Liquid phase kinetic study of the formation and decomposition of methylsulfonyl and cyclohexylsulfonyl radicals in the cyclohexane–MeSO2C1-SO2 System at 150°

✍ Scribed by Abraham Horowitz

• Publisher: John Wiley and Sons
• Year: 1975
• Tongue: English
• Weight: 706 KB
• Volume: 7
• Category: Article
• ISSN: 0538-8066
• DOI: 10.1002/kin.550070612

✦ Synopsis

The thermally and radiolytically induced chain decomposition of methanesulfonyl chloride (MeSO2Cl) in liquid cyclohexane (RH) wasstudied at 150°C. The main products, chlorocyclohexane, sulfur dioxide, and methane, are formed in almost equal yields, and a relatively small amount of methyl chloride is also observed. The formation and addition of SO2 strongly inhibit the chain decomposition reaction. By kinetic analysis it is shown that the formation of the main products can be explained only in terms of a mechanism that postulates the decompostition of MeS02, and that the alternative mechanism of methane and SO2 formation via the methanesulfinic acid is inconsistent with the kinetic behavior of the system. For the reactions Me + MeSOzCl -+ MeCl + MeSO2(2b), Me + RH -+ MeH + R (4), and Me + CCI, -+ MeCCll -+ MeCl + CCI, (15b) the following rate constant ratios are determined; k 2 b / k l = 2.17 f 0.20 and k2b/k15b = 2.63 f 0.52. For the reactions R + MeS02CI -+ RC1 + MeSOz(2a) and R + CCla -+ RCI + CCl, (15a), kzJk,,, is equal to 1.55 f 0.05. In addition the equilibrium constant K , for the reaction R + SO2 @ RS02 (7) is estimated as being equal to (9.4 3) x lo3 mole/].