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  Shock wave study of the thermal dissociations of C3F6 and c-C3F6. II. dissociation of hexafluorocyclopropane and dimerization of CF2.

Cobos, C. J., Sölter, L., Tellbach, E., & Troe, J. (2014). Shock wave study of the thermal dissociations of C3F6 and c-C3F6. II. dissociation of hexafluorocyclopropane and dimerization of CF2. The Journal of Physical Chemistry A, 118(27), 4873-4879. doi:10.1021/jp501577k.

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Item Permalink: http://hdl.handle.net/11858/00-001M-0000-001A-22EB-C Version Permalink: http://hdl.handle.net/11858/00-001M-0000-0027-CA85-C
Genre: Journal Article

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2048394.pdf (Publisher version), 2MB
 
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http://pubs.acs.org/doi/pdf/10.1021/jp501577k (Publisher version)
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Cobos, C. J., Author
Sölter, L.1, Author              
Tellbach, E.2, Author              
Troe, J.1, Author              
Affiliations:
1Emeritus Group of Spectroscopy and Photochemical Kinetics, MPI for Biophysical Chemistry, Max Planck Society, ou_578625              
2Department of Dynamics at Surfaces, MPI for Biophysical Chemistry, Max Planck Society, ou_578600              

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 Abstract: The thermal dissociation of c-C3F6 has been studied in shock waves over the range 620–1030 K monitoring the UV absorption of CF2. The reaction was studied close to its high-pressure limit, but some high-temperature falloff was accounted for. Quantum-chemical and kinetic modeling rationalized the experimental data. The reaction is suggested to involve the 1,3 biradical CF2CF2CF2 intermediate. CF2 formed by the dissociation of c-C3F6 dimerizes to C2F4. The measured rate of this reaction is also found to correspond to the falloff range. Rate constants for 2CF2 → C2F4 as a function of temperature and bath gas concentration [Ar] are given and shown to be consistent with literature values for the high-pressure rate constants from experiments at lower temperatures and dissociation rate constants obtained in the falloff range at higher temperatures. The onset of falloff at intermediate temperatures is analyzed

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Language(s): eng - English
 Dates: 2014-06-062014-07-10
 Publication Status: Published in print
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 Rev. Method: Peer
 Identifiers: DOI: 10.1021/jp501577k
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Title: The Journal of Physical Chemistry A
Source Genre: Journal
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Pages: - Volume / Issue: 118 (27) Sequence Number: - Start / End Page: 4873 - 4879 Identifier: -