Chain branching in the fluorine-hydrogen reaction

Kapralova, G. A.; Trofimova, E. M.; Chaikin, A. M.

doi:10.1007/bf02342579

Cited by 12 publications

(16 citation statements)

References 7 publications

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“…Although there have been quite a number of experimental [2][3][4][5][6][7][8][9][10][11] and theoretical [12][13][14][15][16][17][18][19] investigations on the reaction of fluorine with ethylene, the reaction mechanism remains unclear. If this simple reaction can be understood, the mechanism may be extended to larger systems.…”

Section: Dynamics Of the F 2 Reaction With The Simplest -Bonding Molementioning

confidence: 99%

“…If this simple reaction can be understood, the mechanism may be extended to larger systems. [2][3][4] The released F atom can initiate a series of exothermic chain reactions, which may lead to explosion. Definitive experimental results of this reaction are also extremely desirable as to provide a test of the theories.…”

Section: Dynamics Of the F 2 Reaction With The Simplest -Bonding Molementioning

confidence: 99%

“…Due to the small number of participating atoms, it should be feasible to study this reaction with high level ab initio calculations to reach a precision of the socalled chemical accuracy. Kapralova et al 2 reported the temperature dependence for R1 and showed the rate constant of reaction ͑1͒ can be expressed as follows: k l = 8.0 ϫ 10 −14 exp͑− E a /RT͒ cm 3 molecule -1 s −1 , and E a = 4.6 kcal/mol. Although there have been quite a number of experimental [2][3][4][5][6][7][8][9][10][11] and theoretical [12][13][14][15][16][17][18][19] investigations on the reaction of fluorine with ethylene, the reaction mechanism remains unclear.…”

Section: Dynamics Of the F 2 Reaction With The Simplest -Bonding Molementioning

confidence: 99%

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Dynamics of the F2 reaction with the simplest π-bonding molecule

Xie

Fang

Shao

et al. 2008

The Journal of Chemical Physics

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The reaction of F(2)+C(2)H(4) has been investigated with crossed molecular beam experiments and high level ab initio calculations. For a wide range of collision energies up to 11 kcal/mol, only one reaction channel could be observed in the gas phase. The primary products of this channel were identified as F+CH(2)CH(2)F. The experimental reaction threshold of collision energy was determined to be 5.5+/-0.5 kcal/mol. The product angular distribution was found to be strongly backward, indicating that the reaction time scale is substantially shorter than rotation. The calculated transition state structure suggests an early barrier; such dynamics is consistent with the small product kinetic energy release measured in the experiment. All experimental results consistently support a rebound reaction mechanism, which is suggested by the calculation of the intrinsic reaction coordinate. This work provides a clear and unambiguous description of the reaction dynamics, which may help to answer the question why the same reaction produces totally different products in the condensed phase.

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Section: Dynamics Of the F 2 Reaction With The Simplest -Bonding Molementioning

confidence: 99%

Section: Dynamics Of the F 2 Reaction With The Simplest -Bonding Molementioning

confidence: 99%

Section: Dynamics Of the F 2 Reaction With The Simplest -Bonding Molementioning

confidence: 99%

See 1 more Smart Citation

Dynamics of the F2 reaction with the simplest π-bonding molecule

Xie

Fang

Shao

et al. 2008

The Journal of Chemical Physics

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“…13 The dominant reaction channel begins with formation of the -fluoroethyl radical (CH 2 CH 2 F) intermediate with about 50 kcal/mol of excess energy:…”

Section: Introductionmentioning

confidence: 99%

Formation of β-Fluoroethyl Radical and Closed-Shell Products in Reactions of Photogenerated Fluorine Atoms with Ethene in Solid Argon

1996

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Solid-state reactions of F atoms with ethene molecules were initiated by UV photolysis of dilute solutions of F 2 and C 2 H 4 in solid Ar. Products stabilized in the matrix were detected by infrared spectroscopy. Experiments were conducted at different temperatures in order to distinguish reactions in matrix-isolated F 2 -C 2 H 4 complexes (at 16 K) from reactions of diffusing thermal F atoms (at 26 K). Comparison with the kinetic EPR data (Benderskii, V. A. et al. MendeleeV Commun. 1995, 6, 245) permitted the identification of the infrared spectrum of the β-fluoroethyl radical, which is the main product of the F + C 2 H 4 reaction. Frequencies and absolute absorption intensities of the eight strongest infrared bands of β-C 2 H 4 F are reported. Photolysis of isolated F 2 -C 2 H 4 complexes forms the closed-shell products C 2 H 3 F-HF and trans-and gauche-1,2-C 2 H 4 F 2 with relative yields 0.6:0.2:0.2. Successive addition of two thermal F atoms to an isolated C 2 H 4 molecule forms only the two conformers of 1,2-C 2 H 4 F 2 . The difference between product branching ratios of the latter reaction and the direct photoinduced reaction of F 2 -C 2 H 4 complexes is qualitatively explained by the difference in size of the reaction cages and excess energies of the vibrationally excited intermediate (C 2 H 4 F 2 )*.

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“…This paper is devoted to the study of fluorovinyl radicals formed in the reactions of mobile F atoms with C 2 H 2 molecules. In the gas phase, this reaction leads to the formation of two types of products: [1] It was determined that the dominant channel is the formation of 2-C 2 H 2 F radical (9,10). There are two isomers of this radical, which differ in the location of the F atom with respect to the orbital of unpaired electron:…”

Section: Introductionmentioning

confidence: 99%