Free radical addition to olefins. Part 6. - Addition of sulphur chloride pentafluoride to fluoro-olefins

H. W. Sidebottom; J. M. Tedder; J. C. Walton

doi:10.1039/TF9706602038

Free radical addition to olefins. Part 6. - Addition of sulphur chloride pentafluoride to fluoro-olefins

H. W. Sidebottom^*, J. M. Tedder, J. C. Walton

^*Corresponding author for this work

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Abstract

The light-induced addition of SF₅Cl to fluoro-olefins (E) has been studied in a large series of experiments in which light intensity, temperature and relative concentrations have been varied. The reaction mechanism is the same as that established for ethylene with the following principal chain carrying steps: SF₅·+E⇌_k-2 ^k2SF₅E· SF₅E·+SF ₅Cl→^k3SF₅ECl+SF₅·, and the combination of two SF₅· radicals (k₆) the main chain termination step. The addition to tetrafluoro-, trifluoro- and 1,1-difluoro-ethylene has been investigated and from studies on the latter two compounds the following rate expressions were obtained. (SF₅ECl) log (A₂/A₆^1/2) (1.^1/2 mol^-1/2 s^-1/2) E₂-1/2E₆ (kcal mol^-1) log (A_-2/A₃) (1.^-1 mol) E_-2-E ₃ (kcal mol^-1) SF₅CH₂CF ₂Cl 0.62±0.05 2.0±0.1 4.5±0.5 12.7±1.0 SF₅CHFCF₂Cl 1.40±0.08 3.4±0.2 3.5±0.3 8.4±1.0 * R the gas constant taken to be 1.9872 cal deg. ^-1 mol^-1 and subsequent energies expressed in cal mol ^-1 (1 cal=4.1855 J).

Original language	English
Pages (from-to)	2038-2044
Number of pages	7
Journal	Transactions of the Faraday Society
Volume	66
DOIs	https://doi.org/10.1039/TF9706602038
Publication status	Published - 1 Jan 1970

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@article{9e31d98b9823413b9a789dad656affee,

title = "Free radical addition to olefins. Part 6. - Addition of sulphur chloride pentafluoride to fluoro-olefins",

abstract = "The light-induced addition of SF5Cl to fluoro-olefins (E) has been studied in a large series of experiments in which light intensity, temperature and relative concentrations have been varied. The reaction mechanism is the same as that established for ethylene with the following principal chain carrying steps: SF5·+E⇌k-2 k2SF5E· SF5E·+SF 5Cl→k3SF5ECl+SF5·, and the combination of two SF5· radicals (k6) the main chain termination step. The addition to tetrafluoro-, trifluoro- and 1,1-difluoro-ethylene has been investigated and from studies on the latter two compounds the following rate expressions were obtained. (SF5ECl) log (A2/A61/2) (1.1/2 mol-1/2 s-1/2) E2-1/2E6 (kcal mol-1) log (A-2/A3) (1.-1 mol) E-2-E 3 (kcal mol-1) SF5CH2CF 2Cl 0.62±0.05 2.0±0.1 4.5±0.5 12.7±1.0 SF5CHFCF2Cl 1.40±0.08 3.4±0.2 3.5±0.3 8.4±1.0 * R the gas constant taken to be 1.9872 cal deg. -1 mol-1 and subsequent energies expressed in cal mol -1 (1 cal=4.1855 J).",

author = "Sidebottom, {H. W.} and Tedder, {J. M.} and Walton, {J. C.}",

year = "1970",

month = jan,

day = "1",

doi = "10.1039/TF9706602038",

language = "English",

volume = "66",

pages = "2038--2044",

journal = "Transactions of the Faraday Society",

issn = "0014-7672",

publisher = "Faraday Division of the Chemical Society",

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T1 - Free radical addition to olefins. Part 6. - Addition of sulphur chloride pentafluoride to fluoro-olefins

AU - Sidebottom, H. W.

AU - Tedder, J. M.

AU - Walton, J. C.

PY - 1970/1/1

Y1 - 1970/1/1

N2 - The light-induced addition of SF5Cl to fluoro-olefins (E) has been studied in a large series of experiments in which light intensity, temperature and relative concentrations have been varied. The reaction mechanism is the same as that established for ethylene with the following principal chain carrying steps: SF5·+E⇌k-2 k2SF5E· SF5E·+SF 5Cl→k3SF5ECl+SF5·, and the combination of two SF5· radicals (k6) the main chain termination step. The addition to tetrafluoro-, trifluoro- and 1,1-difluoro-ethylene has been investigated and from studies on the latter two compounds the following rate expressions were obtained. (SF5ECl) log (A2/A61/2) (1.1/2 mol-1/2 s-1/2) E2-1/2E6 (kcal mol-1) log (A-2/A3) (1.-1 mol) E-2-E 3 (kcal mol-1) SF5CH2CF 2Cl 0.62±0.05 2.0±0.1 4.5±0.5 12.7±1.0 SF5CHFCF2Cl 1.40±0.08 3.4±0.2 3.5±0.3 8.4±1.0 * R the gas constant taken to be 1.9872 cal deg. -1 mol-1 and subsequent energies expressed in cal mol -1 (1 cal=4.1855 J).

AB - The light-induced addition of SF5Cl to fluoro-olefins (E) has been studied in a large series of experiments in which light intensity, temperature and relative concentrations have been varied. The reaction mechanism is the same as that established for ethylene with the following principal chain carrying steps: SF5·+E⇌k-2 k2SF5E· SF5E·+SF 5Cl→k3SF5ECl+SF5·, and the combination of two SF5· radicals (k6) the main chain termination step. The addition to tetrafluoro-, trifluoro- and 1,1-difluoro-ethylene has been investigated and from studies on the latter two compounds the following rate expressions were obtained. (SF5ECl) log (A2/A61/2) (1.1/2 mol-1/2 s-1/2) E2-1/2E6 (kcal mol-1) log (A-2/A3) (1.-1 mol) E-2-E 3 (kcal mol-1) SF5CH2CF 2Cl 0.62±0.05 2.0±0.1 4.5±0.5 12.7±1.0 SF5CHFCF2Cl 1.40±0.08 3.4±0.2 3.5±0.3 8.4±1.0 * R the gas constant taken to be 1.9872 cal deg. -1 mol-1 and subsequent energies expressed in cal mol -1 (1 cal=4.1855 J).

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JO - Transactions of the Faraday Society

JF - Transactions of the Faraday Society

ER -

Free radical addition to olefins. Part 6. - Addition of sulphur chloride pentafluoride to fluoro-olefins

Abstract

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