Free radical addition to olefins. Part 19.-Trifluoromethyl radical addition to fluoro-substituted propenes and its absolute rate of addition to ethylene

Hamish C. Low; John M. Tedder; John C. Walton

doi:10.1039/F19767201300

Free radical addition to olefins. Part 19.-Trifluoromethyl radical addition to fluoro-substituted propenes and its absolute rate of addition to ethylene

Hamish C. Low, John M. Tedder, John C. Walton^*

^*Corresponding author for this work

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Abstract

The rates of addition of trifluoromethyl radicals to each end of propene, 1,1,1-trifluoropropene and hexafluoropropene have been determined using a competitive technique, taking as a standard the rate of addition to ethylene. The rate of addition of trifluoromethyl radicals to ethylene (2) has been compared with the rate of combination of trifluoromethyl radicals (6), and a value of k₂/k₆^1/2 = (1.6 ± 0.2) × 10³ exp (-2 900 ± 500 cal mol^-1/RT) dm ^3/2 mol^-1/2 s^-1/2 was determined (1 cal = 4.184 J). CF₃·+CH₂=CH₂→k2 CF ₃CH₂CH₂· (2) CF₃· +CF₃·→k6 C₂F₆. (6) Since the value of k₆ is now well established, a new value of the absolute rate of addition of trifluoromethyl radicals to ethylene and to the other olefins can be computed.

Original language	English
Pages (from-to)	1300-1309
Number of pages	10
Journal	Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases
Volume	72
DOIs	https://doi.org/10.1039/F19767201300
Publication status	Published - 1 Dec 1976

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title = "Free radical addition to olefins. Part 19.-Trifluoromethyl radical addition to fluoro-substituted propenes and its absolute rate of addition to ethylene",

abstract = "The rates of addition of trifluoromethyl radicals to each end of propene, 1,1,1-trifluoropropene and hexafluoropropene have been determined using a competitive technique, taking as a standard the rate of addition to ethylene. The rate of addition of trifluoromethyl radicals to ethylene (2) has been compared with the rate of combination of trifluoromethyl radicals (6), and a value of k2/k61/2 = (1.6 ± 0.2) × 103 exp (-2 900 ± 500 cal mol-1/RT) dm 3/2 mol-1/2 s-1/2 was determined (1 cal = 4.184 J). CF3·+CH2=CH2→k2 CF 3CH2CH2· (2) CF3· +CF3·→k6 C2F6. (6) Since the value of k6 is now well established, a new value of the absolute rate of addition of trifluoromethyl radicals to ethylene and to the other olefins can be computed.",

author = "Low, {Hamish C.} and Tedder, {John M.} and Walton, {John C.}",

year = "1976",

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doi = "10.1039/F19767201300",

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journal = "Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases",

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Free radical addition to olefins. Part 19.-Trifluoromethyl radical addition to fluoro-substituted propenes and its absolute rate of addition to ethylene. / Low, Hamish C.; Tedder, John M.; Walton, John C.
In: Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, Vol. 72, 01.12.1976, p. 1300-1309.

Research output: Contribution to journal › Article › peer-review

TY - JOUR

T1 - Free radical addition to olefins. Part 19.-Trifluoromethyl radical addition to fluoro-substituted propenes and its absolute rate of addition to ethylene

AU - Low, Hamish C.

AU - Tedder, John M.

AU - Walton, John C.

PY - 1976/12/1

Y1 - 1976/12/1

N2 - The rates of addition of trifluoromethyl radicals to each end of propene, 1,1,1-trifluoropropene and hexafluoropropene have been determined using a competitive technique, taking as a standard the rate of addition to ethylene. The rate of addition of trifluoromethyl radicals to ethylene (2) has been compared with the rate of combination of trifluoromethyl radicals (6), and a value of k2/k61/2 = (1.6 ± 0.2) × 103 exp (-2 900 ± 500 cal mol-1/RT) dm 3/2 mol-1/2 s-1/2 was determined (1 cal = 4.184 J). CF3·+CH2=CH2→k2 CF 3CH2CH2· (2) CF3· +CF3·→k6 C2F6. (6) Since the value of k6 is now well established, a new value of the absolute rate of addition of trifluoromethyl radicals to ethylene and to the other olefins can be computed.

AB - The rates of addition of trifluoromethyl radicals to each end of propene, 1,1,1-trifluoropropene and hexafluoropropene have been determined using a competitive technique, taking as a standard the rate of addition to ethylene. The rate of addition of trifluoromethyl radicals to ethylene (2) has been compared with the rate of combination of trifluoromethyl radicals (6), and a value of k2/k61/2 = (1.6 ± 0.2) × 103 exp (-2 900 ± 500 cal mol-1/RT) dm 3/2 mol-1/2 s-1/2 was determined (1 cal = 4.184 J). CF3·+CH2=CH2→k2 CF 3CH2CH2· (2) CF3· +CF3·→k6 C2F6. (6) Since the value of k6 is now well established, a new value of the absolute rate of addition of trifluoromethyl radicals to ethylene and to the other olefins can be computed.

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JF - Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases

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Free radical addition to olefins. Part 19.-Trifluoromethyl radical addition to fluoro-substituted propenes and its absolute rate of addition to ethylene

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