Methyl Iodide Formation Under Postulated Nuclear Reactor Accident Conditions

The formation of methyl iodide under conditions of postulated nuclear reactor accidents is discussed. Although thermodynamic calculations indicate the equilibrium methyl iodide concentrations would be quite low, calculations based on a simple kinetic scheme involving reaction between small hydrocarbon species and iodine indicate that concentrations higher than equilibrium can occur during the course of the reaction. Such calculations were performed over a wide range of initial species concentrations and a range of temperatures representative of some reactor accident situations. These calculations suggest that little methyl iodide would be expected within the core volume where temperatures are maximum. As the gas leaves the core volume and expands into the plenum region, it cools and the concentration of methyl iodide increases. At the intermediate temperatures which might characterize this region, the formation of methyl iodide from thermally induced reactions could reach its maximum rate. The gas continues to cool, however, and it is probable that by the time it leaves the plenum region it has cooled to the point where thermally induced reactions may be of little importance. Although the thermally induced reactions will become slower as the gas expands and cools, the radiation-induced reactions will not be slowed to the same extent. The gases leaving the core carry fission products and hence a radiation source is available to initiate reaction by a temperature-independent process. An investigation of the radiation chemical formation and decomposition of methyl iodide in the presence of steam suggests that radiation-induced methyl iodide formation will generally be rapid under the postulated accident situations. Thus, in the plenum region where thermal reactions have become slow, the radiation-induced reaction can still proceed and may well become the dominant factor. The same situation probably pertains as well to the containment region. (author)