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Rate constants for reactions of haloalkylperoxyl radicals with alkenes

Conference:

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.
Authors:
Shoute, L C.T.; [1]  Alfassi, Z B; [2]  Huie, R E; Neta, P [3] 
  1. Bhabha Atomic Research Centre, Bombay (India). Chemistry Div.
  2. Ben-Gurion Univ. of the Negev, Beersheba (Israel). Dept. of Nuclear Engineering
  3. National Inst. of Standards and Technology, Gaithersburg (United States). Chemical Kinetics and Thermodynamics Div.
Publication Date:
Dec 31, 1994
Product Type:
Conference
Report Number:
CONF-9401116-
Reference Number:
SCA: 400600; PA: AIX-26:062481; EDB-95:131103; SN: 95001457651
Resource Relation:
Conference: TRSP-94: Trombay symposium on radiation and photochemistry, Bombay (India), 17-21 Jan 1994; Other Information: PBD: 1994; Related Information: Is Part Of Trombay symposium on radiation and photochemistry. Preprints vol.2: contributed papers; PB: 407 p.
Subject:
40 CHEMISTRY; FREONS; RADIOLYSIS; ALKENES; CHEMICAL REACTION KINETICS; PEROXY RADICALS; PULSED IRRADIATION
OSTI ID:
100358
Research Organizations:
Department of Atomic Energy, Bombay (India). Board of Research in Nuclear Sciences
Country of Origin:
India
Language:
English
Other Identifying Numbers:
TRN: IN9501077062481
Submitting Site:
INIS
Size:
pp. 1-3
Announcement Date:
Jan 16, 2004

Conference:

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}
}