Oxidation Reactions of Alkyl Radicals

The complex nature of the general rate constant kt has been discussed, together with evidence that conjugate alkenes are formed in the direct bimolecular reaction (6A), and not via the formation of the OOOH radical. 

Oxidation Reactions of Meti rl Radicals.— Reactions (7m) and (5Bm) still merit considerable attention references up to the end of 1973 can be traced through the earlier Report.  

The mechanism of reaction (SBm) continues to (ercise the imagination. Recently, four sets of Arrhenius parameters have beoi obtained from studies of the shock-initiated oxidation of methane coupled with spectroscopic detection of various molecule and radical species the results are summarized in Table 10. Jachimowski and Tsuboi and Wagn offCT no guidance as to the medumism, 

Brabbs and R. S. mokaw, ISth International Combustion Symp., The Combustion Institute, Pittsburid , Pennsylvania, 197S, p. 893. 

Jachimowski X, Bowman A, Tsuboi and Wagner .Brabbsand Brokaw , Higgin and Williams , dark, Ltod, and Matsuda V, Izod, Kistiakowsky, and Matsuda , Dean and Kistiakowsky. Last four sets of results are discussed on pages 199 and 200 of reference 1) 

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Somewhere in the temperature range 450° to 600°C. pyrolysis must compete on nearly equal terms with oxidation of alkyl radicals. The work of Baldwin is therefore particularly important since the rate constants for pyrolysis of alkyl radicals are reasonably well established. There is therefore the strong possibility that we shall soon possess rate constants for oxidation reactions of alkyl radicals at high temperatures. Examination of the oxidation products of the higher alkanes by the Baldwin method should go far toward resolving the problem of the source of fragmentation products at lower temperatures. 

Radical Decompositions and Isommizations Radical Deoompomtions.—At temperature above 650 K, radical decomposition by C—C homolysis competes with oxidation reactions of alkyl radicals, and, from... 

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