Incorporation of non-steady-state unimolecular and chemically activated kinetics into complex kinetic schemes. 1. Isothermal kinetics at constant pressure

Citation
Vd. Knyazev et W. Tsang, Incorporation of non-steady-state unimolecular and chemically activated kinetics into complex kinetic schemes. 1. Isothermal kinetics at constant pressure, J PHYS CH A, 103(20), 1999, pp. 3944-3954
Citations number
31
Language
INGLESE
art.tipo
Article
Categorie Soggetti
Physical Chemistry/Chemical Physics
Journal title
JOURNAL OF PHYSICAL CHEMISTRY A
ISSN journal
1089-5639 → ACNP
Volume
103
Issue
20
Year of publication
1999
Pages
3944 - 3954
Database
ISI
SICI code
1089-5639(19990520)103:20<3944:IONUAC>2.0.ZU;2-Z
Abstract
A general method of accounting for non-steady-state unimolecular kinetics o f reactive species in complex kinetic schemes is described. The method is b ased on dividing the overall population of affected species into virtual co mponents corresponding to individual eigenvectors of the master equation ma trix. It is shown that these individual virtual components are in their res pective steady states and evolve independently of each other. The overall t reatment is significantly simplified by the fact that only several of these virtual components need to be considered explicitly, and the contribution of the remainder can be described jointly as resulting in ordinary chemical branching. The described method reduces the problem of non-steady-state ki netics to a modest kinetic scheme which can be solved by standard technique s.