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Thermochemistry and Kinetics of the Thermal Decomposition of 1‐Chlorohexane
Author(s) -
Quiñonez Elizabeth Gaona,
Tucceri María Eugenia
Publication year - 2017
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.21111
Subject(s) - isodesmic reaction , chemistry , thermochemistry , thermal decomposition , transition state theory , decomposition , density functional theory , standard enthalpy of formation , ab initio , thermodynamics , computational chemistry , kinetics , reaction rate constant , organic chemistry , physics , quantum mechanics
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 ∞ (600–1000 K) = (8 ± 5) × 10 13 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 C 6 H 13 radical were derived from isodesmic and isogiric reactions at high levels of theory.