Abstract

The reactions of OH with dimethyldisulfide (DMDS), dimethylsulfide (DMS), and diethylsulfide (DES) have been investigated applying both a photolytic relative technique and an absolute method using pulse radiolysis combined with kinetic spectroscopy. Furthermore, the reactions of OH with di-tert-butyldisulfide (DTBDS), ethylpropylsulfide (EPS), and dipropylsulfide (DPS) were studied using the absolute method. All measurements were done at room temperature and atmospheric pressure. The relative method using methyl nitrite as OH source was found to give unreliable OH rate constants with organic sulfides. The following absolute OH rate constants were obtained: $$\begin{array}{l} {\rm{k (OH + DMDS) = (300 }} \pm {\rm{ 30) x 1}}{{\rm{0}}^{ - 12}}\\ {\rm{k (OH + DTBDS) = (41 }} \pm {\rm{ 4) x 1}}{{\rm{0}}^{ - 12}}\\ {\rm{k (OH + DMS) = (3}}{\rm{.5 }} \pm {\rm{ 4) x 1}}{{\rm{0}}^{ - 12}}\\ {\rm{k (OH + DES) = (4}}{\rm{.5 }} \pm {\rm{ 5) x 1}}{{\rm{0}}^{ - 12}}\\ {\rm{k (OH + EPS) = (4}}{\rm{.9 }} \pm {\rm{ 5) x 1}}{{\rm{0}}^{ - 12}}\\ {\rm{k (OH + DPS) = (5}}{\rm{.2 }} \pm {\rm{ 5) x 1}}{{\rm{0}}^{ - 12}} \end{array}$$ (units are cm3molecule-1s-1) The data for the sulfides are consistent with the concept of group rate constants. The relative measured rate constants for the reaction of OH with DMS and DES were found to increase with increasing concentrations of added NO. These results provide some indication of the reasons for the difference in reported rate constants for these reactions. Still some discrepancies remain to be resolved.

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