Mechanism of pyrolysis of C2Cl6

✍ Scribed by Maia Weissman; Sidney W. Benson

• Publisher: John Wiley and Sons
• Year: 1980
• Tongue: English
• Weight: 539 KB
• Volume: 12
• Category: Article
• ISSN: 0538-8066
• DOI: 10.1002/kin.550120606

✦ Synopsis

Using published data on the kinetics of pyrolysis of C2Cls 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 is and the reaction is verified to proceed through the two parallel stages suggested earlier whose net reaction is C&ls & C2C14 + C12 ( K A : small; k A: fast) A 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 DHo(C2CIs-CI) is found to be 70.3 f 1 kcal/mol and AHgoo(.C2C15) = 7.7 f 1 kcal/mol. The resulting *-bond energy in CzC14 is 52.5 f 1 kcal/mol.