International Journal of Chemical Kinetics

Volume 25, Issue 11 pp. 913-920

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Rate constants for the addition of the 2-hydroxy-2-propyl radical to alkenes in solution

K. Héberger,

K. Héberger

Physikalisch-Chemisches Institut der Universität Zürich, CH-8057 Zürich, Winterthurerstrasse 190

Central Research Institute for Chemistry of the Hungarian Academy of Sciences, P.O. Box 17, H-1525 Budapest.

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H. Fischer,

Corresponding Author

H. Fischer

Physikalisch-Chemisches Institut der Universität Zürich, CH-8057 Zürich, Winterthurerstrasse 190

Physikalisch-Chemisches Institut der Universität Zürich, CH-8057 Zürich, Winterthurerstrasse 190Search for more papers by this author

K. Héberger,

K. Héberger

Physikalisch-Chemisches Institut der Universität Zürich, CH-8057 Zürich, Winterthurerstrasse 190

Central Research Institute for Chemistry of the Hungarian Academy of Sciences, P.O. Box 17, H-1525 Budapest.

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H. Fischer,

Corresponding Author

H. Fischer

Physikalisch-Chemisches Institut der Universität Zürich, CH-8057 Zürich, Winterthurerstrasse 190

Physikalisch-Chemisches Institut der Universität Zürich, CH-8057 Zürich, Winterthurerstrasse 190Search for more papers by this author

First published: November 1993

https://doi.org/10.1002/kin.550251105

Citations: 43

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Abstract

Absolute rate constants for the addition of the 2-hydroxy-2-propyl radical to 18 substituted alkenes (CH₂ = CXY) were determined at (296 ± 1) K in 2-propanol by time-resolved electronspin-resonance spectroscopy. With alkene substitution the rate constants vary by more than 6 orders of magnitude. For 3,3-dimethyl-but-1-ene the temperature dependence is given by log k/M⁻¹ · s⁻¹ = 6.4 minus;; 19.1/Θ where Θ = 2.303 RT in kJ/mol⁻¹. As shown by a good correlation with the alkene electron affinities, log k₂₉₆/M⁻¹ · s⁻¹ = 6.46 + 1.71 · EA/eV (r = 0.930), 2-hydroxy-2-propyl is a very nucleophilic radical, and its addition rates are highly governed by polar effects. © 1993 John Wiley & Sons, Inc.

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Volume25, Issue11

November 1993

Pages 913-920

Rate constants for the addition of the 2-hydroxy-2-propyl radical to alkenes in solution

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Rate constants for the addition of the 2-hydroxy-2-propyl radical to alkenes in solution

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