Free radical addition to olefins. Part 4. - The light-induced addition of sulphur chloride pentafluoride to ethylene

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

doi:10.1039/TF9696502103

Free radical addition to olefins. Part 4. - The light-induced addition of sulphur chloride pentafluoride to ethylene

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 ethylene (E) has been studied in a series of gas-phase experiments in which concentration, relative light intensity and temperature have been varied. The results can be rationalized by the following chain mechanism in which the addition step (2) is appreciably reversible in the temperature range studied: SF₅Cl + hv → SF₅· + Cl·(1) SF₅· + E⇌SF₅E·(2), (-2) SF₃E· + SF ₅Cl → SF₅ECl + SF₅·(3) Cl· + E → ECl·(4) ECl· + SF₅Cl → ECl₂ + SF₅·(5) SF₅· + SF₅· → S₂F₁₀ (6) From a series of experiments in which both pressure and temperature were varied the following rate expressions were obtained. k₂/k₆^1/2 = (3.9 ± 0.6) exp (-1,900 ± 200/RT)1.^1/2mole^-1/2 sec ^-1/2,‡ k_-2/k₃ = (118 ± 20) exp(-6,660 ± 300/RT)1.^-1 mole.

Original language	English
Pages (from-to)	2103-2109
Number of pages	7
Journal	Transactions of the Faraday Society
Volume	65
DOIs	https://doi.org/10.1039/TF9696502103
Publication status	Published - 1 Dec 1969

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@article{c6423c6d5dad4ad9b6038975269bb977,

title = "Free radical addition to olefins. Part 4. - The light-induced addition of sulphur chloride pentafluoride to ethylene",

abstract = "The light-induced addition of SF5Cl to ethylene (E) has been studied in a series of gas-phase experiments in which concentration, relative light intensity and temperature have been varied. The results can be rationalized by the following chain mechanism in which the addition step (2) is appreciably reversible in the temperature range studied: SF5Cl + hv → SF5· + Cl·(1) SF5· + E⇌SF5E·(2), (-2) SF3E· + SF 5Cl → SF5ECl + SF5·(3) Cl· + E → ECl·(4) ECl· + SF5Cl → ECl2 + SF5·(5) SF5· + SF5· → S2F10 (6) From a series of experiments in which both pressure and temperature were varied the following rate expressions were obtained. k2/k61/2 = (3.9 ± 0.6) exp (-1,900 ± 200/RT)1.1/2mole-1/2 sec -1/2,‡ k-2/k3 = (118 ± 20) exp(-6,660 ± 300/RT)1.-1 mole.",

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

year = "1969",

month = dec,

day = "1",

doi = "10.1039/TF9696502103",

language = "English",

volume = "65",

pages = "2103--2109",

journal = "Transactions of the Faraday Society",

issn = "0014-7672",

publisher = "Faraday Division of the Chemical Society",

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TY - JOUR

T1 - Free radical addition to olefins. Part 4. - The light-induced addition of sulphur chloride pentafluoride to ethylene

AU - Sidebottom, H. W.

AU - Tedder, J. M.

AU - Walton, J. C.

PY - 1969/12/1

Y1 - 1969/12/1

N2 - The light-induced addition of SF5Cl to ethylene (E) has been studied in a series of gas-phase experiments in which concentration, relative light intensity and temperature have been varied. The results can be rationalized by the following chain mechanism in which the addition step (2) is appreciably reversible in the temperature range studied: SF5Cl + hv → SF5· + Cl·(1) SF5· + E⇌SF5E·(2), (-2) SF3E· + SF 5Cl → SF5ECl + SF5·(3) Cl· + E → ECl·(4) ECl· + SF5Cl → ECl2 + SF5·(5) SF5· + SF5· → S2F10 (6) From a series of experiments in which both pressure and temperature were varied the following rate expressions were obtained. k2/k61/2 = (3.9 ± 0.6) exp (-1,900 ± 200/RT)1.1/2mole-1/2 sec -1/2,‡ k-2/k3 = (118 ± 20) exp(-6,660 ± 300/RT)1.-1 mole.

AB - The light-induced addition of SF5Cl to ethylene (E) has been studied in a series of gas-phase experiments in which concentration, relative light intensity and temperature have been varied. The results can be rationalized by the following chain mechanism in which the addition step (2) is appreciably reversible in the temperature range studied: SF5Cl + hv → SF5· + Cl·(1) SF5· + E⇌SF5E·(2), (-2) SF3E· + SF 5Cl → SF5ECl + SF5·(3) Cl· + E → ECl·(4) ECl· + SF5Cl → ECl2 + SF5·(5) SF5· + SF5· → S2F10 (6) From a series of experiments in which both pressure and temperature were varied the following rate expressions were obtained. k2/k61/2 = (3.9 ± 0.6) exp (-1,900 ± 200/RT)1.1/2mole-1/2 sec -1/2,‡ k-2/k3 = (118 ± 20) exp(-6,660 ± 300/RT)1.-1 mole.

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U2 - 10.1039/TF9696502103

DO - 10.1039/TF9696502103

M3 - Article

AN - SCOPUS:0041868986

SN - 0014-7672

VL - 65

SP - 2103

EP - 2109

JO - Transactions of the Faraday Society

JF - Transactions of the Faraday Society

ER -

Free radical addition to olefins. Part 4. - The light-induced addition of sulphur chloride pentafluoride to ethylene

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