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Titolo:
The reaction between ethyl and molecular oxygen II: Further analysis
Autore:
Miller, JA; Klippenstein, SJ;
Indirizzi:
Sandia Natl Labs, Combust Res Facil, Livermore, CA 94551 USA Sandia Natl Labs Livermore CA USA 94551 es Facil, Livermore, CA 94551 USA
Titolo Testata:
INTERNATIONAL JOURNAL OF CHEMICAL KINETICS
fascicolo: 11, volume: 33, anno: 2001,
pagine: 654 - 668
SICI:
0538-8066(200111)33:11<654:TRBEAM>2.0.ZU;2-G
Fonte:
ISI
Lingua:
ENG
Soggetto:
C2H5+O-2 REACTION; PRESSURE-DEPENDENCE; UNIMOLECULAR REACTIONS; CHEMICAL ACTIVATION; RATE COEFFICIENTS; REACTION-KINETICS; MASTER EQUATION; C2H4 YIELD; MECHANISM; COMBUSTION;
Tipo documento:
Article
Natura:
Periodico
Settore Disciplinare:
Physical, Chemical & Earth Sciences
Citazioni:
38
Recensione:
Indirizzi per estratti:
Indirizzo: Miller, JA Sandia Natl Labs, Combust Res Facil, Livermore, CA 94551 USA Sandia Natl Labs Livermore CA USA 94551 ivermore, CA 94551 USA
Citazione:
J.A. Miller e S.J. Klippenstein, "The reaction between ethyl and molecular oxygen II: Further analysis", INT J CH K, 33(11), 2001, pp. 654-668

Abstract

The present investigation is a rather substantial extension and elaboration of our previous work on the same reaction, In this article we accomplish four primary objectives:1. We show quantitatively how sensitive the high-temperature rate coefficient k(T) is to E-02, the threshold energy of the transition state for direct molecular elimination of HO2 from ethylperoxy radical (C2H5O2), thus deducing a value of E-02 = -3.0 kcal/mol (measured from reactants),2. We derive the result that k(0)(T) approximate to k ' (infinity)(T) in the high-temperature regime, where k(0)(T) is the zero-pressure rate coefficient, and k ' (infinity)(T) is the infinite-pressure rate coefficient for the bimolecular channel.3. Most importantly. we discuss the three different regimes of the reaction (low-temperature, transition, and high-temperature) in terms of the eigenvectors and eigenvalues of G, the transition matrix of the master equation,The transition regime is shown to be a region of avoided crossing between the two chemically significant eigenvalue curves in which the thermal rate coefficient kj,p) jumps from one eigenvalue to the other. This jump is accompanied by a "mixing" of the corresponding eigenvectors, through which botheigenvectors deplete the reactant. The onset of the high-temperature regime is triggered by reaching the "stabilization limit" of the ethylperoxy adduct, a limit that is induced by a shift in equilibrium of the stabilizationreaction, our identification of the prompt and secondary HO2 formed by thereaction with these eigenvalue/eigenvector pairs leads to good agreement between theory and the experiments of Clifford et al. (J Phys Chem A 2000, 104, 11549-11560).4. Lastly, we describe the master equation results in terms of a set of elementary reactions and phenomenological rate coefficients. (C) 2001 John Wiley & Sons, Inc.

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Documento generato il 29/11/20 alle ore 01:49:01