Chemically and thermally activated decomposition of secondary butyl radical

Citation
Vd. Knyazev et W. Tsang, Chemically and thermally activated decomposition of secondary butyl radical, J PHYS CH A, 104(46), 2000, pp. 10747-10765
Citations number
98
Language
INGLESE
art.tipo
Article
Categorie Soggetti
Physical Chemistry/Chemical Physics
Journal title
JOURNAL OF PHYSICAL CHEMISTRY A
ISSN journal
1089-5639 → ACNP
Volume
104
Issue
46
Year of publication
2000
Pages
10747 - 10765
Database
ISI
SICI code
1089-5639(20001123)104:46<10747:CATADO>2.0.ZU;2-L
Abstract
Experimental literature data on the chemically and thermally activated deco mposition of sec-C4H9 radical were analyzed by weak collision master equati on modeling. A reaction model with very little flexibility in its propertie s was created on the basis of ab initio calculations and experimental kinet ic and thermochemical data. Rate constants and branching fractions for the: chemically activated reaction were calculated using the virtual component f ormalism. The resultant model quantitatively describes (1) data on the stab ilization-to-decomposition ratios as functions of temperature and pressure obtained in experiments using H + butene reactions as the sources of chemic al activation and (2) experimental data on the thermal decomposition bf sec -C4H9 radicals. Values of (DeltaE)(down), the average energy transferred pe r deactivating collision, derived from modeling of experimental data demons trate strong positive temperature dependencies for a variety of bath gases. Qualitative shapes of falloff curves for the chemically activated reaction were analyzed. Comparison of the weak collision model with the results of the modified strong collision treatment demonstrates the inadequacy of the latter.