CHEMILUMINESCENT REACTIONS OF OZONE WITH METHYL MERCAPTAN AND HYDROGEN SULFIDE
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Date
1981
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Ohio State University
Abstract
The chemiluminescence resulting from the reaction of $O_{3}$ with the simple sulfides, $CH_{3}SH$ and $H_{2}S$, has been studied at low pressures in a beam-gas apparatus. The fluorescence and vibrationally resolved phosphorescence from $SO{^{*}}{_{2}}$ produced in the reaction were monitored as a function of the pressure of the oxidizer, fuel and bath gas over a total pressure range from $5\times10^{-3}$ to $> 10^{-1}$ torr. The observed pressure dependencies provide estimates of the relative contributions of the long-lived $^{1}B_{1}$ and short-lived $^{1}A_{2}$ states to the total fluorescence band from $2800 - 5200$ \AA. The data also demonstrate that the $^{1}A_{2}$ state is quenched to the triplet manifold and help to elucidate the mechanism for intersystem crossing in $SO_{2}$. At longer wave lengths, structured emission for the reaction of $H_{2}S$ is observed and is tentatively identified as HSO. For $CH_{3}SH$ as the reactant, the meinel bands of DH are observed in the wave length region. These data are employed in developing a mechanism for the ozonolysis of these simple sulfides.
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