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Redox Reactions - doe-std-1128-98_ch10037
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DOE Standard Guide of Good Practices for Occupational Radiological Protection In Plutonium Facilities
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Chemical Versus Radiological Hazards - doe-std-1128-98_ch10039


DOE-STD-1128-98
chemistry of plutonium nitrate solutions may be found in Miner and
Seed (1966). In dilute solution (0.1M), GH2 is about 0.5 and GO2
increases to 1.45. Self-reduction of Plutonium hexafluoride as the
solid phase amounts to about 1.5% of the material per day
(Weinstock and Malm, 1956). See Cleveland (1970) Chapter 2, for
more information.
2.5.2.3 Miscellaneous Radiolytic Reactions
A serious limitation to the use of organic ion exchange materials is
their radiation stability. Brookhaven National Laboratory reviewed
the literature and summarized the effect of ionizing radiation on both
organic and inorganic ion exchange materials (Gangwer et al., 1977).
Extraction of plutonium (IV) from 3M HNO3 into 30 vol% tributyl
phosphate in kerosene at 5C decreased the extraction coefficient by
a factor of two when irradiated to a dose of 3.6 x 107 R (Tsujino and
Ishihara, 1966). The mechanical properties of thin plastic films such
as polyethylene and polyvinyl chloride degrade with exposure to
plutonium. Cellulose vacuum-cleaner bags will disintegrate in less
than a month if used for housekeeping purposes in plutonium-
contaminated gloveboxes. Leachability of plutonium-containing
wastes could be affected by the production of nitric acid for air-
equilibrated dilute salt solutions (Rai et al., 1980).
2.5.2.4 Helium Retention and Release
Helium introduced by alpha-bombardment of plutonium and the
alloys and compounds of plutonium can cause lattice expansion. This
was first observed for plutonium oxides, carbides, and nitrides by
Rand et al. (1962) and was later observed for two plutonium carbide
phases. Helium is retained in vitrified compounds. The retention and
release behavior of helium in plasma-torch-fused Pu02 microspheres
for SNAP is an important parameter in the design of the heat source.
Approximately 530 cm3 at standard temperature and pressure (STP)
per year-kg are produced by 238Pu02 (Stark, 1970). Microspheres of
80% 238PuO2and 20% 239PuO2 that were approximately 50 mm in
diameter, prepared by the sol-gel process, released 92.8% of the
helium in 8 months at room temperature (Northrup et al., 1970).
Metals at temperatures well below the melting point trap the
insoluble helium gas in tiny bubbles, which are more or less evenly
distributed through the matrix material (Stevens et al., 1988). Helium
buildup in weapon-grade material is approximately 4 standard cm3
per year-kg.
2.6
OCCUPATIONAL HAZARDS
The major industrial hazard in plutonium facilities is the potential for loss of control
of a highly toxic substance, resulting in either the inhalation or ingestion of
plutonium or one of its compounds by personnel, or the exposure to excessive
radiation from a criticality accident. The possibility of a fire or explosion in a
2-24


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