Ethane mercury photosensitized oxidation

Gray61 and Nalbandyan94 studied the mercury photosensitized oxidation of ethane in a flow system and showed that ethyl hydroperoxide was the chief initial product. Gray61 similarly obtained considerable amounts of methyl hydroperoxide in the photosensitized oxidation of methane. However, Watson and Darwent127 pointed out that the chain mechanism they proposed ... 

To perform the dissociation of the hydrocarbon to alkyl radicals with C—C bond scission, a hydrocarbon molecule should absorb light with the wavelength 270-370 nm. However, alkanes do not absorb light with such wavelength. Therefore, photosensitizers are used for free radical initiation in hydrocarbons. Mercury vapor has been used as a sensitizer for the generation of free radicals in the oxidized hydrocarbon [206-212], Nalbandyan [212-214] was the first to study the photooxidation of methane, ethane, and propane using Hg vapor as photosensitizer. Hydroperoxide was isolated as the product of propane oxidation at room temperature. The quantum yield of hydroperoxide was found to be >2, that is, oxidation occurs with short chains. The following scheme of propane photoxidation was proposed [117] ... 

Gray [215] studied the photooxidation of methane and ethane at room temperature in the gas phase using Hg as a photosensitizer. Hydroperoxide was found as the product of oxidation. Along with hydroperoxide, ozone was also found as the product of photooxidation. It was supposed to be due to the reaction of excited mercury atoms with dioxygen. 

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