Direct measurement of the rate of reaction of the methyl radical with sulphur dioxide

Mutual interactions of the methyl and methylperoxy radicals studied by flash photolysis and kinetic spectroscopy

“…To make the test as severe as possible, the lowest value of h~ [20] and the highest value of 1214 [23] were selected from the literature. For comparison a parallel set of calculations was performed with the estimate (5), (8), and (14), respectively, showing that more than half of the wastage of methyl radicals occurs by mutual combination (2) and that interaction with methylperoxy radicals (5) is of secondary importance for either value of k14. Furthermore, the relative contribution of reaction (14) is only doubled when the oxygen concentration is reduced by a factor of 30.…”

“…They estimated the value of n to be 0.59 f 0.04 [7] and 0.72 f 0.07 [8] with a band pass of 0.20 nm in two sets of experiments in one apparatus, and derived a value of the rate constant k2 = (3.37 f 0.46) X 1O1O l./mol sec [7]. In the present apparatus the value of n has been estimated under a variety of conditions by both the variable band pass method and the variable path length method.…”

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

“…In the gas phase the rate constant for the addition of methyl radicals to SO2 was found to be (1.75 f 0.25) X los l./mole.sec at room temperature [17]. Under the experimental conditions of this work (higher temperature and liquid phase) this rate constant may well be expected to be higher by an order of magnitude or even more.…”

“…Recently the last of these methods was employed in these laboratories in the study of the reactions of RSOz radicals in liquid cyclohexane [6]. The main advantage of the liquid phase study is that it is free from some of the complications encountered in the gas-phase photochemical studies of the hydrocarbon-SO2 systems 17-10] such as aerosol formation.…”

Radiolytic decomposition of methanesulfonyl chloride in liquid cyclohexane. A kinetic determination of the bond dissociation energies D(ME‐SO2) and D(c‐C6H11‐SO2)

“…sec [19]. Also, as transfer type reactions are not affected by the change of medium from the gas phase to nonpolar liquids [20], the k4 value of 1 X lo4 l./mole .…”