Preliminary results on the hydrolysis and carbonate complexation of dioxoplutonium(V) Page: 4 of 22
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2
1. INTRODUCTION
The pentavalent oxidation state of plutonium in aqueous solution was
discovered in 1944' This oxidation state is thermodynamically unstable
with respect to disproportionation into the +4 and +6 oxidation states in
acidic solutions. As can be seen from Eq I, the equilibrium of the
disproportionat ion reaction is pH dependent.
PuO2* + Pu02* + 4H+ T---' Pu4* + Puo,2, + 2 H O (I)
Pu(V) can also react with Pu(Ill) at a rate 35 times faster than the
disproportionation reaction3 at the same pH, as shown in Eq 2
Pu0 Pu3+ 4H* 2Pu4+ + 2H20 (2)
The study of Pu(V) is further complicated by the rapid equilibrium reaction
which occurs when plutonium exists in several oxidation states.
Pu02+ + Pu4+ " Puo.2+ . Pu3+ (3)
Until recently, essentially all plutonium chemistry was performed under
acidic conditions. Consequently, the pentavalent oxidation state was
considered unimportant and has not been extensively Investigated.
However, recent solubility studies of plutonium in near neutral
aqueous solutions have shown that Pu(V) Is a dominant soluble species.4,5
These solubility studies were conducted in groundwater from a well on
the Nevada Test Site known as J- 13 (see Table I for composition6) and
from 0.1 M NaC104. The results have shown that 40 to 82 per cent of the
soluble plutonium exists in the +5 oxidation state at pH 7 and 250C. The
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Bennett, D. A.; Hoffman, D. C.; Nitsche, H. & Silva, R. J. Preliminary results on the hydrolysis and carbonate complexation of dioxoplutonium(V), article, November 1, 1987; California. (https://digital.library.unt.edu/ark:/67531/metadc690120/m1/4/: accessed April 19, 2024), University of North Texas Libraries, UNT Digital Library, https://digital.library.unt.edu; crediting UNT Libraries Government Documents Department.