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Vibrational nonequilibrium and electronic excitation in the reaction of hydrogen with oxygen behind a shock wave

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Abstract

A theoretical analysis of ignition and combustion processes in a hydrogen-oxygen mixture behind a shock wave is presented (1000 K ≤ T ≤ 2500 K; 2.0 atm ≥ P ≥ 0.3 atm). The experiments performed using stoichiometric mixtures with the detection of OH (2Σ+) and rich mixtures with the detection of OH (2Π) were interpreted in terms of a general kinetic approach. In this case, the apparent rate constant of the chain branching reaction H + O2 → O + OH was the only adjustable parameter. It was found that this rate constant increased with decreasing hydrogen content and exceeded equilibrium values. In this context, the mechanism of chain branching, which occurs through the formation of the vibrationally excited radical HO2(v), and the role of secondary vibrationally nonequilibrium O2 and O2(1Δ) molecules and the reaction H + O2(1Δ) → O + OH are discussed. New mechanisms of the formation and quenching of electronically excited OH(2Σ+) radicals, O(1 D) atoms, and O2(1Δ) molecules are considered. The results of a nonempirical (ab initio) analysis of molecular systems and the corresponding estimations of reaction rate constants were widely used.

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Authors and Affiliations

  1. Institute of Problems of Chemical Physics, Russian Academy of Sciences, Chernogolovka, Moscow oblast, 142432, Russia

    O. V. Skrebkov & S. P. Karkach

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  1. O. V. Skrebkov
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  2. S. P. Karkach
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Original Russian Text © O.V. Skrebkov, S.P. Karkach, 2007, published in Kinetika i Kataliz, 2007, Vol. 48, No. 3, pp. 388–396.

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Skrebkov, O.V., Karkach, S.P. Vibrational nonequilibrium and electronic excitation in the reaction of hydrogen with oxygen behind a shock wave. Kinet Catal 48, 367–375 (2007). https://doi.org/10.1134/S0023158407030044

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