Premium
Mechanism of pyrolysis of C 2 Cl 6
Author(s) -
Weissman Maia,
Benson Sidney W.
Publication year - 1980
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.550120606
Subject(s) - chemistry , dissociation (chemistry) , pyrolysis , activation energy , rate equation , kinetics , bond dissociation energy , reaction mechanism , chemical kinetics , thermodynamics , organic chemistry , catalysis , physics , quantum mechanics
Using published data on the kinetics of pyrolysis of C 2 Cl 6 and estimated rate parameters for all the involved radical reactions, a mechanism is proposed which accounts quantitatively for all the observations:The steady‐state rate law valid for after about 0.1% reaction isand the reaction is verified to proceed through the two parallel stages suggested earlier whose net reaction isA reported induction period obtained from pressure measurements used to follow the rate is shown to be compatible with the endothermicity of reaction A, giving rise to a self‐cooling of the gaseous mixture and thus an overall pressure decrease. From the analysis, the bond dissociation energy DH 0 (C 2 Cl 5 Cl) is found to be 70.3 ± 1 kcal/mol and Δ H f300 0 (·C 2 Cl 5 ) = 7.7 ± 1 kcal/mol. The resulting πbond energy in C 2 Cl 4 is 52.5 ± 1 kcal/mol.