Thermochemistry and kinetics of the thermal decomposition of 1-chlorohexane

GAONA QUIÑONEZ, JUANA ELIZABETH; MARIA EUGENIA TUCCERI

INTERNATIONAL JOURNAL OF CHEMICAL KINETICS

JOHN WILEY & SONS INC

Lugar: New York; Año: 2017

0538-8066

A theoretical kinetic study of the thermal decomposition of 1-chlorohexane in gas-phase between 600 and 1000 K was performed. Transition-state theory and unimolecular reaction rate theory were combined with molecular information provided by quantum chemical calculations. Particularly, the B3LYP, BMK, M05-2X and M06-2X formulations of the density functional theory, DFT, and the high level ab initio methods G3B3 and G4 were employed. The possible reaction channels for the thermal decomposition of 1-chlorohexane were investigated and the reaction takes place through the elimination of HCl with the formation of 1-hexene. The derived high-pressure limit rate coefficients are k∞(600-1000K) = (8 ± 5) x1013 exp[-((56.7 ± 0.4) kcal mol-1/RT)] s-1. The pressure effect over the reaction was analyzed from the calculation of the low-pressure limit rate coefficients and the falloff curves. In addition, the standard enthalpies of formation at 298 K of -46.9 ± 1.5 kcal mol-1 for 1-chlorohexane and 5.8 ± 1.5 kcal mol-1 for C6H13 radical, were derived from isodesmic and isogiric reactions at high levels of theory.