Abstract
Haloalkylperoxyl radicals were produced by radiolytic reduction of haloalkyl iodide or chloride in aerated methanolic solutions. Rate constants for these radicals with alkenes were determined by competition kinetics using chlorpromazine as reference. The rate constant increases with increase in the number of fluorine atoms at C{sub {alpha}} of the peroxyl radical and the effect of fluorine substitution on the rate constant is strong up to {beta}-carbon. A reasonable correlation was obtained between log k and the Taft substituent constants {sigma}{sup *} for each of the radicals. A small change in the reaction constant {rho}{sup *} exhibited by different radicals is taken as an indication that addition to the double predominates over abstraction in the reaction. A probable involvement of charge-transfer in the reaction is also indicated by the Rehm-Weller plot. (author). 3 refs., 1 tab.
Shoute, L C.T.;
[1]
Alfassi, Z B;
[2]
Huie, R E;
Neta, P
[3]
- Bhabha Atomic Research Centre, Bombay (India). Chemistry Div.
- Ben-Gurion Univ. of the Negev, Beersheba (Israel). Dept. of Nuclear Engineering
- National Inst. of Standards and Technology, Gaithersburg (United States). Chemical Kinetics and Thermodynamics Div.
Citation Formats
Shoute, L C.T., Alfassi, Z B, Huie, R E, and Neta, P.
Rate constants for reactions of haloalkylperoxyl radicals with alkenes.
India: N. p.,
1994.
Web.
Shoute, L C.T., Alfassi, Z B, Huie, R E, & Neta, P.
Rate constants for reactions of haloalkylperoxyl radicals with alkenes.
India.
Shoute, L C.T., Alfassi, Z B, Huie, R E, and Neta, P.
1994.
"Rate constants for reactions of haloalkylperoxyl radicals with alkenes."
India.
@misc{etde_100358,
title = {Rate constants for reactions of haloalkylperoxyl radicals with alkenes}
author = {Shoute, L C.T., Alfassi, Z B, Huie, R E, and Neta, P}
abstractNote = {Haloalkylperoxyl radicals were produced by radiolytic reduction of haloalkyl iodide or chloride in aerated methanolic solutions. Rate constants for these radicals with alkenes were determined by competition kinetics using chlorpromazine as reference. The rate constant increases with increase in the number of fluorine atoms at C{sub {alpha}} of the peroxyl radical and the effect of fluorine substitution on the rate constant is strong up to {beta}-carbon. A reasonable correlation was obtained between log k and the Taft substituent constants {sigma}{sup *} for each of the radicals. A small change in the reaction constant {rho}{sup *} exhibited by different radicals is taken as an indication that addition to the double predominates over abstraction in the reaction. A probable involvement of charge-transfer in the reaction is also indicated by the Rehm-Weller plot. (author). 3 refs., 1 tab.}
place = {India}
year = {1994}
month = {Dec}
}
title = {Rate constants for reactions of haloalkylperoxyl radicals with alkenes}
author = {Shoute, L C.T., Alfassi, Z B, Huie, R E, and Neta, P}
abstractNote = {Haloalkylperoxyl radicals were produced by radiolytic reduction of haloalkyl iodide or chloride in aerated methanolic solutions. Rate constants for these radicals with alkenes were determined by competition kinetics using chlorpromazine as reference. The rate constant increases with increase in the number of fluorine atoms at C{sub {alpha}} of the peroxyl radical and the effect of fluorine substitution on the rate constant is strong up to {beta}-carbon. A reasonable correlation was obtained between log k and the Taft substituent constants {sigma}{sup *} for each of the radicals. A small change in the reaction constant {rho}{sup *} exhibited by different radicals is taken as an indication that addition to the double predominates over abstraction in the reaction. A probable involvement of charge-transfer in the reaction is also indicated by the Rehm-Weller plot. (author). 3 refs., 1 tab.}
place = {India}
year = {1994}
month = {Dec}
}