Catalogo Articoli (Spogli Riviste)
OPAC HELP
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:
 05388066(200111)33:11<654:TRBEAM>2.0.ZU;2G
 Fonte:
 ISI
 Lingua:
 ENG
 Soggetto:
 C2H5+O2 REACTION; PRESSUREDEPENDENCE; UNIMOLECULAR REACTIONS; CHEMICAL ACTIVATION; RATE COEFFICIENTS; REACTIONKINETICS; 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. 654668
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 hightemperature rate coefficient k(T) is to E02, the threshold energy of the transition state for direct molecular elimination of HO2 from ethylperoxy radical (C2H5O2), thus deducing a value of E02 = 3.0 kcal/mol (measured from reactants),2. We derive the result that k(0)(T) approximate to k ' (infinity)(T) in the hightemperature regime, where k(0)(T) is the zeropressure rate coefficient, and k ' (infinity)(T) is the infinitepressure rate coefficient for the bimolecular channel.3. Most importantly. we discuss the three different regimes of the reaction (lowtemperature, transition, and hightemperature) 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 hightemperature 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, 1154911560).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.
ASDD Area Sistemi Dipartimentali e Documentali, Università di Bologna, Catalogo delle riviste ed altri periodici
Documento generato il 29/11/20 alle ore 01:49:01