Energy randomization in the reactions of F atoms at the carboxyl sites of CH3COOH and CF3COOH

doi:10.1016/0301-0104(81)80054-7

Chemical Physics

Volume 58, Issue 2, 15 June 1981, Pages 175-183

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Abstract

The HF and DF vibrational distributions for the hydrogen abstraction reactions between F atoms and CH₃COOD, CD₃COOH, CF₃COOD and CF₃COO have been measured by arrested relaxation infrared chemiluminescence. Phase space calculations have been carried out which accurately reproduce the dis observed for the reactions at the carboxyl site in each case. The calculations suggest that the energy is not completely randomised during the acetic a whereas the trifluoroacetic acid reactions show ergodic behaviour.

References (18)

L.C. Krishner et al.
J. Chem. Phys.
(1971)
M.G. Moss et al.
J. Chem. Phys.
(1980)
B.E. Holmes et al.
Physical chemistry of fast reactions
J.D. McDonald
Ann. Rev. Phys. Chem.
(1979)
H.M. Frey et al.
D. Bogan et al.
ACS Symposium Series 66 on Fluorine Containing Radicals
(1978)
J.M. Parson et al.
J. Chem. Phys.
(1972)
J.M. Parson et al.
J. Chem. Phys.
(1973)
K. Shobotake et al.
J. Chem. Phys.
(1973)
K. Shobotake et al.
J. Chem. Phys.
(1973)
K. Shobotake et al.
J. Chem. Phys.
(1973)
R.J. Buss et al.
Faraday Disc. Chem. Soc.
(1979)
J.M. Farrar et al.
J. Chem. Phys.
(1975)
J.G. Moehlmann et al.
J. Chem. Phys.
(1974)
J.G. Moehlmann et al.
J. Chem. Phys.
(1975)
J.F. Durana et al.
J. Chem. Phys.
(1976)
J.C. Polanyi
Accounts Chem. Res.
(1972)

There are more references available in the full text version of this article.

Cited by (5)

Infrared fluorescence from nascent CO<inf>2</inf> and COF<inf>2</inf> photoproducts in IR multiphoton dissociation of trifluoroacetic acid
1993, Chemical Physics Letters
Infrared multiphoton dissociation of trifluoroacetic acid by pulsed CO₂ laser yields HF, COF₂ CO₂, CO, F₃ CCO₂CF₂H and C₂F₄ as photoproducts. Infrared fluorescence from the photoproducts, CO₂ and COF₂, is observed and analysed. Intermolecular V—V and V—R/T relaxation rate constants for CO₂ decay are found to be 1.7×10⁵ and 1.4×10⁴s⁻¹ Torr⁻¹, whereas for COF₂ decay these two relaxation rate constants are 7.3×10⁴ and 8.9×10³s⁻¹ Torr⁻¹, respectively.
Detailed energy partitioning in the decomposition of chemically energized C<inf>2</inf>H<inf>3</inf>F
1982, Chemical Physics
The HF product energy distribution in the reaction of F atoms with ·C₂H₃ radicals has been directly measured using a modification of the arrested relaxation infrared chemiluminescence technique in which the vinyl radicals are prepared and react to form the observed products in successive chemical reactions. The experimentally observed vibrational and rotational distributions are correctly reproduced by a calculation in which the reaction exoergicity is partitioned statistically among the products of the unimolecular decomposition of energized vinyl fluoride. Some properties of the transition state for this process are thereby elucidated. The statistical energy partitioning likely results from the relatively high (125 kcal mol⁻¹) excitation of the vinyl fluoride intermediate.
The dynamics of the F/HNCO and F/HNF reactions
1981, Chemical Physics
Spectroscopy and photochemistry of free radicals formed by the reaction of F atoms with small molecules
1985, Reviews of Chemical Intermediates
Energy distributions in the HF and CO products of the reaction of F atoms with HCO
1984, The Journal of Chemical Physics

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Energy randomization in the reactions of F atoms at the carboxyl sites of CH3COOH and CF3COOH☆

Abstract

J. Chem. Phys.

J. Chem. Phys.

Physical chemistry of fast reactions

Ann. Rev. Phys. Chem.

ACS Symposium Series 66 on Fluorine Containing Radicals

J. Chem. Phys.

J. Chem. Phys.

J. Chem. Phys.

J. Chem. Phys.

J. Chem. Phys.

Faraday Disc. Chem. Soc.

J. Chem. Phys.

J. Chem. Phys.

J. Chem. Phys.

J. Chem. Phys.

Accounts Chem. Res.

Energy randomization in the reactions of F atoms at the carboxyl sites of CH₃COOH and CF₃COOH☆