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Earlier experimental results on the kinetics of relaxation to equilibrium in R + O 2 a RO 2 reactions (R ) CH 3 , C 2 H 5 , i-C 3 H 7 , t-C 4 H 9 , CH 2 Cl, CHCl 2 , and CCl 3 ) are reanalyzed using an improved kinetic mechanism which accounts for further reactions of the RO 2 adduct. Reaction enthalpy ∆H°2 98 (R + O 2 a RO 2 ) values are obtained from the third-law treatment of the temperature dependencies of the equilibrium constants K P (T) resulting from the reinterpretation of the original kinetic data. The R-O 2 bond strengths for alkyl and chloroalkyl radicals (R ) ‚C(CH 3 ) i Cl j H k , i + j + k ) 3) can be represented by a linear function of the numbers of C-C (N C-C ) and C-Cl (N C-Cl ) bonds at the C atom forming the C-O bond:). The values of ∆H°2 98 (R + O 2 a RO 2 ) are used to calculate the enthalpies of formation for the RO 2 peroxy radicals and ROOH hydroperoxides.

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