Hydrocarbon autoxidation, absolute rate constants for

Adamic K, Howard JA, Ingold KU (1969) Absolute rate constants for hydrocarbon autoxidation. XVI. 

Furimsky E, Howard JA, Selwyn J (1980) Absolute rate constants for hydrocarbon autoxidation. 28. A low temperature kinetic electron spin resonance study of the self- reactions of isopropylperoxy and related secondary alkylperoxy radicals in solution. Can J Chem 58 677-680 Gebicki JM, Allen AO (1969) Relationship between critical micelle concentration and rate of radiolysis of aqueous sodium linolenate. J Phys Chem 73 2443-2445 Gebicki JM, Bielski BHJ (1981) Comparison of the capacities of the perhydroxyl and the superoxide radicals to initiate chain oxidation of linoleic acid. J Am Chem Soc 103 7020-7022 Gilbert BC, Holmes RGG, Laue HAH, Norman ROC (1976) Electron spin resonance studies, part L. Reactions of alkoxyl radicals generated from alkylhydroperoxidesand titanium(lll) ion in aqueous solution. J Chem Soc Perkin Trans 2 1047-1052... 

Howard, J. A. Schwahn, W. J. Ingold, K. U. Absolute Rate Constants for Hydrocarbons autoxidation. VII. The Reactivities of Peroxy Radicals towards Hydrocarbons and Hydroperoxides, In Preprints of the International Oxidation Simposium. San Francisco, California. 1967 1, 3. 

S. Korcek, J.H.B. Chenier, J.A. Howard, K.U Ingold. Absolute rate constants for hydrocarbon autoxidation. XXL Activation energies for propagation and the correlation of propagation rate constants with carbon-hydrogen bond strengths. Canadian Journal of Chemistry 50(14), 2167-2174 (1972). 

Because of the importance of hydroperoxy radicals in autoxidation processes, their reactions with hydrocarbons arc well known. However, reactions with monomers have not been widely studied. Absolute rate constants for addition to common monomers are in the range 0.09-3 M"1 s"1 at 40 °C. These are substantially lower than kL for other oxygen-centered radicals (Table 3.7). 454... 

This difficulty has now been overcome. Howard, Schwalm, and Ingold (24) show that the rate constant for reaction of any alkylperoxy radical with any hydrocarbon can be determined (by the sector method) by carrying out the autoxidation of the hydrocarbon in the presence of >0.1 M hydroperoxide corresponding to the chosen radical. All the absolute propagation and termination constants for the co-oxidation of cumene and Tetralin were thus determined. Our Tetralin-cumene work suggests that their results agree well with the best we have been able to get... 

A New Method for Determining the Absolute Rate Constants of Autoxidation of Some Hydrocarbons... 

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