Reduction of Organics By Solvated Electrons
A recent area of work has been the destruction of toxic organic compounds by irradiation; after irradiation, "dioxins" (polychlorodibenzo-p-dioxins) are dechloroinated in the same way as PCBs can be converted to biphenyl an inorganic chloride. This is because the solvated electrons react with the organic compound to form a radical anion, which decomposes by the loss of a chloride anion. If a deoxygenated mixture of PCBs in isopropanol or mineral oil is irradiated with gamma rays, then the PCBs will be dechlorinated to form inorganic chloride and biphenyl. The reaction works best in isopropanol if potassium hydroxide (caustic potash) is added. The base deprotonates the hydroxydimethylmethyl radical to be converted into acetone and a solvated electron, as the result the G value (yield for a given energy due to radiation deposited in the system) of chloride can be increased because the radiation now starts a chain reaction, each solvated electron formed by the action of the gamma rays can now convert more than one PCB molecule. If oxygen, acetone, nitrous oxide, sulfur hexafluoride or nitrobenzene is present in the mixture, then the reaction rate is reduced. This work has been done recently in the USA, often with used nuclear fuel as the radiation source.
In addition to the work on the destruction of aryl chlorides it has been shown that aliphatic chlorine and bromine compounds such as perchloroethylene, Freon (1,1,2-trichloro-1,2,2-trifluoroethane) and halon-2402 (1,2-dibromo-1,1,2,2-tetrafluoroethane) can be dehalogenated by the action of radiation on alkaline isopropanol solutions. Again a chain reaction has been reported.
In addition to the work on the reduction of organic compounds by irradiation, some work on the radiation induced oxidation of organic compounds has been reported. For instance the use of radiogenic hydrogen peroxide (formed by irradiation) to remove sulfur from coal has been reported. In this study it was found that the addition of manganese dioxide to the coal increased the rate of sulfur removal. The degradation of nitrobenzene under both reducing and oxidising conditions in water has been reported.
Read more about this topic: Radiation Chemistry
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