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Dissociation of molecules by ionizing radiation
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 spectrum) light is used. 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.

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. A study conducted in 1976 found an order of magnitude estimate can be made of the average hydrogen production rate that could be obtained by utilizing the energy liberated via radioactive decay. Based on the primary molecular hydrogen yield of 0.45 molecules/100 eV, it would be possible to obtain 10 tons per day. Hydrogen production rates in this range are not insignificant, but are small compared with the average daily usage (1972) of hydrogen in the U. S. of about 2 x 10^4 tons. Addition of a hydrogen atom donor could increase this about a factor of six. It was shown that the addition of a hydrogen atom donor such as formic acid enhances the G value for hydrogen to about 2.4 molecules per 100 eV absorbed. The same study concluded that designing such a facility would likely be too unsafe to be feasible.

Gas generation by radiolytic decomposition of hydrogen containing materials has been an area of concern for the transport and storage of radioactive materials and waste for a number of years. Potentially combustible and corrosive gases can be generated while at the same time, chemical reactions can remove hydrogen, and these reactions can be enhanced by the presence of radiation. The balance between these competing reactions is not well known at this time.

A suggestion has been made that in the early stages of the Earth's development when its radioactivity was almost two orders of magnitude higher than at present, radiolysis could have been the principal source of atmospheric oxygen, which ensured the conditions for the origin and development of life. Molecular hydrogen and oxidants produced by the radiolysis of water may also provide a continuous source of energy to subsurface microbial communities (Pedersen, 1999). Such speculation is supported by a discovery in the Mponeng Gold Mine in South Africa, where the researchers found a community dominated by a new phylotype of Desulfotomaculum, feeding on primarily radiolytically produced H2.

Pulse radiolysis is a recent method of initiating fast reactions to study reactions occurring on a timescale faster than approximately one hundred microseconds, when simple mixing of reagents is too slow and other methods of initiating reactions have to be used. The technique involves exposing a sample of material to a beam of highly accelerated electrons, where the beam is generated by a linac. It has many applications. It was developed in the late 1950s and early 1960s by John Keene in Manchester and Jack W. Boag in London.

Flash photolysis is an alternative to pulse radiolysis that uses high power light pulses (e. g. from an excimer laser) rather than beams of electrons to initiate chemical reactions. Typically ultraviolet light is used which requires less radiation shielding than required for the X rays emitted in pulse radiolysis.