Mechanism of the Formation of Halogen Monoxides During Flash Photolysis of Halogen + Oxygen Mixtures

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The mechanism of the formation of BrO and ClO in the flash photolysis of halogen + oxygen mixtures was investigated. It was found that the predominant mechanism for the production of BrO (about 90% in our experiments) involves the absorption of light by the oxygen molecules. The O^*_2 or the oxygen atoms produced create ozone, which in turn produces BrO when photolyzed. It is possible that some of O^*_2 or O produces BrO directly and not via an ozone intermediate. About 10% of the BrO is produced when two quanta of radiant energy are absorbed by the Br_2 molecule. The highly energetic molecule formed in this way is capable of breaking the O-O bond and forming BrO. The reaction between the excited Br atoms and O_2, suggested by Durie & Ramsey (1958), does not occur. It seems likely that IO is formed by a mechanism similar to that of BrO. On the other hand, CIO is produced predominantly in a reaction of Cl(^2P_3/2) atoms with O_2, as suggested by Porter & Wright (1953). Chlorine and bromine absorption spectra were measured down to 1880 and 1930 Å, respectively.

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