High-energy transformations of polyfluoroalkanes. IX pyrolysis of 1,1-difluoroethane
Journal Article
·
· Russian Journal of General Chemistry
OSTI ID:198151
- St. Petersburg State Univ. (Russian Federation); and others
Kinetics of the unimolecular thermal dehydrofluorination of 1,1-difluoroethane in a flow reactor is reported. The first-order rate constant is determined; logk[1/c]=(-60,000{plus_minus}2000)/4.569{center_dot}T + 13.33{plus_minus}0.10. 1,1-Difluoroethylene, as a by-product of the pyrolysis of 1,1-difluoroethane, is formed by a radical mechanism, for which a heterogeneous, initiation state is proposed. MNDO calculations show the predominant formation of the CH{sub 3}-CF{sub 2} radical at the initiation stage. For this radical, rate constants of unimolecular 1{r_arrow}2 and 2{r_arrow}1 hydrogen shifts are determined within the framework of the PPKM statistical theory. 17 refs., 4 figs., 2 tabs.
- OSTI ID:
- 198151
- Journal Information:
- Russian Journal of General Chemistry, Vol. 64, Issue 1; Other Information: PBD: 10 Jul 1994; TN: Translated from Zhurnal Obshchei Khimii; 64: No. 1, 86-92(Jan 1994)
- Country of Publication:
- United States
- Language:
- English
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