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Teoret. i eksperim. khimiya. 2006. Vol.42 No. 5. p. 295-299

Substrate Selectivity and Mechanism of Alkanes Oxidation
by Peroxynitrous Acid in Aqueous Solution


E. S. Rudakov1, V. P. Tretyakov1, V. L. Lobachev1, L. A. Minko1, Ya. V. Matvienko2, V. G. Popov1

1 L. M. Litvinenko Institute of Physical-Organic and Coal Chemistry, National Academy of Sciences of Ukraine
Vul. R. Luxemburg , 70, Donetsk 83114, Ukraine. E-mail: rudakov@skif.net

2 Donetsk National University
Vul. Universytetska, 24, Donetsk 83055, Ukraine

The relative rate constants (krel) of alkanes (RH) oxidation by peroxynitrous acid (HOONO) in aqueous solutions were measured at 25 oC. The values krel for reactions of RH with HOONO and with OH-radicals in row of the C2-C7-alkanes and kinetic isotope effects (с-С6Н12/с-С6D12) coincided. However the value of krel for methane turned out to be less than in its reaction with OH-radicals. The probable mechanisms of the reactions were discussed.

Key word peroxynitrous acid, alkanes, oxidation, kinetics, mechanism, reactions in solution and gas phase.