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Page Title: Effects of Radiation on Water Chemistry (Synthesis)
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Effects of Radiation on Water Chemistry (Synthesis)
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Chemistry Volume 2 of 2
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Figure 1  Change in pH, Gas Concentration, and Nitrogen Compounds With Excess Oxygen Added

radiation 3H2 N2 2NH3 (ammonia) NH3 H2O NH4 OH radiation 2N2 5O2 2H2O 4HNO3 Reactor Water Chemistry DOE-HDBK-1015/2-93 EFFECTS OF RADIATION ON WATER CHEMISTRY (SYNTHESIS) Rev. 0 CH-03 Page 7 After essentially all of the oxygen has been consumed by reaction with hydrogen, the nitrogen contained in air will remain.  For small air additions, some hydrogen will also remain; thus, the reactor coolant will contain both dissolved hydrogen and dissolved nitrogen.  These two gases do  not react in an unirradiated solution at low temperature and pressure.  When exposed to radiation, however, the gases do react by the following reaction. (3-14) Again,  this  is  an  equilibrium  reaction,  and  radiation  induces  the  reaction  in  both  directions. Ammonia (NH ) produced by this reaction combines with water to form ammonium hydroxide 3 (NH  OH). 4 (3-15) Under the operating conditions of reactor coolant, Reaction (3-14) is far from complete.  In most  cases, less than about 10 percent of the nitrogen will be converted to ammonia.  If no additional base were added to reactor coolant, Reaction (3-14) would be sufficient to cause the coolant to be mildly basic, pH 9.  In the presence of added base, however, the reaction has only a very slight and negligible effect on pH. If the base NH  were used to control reactor coolant pH, the reverse of Reaction (3-14) would 3 be more important.  The reverse step of this reaction requires that some of the ammonia added to the coolant decompose into N   and H  .  Because operating conditions favor this step of the 2 2 equilibrium, rather than formation of NH , it would be expected that most of the ammonia added 3 would decompose.  However, the rate of the ammonia decomposition reaction is slow, and the pH of reactor coolant can be maintained in the required range.  It should also be noted that the decomposition  of NH   would produce hydrogen gas in significant concentrations in reactor 3 coolant (sufficient to satisfy normal H   requirements). 2 In the event that a large quantity of air is injected into the reactor coolant system, the inventory of  dissolved  hydrogen  would  be  rapidly  depleted  by  Reaction  (3-13).    If  the  amount  of  air injected is sufficiently large, there could be oxygen remaining in the coolant after depletion of the hydrogen.  In this case, another reaction is available to the oxygen and nitrogen in the air. (3-16) Nitric acid (HNO  ) produced by this reaction will neutralize any base contained in the coolant, 3 and if sufficient acid is produced, the coolant will acquire an acidic pH.

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