Shock wave and modeling study of the thermal decomposition reactions of 
pentafluoroethane and 2-H-heptafluoropropane.

Cobos, C. J.; Sölter, L.; Tellbach, E.; Troe, J.

doi:10.1039/c3cp54274b

アイテム詳細

登録内容を編集ファイル形式で保存

一時保存へ追加

タグ情報を表示リリース履歴を表示詳細要約

公開

学術論文

Shock wave and modeling study of the thermal decomposition reactions of pentafluoroethane and 2-H-heptafluoropropane.

MPS-Authors

/persons/resource/persons15934

Troe, J.
Emeritus Group of Spectroscopy and Photochemical Kinetics, MPI for Biophysical Chemistry, Max Planck Society;

External Resource

http://pubs.rsc.org/en/content/articlepdf/2014/cp/c3cp54274b
(出版社版)

Fulltext (restricted access)

There are currently no full texts shared for your IP range.

フルテキスト (公開)

2033288.pdf
(出版社版), 2MB

付随資料 (公開)

There is no public supplementary material available

引用

Cobos, C. J., Sölter, L., Tellbach, E., & Troe, J. (2014). Shock wave and modeling study of the thermal decomposition reactions of pentafluoroethane and 2-H-heptafluoropropane. Physical Chemistry Chemical Physics, 16(21), 9797-9807. doi:10.1039/c3cp54274b.

引用: https://hdl.handle.net/11858/00-001M-0000-0019-BCD1-F

要旨

The thermal decomposition reactions of CF3CF2H and CF3CFHCF3 have been studied in shock waves by monitoring the appearance of CF2 radicals. Temperatures in the range 1400-2000 K and Ar bath gas concentrations in the range (2-10) Chi 10(-5) mol cm(-3) were employed. It is shown that the reactions are initiated by C-C bond fission and not by HF elimination. Differing conclusions in the literature about the primary decomposition products, such as deduced from experiments at very low pressures, are attributed to unimolecular falloff effects. By increasing the initial reactant concentrations in Ar from 60 to 1000 ppm, a retardation of CF2 formation was observed while the final CF2 yields remained close to two CF2 per C2F5H or three CF2 per C3F7H decomposed. This is explained by secondary bimolecular reactions which lead to comparably stable transient species like CF3H, releasing CF2 at a slower rate. Quantum-chemical calculations and kinetic modeling help to identify the reaction pathways and provide estimates of rate constants for a series of primary and secondary reactions in the decomposition mechanism.