Radiolytic decomposition of methanesulfonyl chloride in liquid cyclohexane. A kinetic determination of the bond dissociation energies D(ME-SO2) and D(c-C6H11-SO2)
✍ Scribed by Abraham Horowitz
- Publisher
- John Wiley and Sons
- Year
- 1976
- Tongue
- English
- Weight
- 645 KB
- Volume
- 8
- Category
- Article
- ISSN
- 0538-8066
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✦ Synopsis
The gamma radiation induced decomposition of MeS02C1 in cyclohexane (RH) was studied Throughout this temperature range the reaction proceeds by a free between 60 and 150°C. radical chain mechanism. Its propagation is described by the following reactions:
The kinetic analysis of the results of the experiments with added SOZ, which were carried out in the temperature range of 80 to 15O"C, gives 14.94 =k 0.92 and 11.91 f 0.82 kcal/mole for D(Me-S02) and D(c-C6H11-S02), respectively. These bond dissociation energies are considerably lower than the gas-phase values, and the possible cause of this difference is discussed. Present results also seem to indicate that D(MeS02-H) does not exceed 95 kcal/mole. Competitive experiments with added tetrachloroethylene result in log kZa (l./mole . sec) = 9.07 & 0.17 -(4.92 & 0.21)/0 where e = 2.303RT in kcal/mole.