Liquid phase kinetic study of the formation and decomposition of methylsulfonyl and cyclohexylsulfonyl radicals in the cyclohexane–MeSO2C1-SO2 System at 150° |
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Authors: | Abraham Horowitz |
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Abstract: | The thermally and radiolytically induced chain decomposition of methanesulfonyl chloride (MeSO2Cl) in liquid cyclohexane (RH) was studied 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 decomposition of MeSO2, 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 + MeSO2Cl → MeCl + MeSO2(2b), Me + RH → MeH + R (4), and Me + CCl4 → MeCCl4 → MeCl + CCl3 (15b) the following rate constant ratios are determined; k2b/k4=2.17±0.20 and k2b/k15b=2.63±0.52. For the reactions R + MeSO2Cl → RCl + MeSO2(2a) and R + CCl4 → RCl + CCl3 (15a), k2a/k15a is equal to 1.55±0.05. In addition the equilibrium constant K7 for the reaction R + SO2 ? RSO2 (7) is estimated as being equal to (9.4±3) × 103 mole/l. |
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