Kinetics and Catalysis

, Volume 41, Issue 2, pp 186–195 | Cite as

Kinetics, substrate selectivity, and mechanisms of alkane and alkylbenzene reactions with peroxynitrous acid in the gas phase and solution

  • V. L. Lobachev
  • E. S. Rudakov


Specific features of the kinetics of alkane and alkylbenzene oxidation with HOONO formed in the H2O2-NaNO2 system (pH 4.27) are quantitatively explained assuming the simultaneous occurrence of reactions in the gas and liquid phases. A model of the kinetic distribution method is developed and verified that accounts for the equilibrium distribution of a substrate and a reagent between phases and their interaction in both phases. Relative rate constants for the oxidation ofn-alkanes (C3-C8), isobutane, cyclopentane, cyclohexane, benzene, and alkylbenzenes are measured over a wide range of the volume ratios of the gas and liquid phases (λ = Vg/V1). Relative rate constants for the oxidation of alkanes in the gas phase and alkylbenzenes in gas and solution were determined. Similarity in substrate selectivities and kinetic isotope effects of the gasphase reactions of alkanes and arenes with peroxynitrous acid andOH radicals suggest that hydroxyl radical or the ˙OH...NO2 radical pair is an active species in the gas phase. In solution, alkylbenzenes react nonselectively with HOONO, as well as with ˙OH radicals. In contrast to the liquid-phase oxidation of arenes, the liquidphase oxidation of all alkanes under study insignificantly contribute (5–15%) to the overall rate of the substrate consumption.


Alkane H202 Isobutane Alkylbenzenes Acetate Buffer Solution 
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Copyright information

© MAIK “Nauka/Interperiodica” 2000

Authors and Affiliations

  • V. L. Lobachev
    • 1
  • E. S. Rudakov
    • 1
  1. 1.Litvinenko Institute for Physicoorganic and Coal ChemistryNational Academy of Sciences of UkraineDonetskUkraine

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