Radiolysis

Radiolysis is the dissociation of molecules by ionizing radiation. It is the cleavage of one or several chemical bonds resulting from exposure to high-energy flux. The radiation in this context is associated with ionizing radiation; radiolysis is therefore distinguished from, for example, photolysis of the Cl2 molecule into two Cl-radicals, where (ultraviolet or visible) light is used. Radiolysis is the dissociation of molecules by ionizing radiation. It is the cleavage of one or several chemical bonds resulting from exposure to high-energy flux. The radiation in this context is associated with ionizing radiation; radiolysis is therefore distinguished from, for example, photolysis of the Cl2 molecule into two Cl-radicals, where (ultraviolet or visible) light is used. For example, water dissociates under alpha radiation into a hydrogen radical and a hydroxyl radical, unlike ionization of water which produces a hydrogen ion and a hydroxide ion. The chemistry of concentrated solutions under ionizing radiation is extremely complex. Radiolysis can locally modify redox conditions, and therefore the speciation and the solubility of the compounds. Of all the radiation-chemical reactions that have been studied, the most important is the decomposition of water. When exposed to radiation, water undergoes a breakdown sequence into hydrogen peroxide, hydrogen radicals, and assorted oxygen compounds, such as ozone, which when converted back into oxygen releases great amounts of energy. Some of these are explosive. This decomposition is produced mainly by the alpha particles, which can be entirely absorbed by very thin layers of water. It is believed that the enhanced concentration of hydroxyl present in irradiated water in the inner coolant loops of a light-water reactor must be taken into account when designing nuclear power plants, to prevent coolant loss resulting from corrosion. The current interest in nontraditional methods for the generation of hydrogen has prompted a revisit of radiolytic splitting of water, where the interaction of various types of ionizing radiation (α, β, and γ) with water produces molecular hydrogen. This reevaluation was further prompted by the current availability of large amounts of radiation sources contained in the fuel discharged from nuclear reactors. This spent fuel is usually stored in water pools, awaiting permanent disposal or reprocessing. The yield of hydrogen resulting from the irradiation of water with β and γ radiation is low (G-values = <1 molecule per 100 electronvolts of absorbed energy) but this is largely due to the rapid reassociation of the species arising during the initial radiolysis. If impurities are present or if physical conditions are created that prevent the establishment of a chemical equilibrium, the net production of hydrogen can be greatly enhanced. Another approach uses radioactive waste as an energy source for regeneration of spent fuel by converting sodium borate into sodium borohydride. By applying the proper combination of controls, stable borohydride compounds may be produced and used as hydrogen fuel storage medium.