Pulsradiolytische Untersuchung von Dimethylthioäther und Dimethylsulfoxyd in wäßriger Lösung

Abstract

The following absolute rate constants of the reactions of eaq ⊖ and OH with dimethylthioether and dimethylsulfoxide have been determined: k (eaq ⊖ + CH3SCH3) =2.0·107 mol-1 l sec-1; k(e⊖+ CH3SOCH3) =1.7·106; k(OH+CH3SCH3) =5.2·109; k(OH+CH3SOCH3) =4.2·109. The acid and basic components of the equilibrium are formed in the reactions of OH+CH3SCH3 and eaq ⊖ +CH3SOCH3, respectively. The anion absorbs at 3500 Å. The ρK value of the equilibrium was found to be equal to 10.2. The CH2SCH3 radical (2900 Å) and the ions CH3SCH3 ⊕ or (CH3SCH3)2⊕ (4700 Å) are also formed in the reaction between OH and CH3SCH3. High thioether and low OH⊖ concentrations favour the formation of the positive ion which is believed to result from a reaction between CH3SOHCH3 and CH3SCH3.