Quantum-Chemical Kinetic Study of the Unimolecular Decomposition Reactions of 1-Bromo-3-Chloropropane

LARISA L. B. BRACCO; MARÍA EUGENIA TUCCERI; MARÍA PAULA BADENES; CARLOS JORGE COBOS

JOURNAL OF PHYSICAL CHEMISTRY A

AMER CHEMICAL SOC

Lugar: Washington; Año: 2022 vol. 126 p. 2103 - 2110

1089-5639

The pressure and temperature dependence of the thermal decomposition of 1-bromo-3-chloropropane has been theoretically investigated. The reaction takes place majorly through the elimination of HBr. Molecular properties of 1-bromo-3-chloropropane and transition states were derived from MN15/6-311++G(3df,3pd) and G4 quantum-chemical calculations. The resulting rate constants obtained from the unimolecular reaction rate theory for the high- and low-pressure limits of reaction BrCH2CH2CH2Cl → CH2CHCH2Cl + HBr at 400?1000 K were k∞ = 6.1 × 1013 exp(−57.2 kcal mol?1/RT) s?1 and k0 = [BrCH2CH2CH2Cl] 1.45 × 10?1 (T/1000 K)−7.9 exp(−55.9 kcal mol?1/RT) cm3 molecule?1 s?1. A value of −26.3 ± 1.0 kcal mol?1 for the standard enthalpy of formation of 1-bromo-3-chloropropane at 298 K was derived