce{sup III}(nta){sub 2}{sup 3-}. The logarithm of the stability constant of Ce{sup IV}(nta){sub 2}{sup 2-} was calculated to be 38.6 {+-} 0.8 for I = 0 from the redox potential shift of Ce(IV)/Ce(III) in the NTA solution. The value was in good accordance with the stability constant of the Np{sup IV}(nta){sub 2}{sup 2-} complex, demonstrating that the aqueous coordination chemistry of Ce(IV) with NTA is quite similar to that of An(IV). These results strongly suggest that a negative shift of the Pu(IV)/Pu(III) redox potential in the NTA solution should make Pu(IV) more stable than Pu(III) even in a reducing environment.
- Research Organization:
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- Sponsoring Organization:
- Doe - Office Of Science
- DOE Contract Number:
- DE-AC02-98CH10886
- OSTI ID:
- 990253
- Report Number(s):
- BNL-93847-2010-JA; RAACAP; R&D Project: EE-639-EEDA; KP1504010; TRN: US201020%%256
- Journal Information:
- Radiochimica Acta, Vol. 98, Issue 7; ISSN 0033-8230
- Country of Publication:
- United States
- Language:
- English
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