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Plutonium Nitrate, Oxalate, Peroxide, and Fluorides - doe-std-1128-98_ch10027
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DOE-STD-1128-98
Table 2.6. Solubilities and Properties of Selected Compounds
Measured Solubility
Bulk Density, g Pu/L
Sintered
Media
Compound
Medium
g/PuL
Filter Cake
Dry Compound
Porosity, m(a)
Flouride (III)
1M HF 1M HCl
0.03
--
1-2.5
15-20
0.70
0.6-0.8
0.5-2.0
15-20
Fluoride (IV)
2M HF 2M HNO3
0.5M C2O42- - 3M HNO3
0.01
0.6-0.8
-
15-20
Oxalate (III)
0.1M C2O42- - 4M HNO3
0.003
0.5-0.6
0.6
15-20
Oxalate (IV)
Peroxide (IV)
3M H2O2 - 1M HNO3
0.10
0.10-0.6
-
30-80
(a) Sintered media porosity required to remain precipitate.
Plutonium hexafluoride is the only volatile plutonium compound (bp 62C)
and is marginally stable. It can be prepared by oxidizing PuF4with F2 at an
elevated temperature (Weinstock and Malm, 1956). It can also be prepared at
low temperatures by a fluorinating agent, fluorine dioxide (Malm et al.,
1984). Plutonium waste treatment and decontamination may benefit from
processes using photolysis or microwave discharge to produce active fluorine
species from FOOF or CF4/O2 mixtures, which will react with plutonium or
plutonium dioxide to form PuF6(Martz et al., 1991).
2.3.3.2 Plutonium Dioxide
Plutonium dioxide may now be the most important and most
thoroughly studied of all plutonium compounds. Due to its chemical
stability and relative inertness, it is the preferred form for shipping
and storing plutonium at the present time. Direct oxide reduction
(DOR) of PuO2 is part of the integrated pyrochemical system used at
the Los Alamos National Laboratory (LANL) (Christensen and
Mullins, 1983; Mullins et al., 1982). Plutonium dioxide is formed
when plutonium or its compounds (except the phosphates) are
ignited in air, and often results when oxygen-containing compounds
are heated in vacuo or in an inert atmosphere to 1000C (Cleveland,
1970). The properties of PuO2 are reported by Moseley and Wing
(1965).
Loose PuO2 powder, as formed by calcination, usually has a density
of about 2 g/cm3. If the oxide is pressed and sintered into pellets, it
may have a density of about 10.3 to 11.0 g/cm3. Surface
measurements of typical oxides prepared from the calcination of
plutonium (IV) oxalate at various temperatures range from 10 to 60
m2/g. Caldwell (1961) found that the surface area decreased with
increasing temperatures. Plutonium oxide fired at temperatures
>600C is difficult to rapidly or completely dissolve in common
2-14


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