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Radiolysis Reactions
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Design Considerations - index
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Modeling the Behavior of Tritium


DOE-HDBK-1132-99
common type of radiolysis-driven reactions should result in the gradual, low-
level build-up of tritiated nitrous and nitric acids on the surfaces of most tritium
contaminated materials. Over the long-term, it should further be expected that
these tritiated nitrous and nitric acids will be broken down into tritiated ammonia
compound dissolved into the surface bound layers of water vapor.
For the most part, this particular type of reaction sequence does not normally
present itself as a problem in day-to-day tritium operations because (1) the
overall production efficiency for these types of reactions is relatively low, and
(2) the materials used for the construction of most tritium-handling systems are
not susceptible to attack by nitrous and/or nitric acids or by tritiated ammonia
compounds. By contrast, however, it should be noted that other types of
radiolysis-driven reactions can expected to occur with tritium in the presence of
compounds containing chlorides and/or fluorides, and these can easily lead to
chloride/fluoride induced stress corrosion cracking. (See, for example, the
discussion on " rganics"in Section 2.10.6, below.)
O
One additional point that is worth noting about radiolysis-driven reactions is that
their long-term potential for causing damage should not be underestimated.
Although the overall production efficiency for these types of reactions might be
expected to be relatively low, the generation of products from these types of
reactions can, on the other hand, be expected to occur continuously over
relatively long periods of time (i.e., 10-20 years, or more). As a consequence,
the long-term effects from these types of reactions can be difficult to predict,
especially because very little is known about the long-term, synergistic effects
of low-level, tritium micro-chemistry. (See Section 2.10.6.)
Le Chatelier' Principle . A chemical restatement of Newton' Third Law of
s
s
Motion, Le Chatelier' Principle states that when a system at equilibrium is
s
subjected to a perturbation, the response will be such that the system
eliminates the perturbation by establishing a new equilibrium. When applied to
situations like those depicted in Equations (5) and (6), Le Chatelier' Principle
s
states that, when the background tritium levels are increased in nature (by
atmospheric testing, for example), the reactions will be shifted to the right in
I-96


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