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Kinetic study of the reduction of neptunium(VI) and plutonium(VI) by iodide ion in aqueous perchlorate media

Journal Article · · Inorg. Chem.; (United States)
DOI:https://doi.org/10.1021/ic50171a012· OSTI ID:7143447
The title reactions proceed with the stoichiometry 2AnO/sub 2//sup 2 +/ + 2I/sup -/ = 2nO/sub 2//sup +/ + I/sub 2/. The empirical form of the rate law for these reactions is first order in AnO/sub 2//sup 2 +/ and I/sup -/ and independent of hydrogen ion concentration with a small Harned-type factor that arises from the replacement of Li=+lO/sub 4/ by NaI. At 25/sup 0/C and ..mu.. = 1.00, the values for the apparent second-order rate constants are 530 +- 6 and 17.0 +- 0.1 M/sup -1/ s/sup -1/ for NpO/sub 2//sup 2 +/ and PuO/sub 2//sup 2 +/, respectively. The apparent activation parameters for the reduction of NpO/sub 2//sup 2 +/ are ..delta..H* = 12.2 +- 0.3 kcal/mole and ..delta..S* = -6 +- 1 eu and for the reduction of PuO/sub 2//sup 2 +/ are ..delta..H* = 13.8 +- 0.1 kcal/mole and ..delta..S* = -8.0 +- 0.4 eu. The results are discussed in terms of and found to be consistent with the Marcus cross relations.
Research Organization:
Argonne National Lab., IL
OSTI ID:
7143447
Journal Information:
Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 16:5; ISSN INOCA
Country of Publication:
United States
Language:
English