Thermal Decomposition of 3-Bromopropene. A Theoretical Kinetic Investigation.
J Phys Chem A
; 120(15): 2285-94, 2016 Apr 21.
Article
em En
| MEDLINE
| ID: mdl-27023718
A detailed kinetic study of the gas-phase thermal decomposition of 3-bromopropene over wide temperature and pressure ranges was performed. Quantum chemical calculations employing the density functional theory methods B3LYP, BMK, and M06-2X and the CBS-QB3 and G4 ab initio composite models provide the relevant part of the potential energy surfaces and the molecular properties of the species involved in the CH2âCH-CH2Br â CH2âCâCH2 + HBr (1) and CH2âCH-CH2Br â CH2âCH-CH2 + Br (2) reaction channels. Transition-state theory and unimolecular reaction rate theory calculations show that the simple bond fission reaction ( 2 ) is the predominant decomposition channel and that all reported experimental studies are very close to the high-pressure limit of this process. Over the 500-1400 K range a rate constant for the primary dissociation of k2,∞ = 4.8 × 10(14) exp(-55.0 kcal mol(-1)/RT) s(-1) is predicted at the G4 level. The calculated k1,∞ values lie between 50 to 260 times smaller. A value of 10.6 ± 1.5 kcal mol(-1) for the standard enthalpy of formation of 3-bromopropene at 298 K was estimated from G4 thermochemical calculations.
Texto completo:
1
Coleções:
01-internacional
Base de dados:
MEDLINE
Tipo de estudo:
Prognostic_studies
Idioma:
En
Revista:
J Phys Chem A
Assunto da revista:
QUIMICA
Ano de publicação:
2016
Tipo de documento:
Article
País de afiliação:
Argentina
País de publicação:
Estados Unidos