AN FTIR PRODUCT STUDY OF THE PHOTOOXIDATION OF DIMETHYL DISULFIDE

The products of the 254 nm photolysis of ppm levels of DMDS have been studied as a function of the O2 partial pressure at 760 Torr (N2 + O2) and 298 +/- 2 K. The major sulfur containing compounds detected were SO2 and CH3SO3H (methane sulfonic acid, MSA) and the major carbon cont aining compounds were CO, HCHO, CH3OH and CH3OOH (methyl hydroperoxide ). Within the experimental error limits the observed sulfur and carbon balances were approximately 100%. CH3OOH has been observed for the fi rst time in such a photooxidation system. Its observation provides evi dence for the formation of CH3 radicals by the further oxidation of th e CH3S radicals formed in the primary photolysis step. From the behavi or of the DMDS photolysis products as a function of the O2 partial Pre ssure, O3 concentration and added OH radical source it is postulated t hat the further reactions of CH3SOH (methyl sulfenic acid), formed in the reaction OH + CH3SCCH3 --> CH3SOH + CH3S, are the main source of M SA in the 254 nm photolysis of DMDS. Some of the possible implications of the results of this study for the degradation mechanisms of other atmospherically important organic sulfur compounds, in particular DMS, are briefly considered.