Halogenated alkylperoxyl radicals as oxidants: Effects of solvents and of substituents on rates of electron transfer

Zeev B. Alfassi; S. Mosseri; P. Neta

doi:10.1021/j100296a056

Halogenated alkylperoxyl radicals as oxidants: Effects of solvents and of substituents on rates of electron transfer

Zeev B. Alfassi, S. Mosseri, P. Neta

Unit of Nuclear Engineering

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

40 Scopus citations

Abstract

The peroxyl radicals CCl₃Ȯ₂, CHCl₂Ȯ₂, CH₂ClȮ₂, CCl₃CCl₂Ȯ₂, CFCl₂Ȯ₂, CH₃CCl₂Ȯ₂, CF₃CHClȮ₂, and CBr₃Ȯ₂ were produced by pulse radiolysis of aerated solutions of the appropriate halogen compound in 2-propanol or 2-propanol-water solutions. Rate constants for one-electron oxidation of chloropromazine by these radicals were determined by kinetic spectrophotometry in various solvent mixtures. The second-order rate constants were found to vary from 1 × 10⁵ to 1 × 10⁹ M^-1 s^-1. They depend very strongly on the solvent polarity and a reasonable correlation is obtained between log k for a certain peroxyl radical and the dielectric constant of the solvent mixture. The rate constants in the same solvent are strongly dependent of the substituents on the methylperoxyl radical and give a good correlation with the polar substituent constants σ*.

Original language	English
Pages (from-to)	3383-3385
Number of pages	3
Journal	Journal of Physical Chemistry
Volume	91
Issue number	12
DOIs	https://doi.org/10.1021/j100296a056
State	Published - 1 Jan 1987

ASJC Scopus subject areas

General Engineering
Physical and Theoretical Chemistry

Access to Document

10.1021/j100296a056

Cite this

@article{75c02330eb7e492caf2dac13e1c949c2,

title = "Halogenated alkylperoxyl radicals as oxidants: Effects of solvents and of substituents on rates of electron transfer",

abstract = "The peroxyl radicals CCl3Ȯ2, CHCl2Ȯ2, CH2ClȮ2, CCl3CCl2Ȯ2, CFCl2Ȯ2, CH3CCl2Ȯ2, CF3CHClȮ2, and CBr3Ȯ2 were produced by pulse radiolysis of aerated solutions of the appropriate halogen compound in 2-propanol or 2-propanol-water solutions. Rate constants for one-electron oxidation of chloropromazine by these radicals were determined by kinetic spectrophotometry in various solvent mixtures. The second-order rate constants were found to vary from 1 × 105 to 1 × 109 M-1 s-1. They depend very strongly on the solvent polarity and a reasonable correlation is obtained between log k for a certain peroxyl radical and the dielectric constant of the solvent mixture. The rate constants in the same solvent are strongly dependent of the substituents on the methylperoxyl radical and give a good correlation with the polar substituent constants σ*.",

author = "Alfassi, {Zeev B.} and S. Mosseri and P. Neta",

year = "1987",

month = jan,

day = "1",

doi = "10.1021/j100296a056",

language = "English",

volume = "91",

pages = "3383--3385",

journal = "Journal of Physical Chemistry",

issn = "0022-3654",

publisher = "American Chemical Society",

number = "12",

}

TY - JOUR

T1 - Halogenated alkylperoxyl radicals as oxidants

T2 - Effects of solvents and of substituents on rates of electron transfer

AU - Alfassi, Zeev B.

AU - Mosseri, S.

AU - Neta, P.

PY - 1987/1/1

Y1 - 1987/1/1

N2 - The peroxyl radicals CCl3Ȯ2, CHCl2Ȯ2, CH2ClȮ2, CCl3CCl2Ȯ2, CFCl2Ȯ2, CH3CCl2Ȯ2, CF3CHClȮ2, and CBr3Ȯ2 were produced by pulse radiolysis of aerated solutions of the appropriate halogen compound in 2-propanol or 2-propanol-water solutions. Rate constants for one-electron oxidation of chloropromazine by these radicals were determined by kinetic spectrophotometry in various solvent mixtures. The second-order rate constants were found to vary from 1 × 105 to 1 × 109 M-1 s-1. They depend very strongly on the solvent polarity and a reasonable correlation is obtained between log k for a certain peroxyl radical and the dielectric constant of the solvent mixture. The rate constants in the same solvent are strongly dependent of the substituents on the methylperoxyl radical and give a good correlation with the polar substituent constants σ*.

AB - The peroxyl radicals CCl3Ȯ2, CHCl2Ȯ2, CH2ClȮ2, CCl3CCl2Ȯ2, CFCl2Ȯ2, CH3CCl2Ȯ2, CF3CHClȮ2, and CBr3Ȯ2 were produced by pulse radiolysis of aerated solutions of the appropriate halogen compound in 2-propanol or 2-propanol-water solutions. Rate constants for one-electron oxidation of chloropromazine by these radicals were determined by kinetic spectrophotometry in various solvent mixtures. The second-order rate constants were found to vary from 1 × 105 to 1 × 109 M-1 s-1. They depend very strongly on the solvent polarity and a reasonable correlation is obtained between log k for a certain peroxyl radical and the dielectric constant of the solvent mixture. The rate constants in the same solvent are strongly dependent of the substituents on the methylperoxyl radical and give a good correlation with the polar substituent constants σ*.

UR - http://www.scopus.com/inward/record.url?scp=33845281195&partnerID=8YFLogxK

U2 - 10.1021/j100296a056

DO - 10.1021/j100296a056

M3 - Article

AN - SCOPUS:33845281195

SN - 0022-3654

VL - 91

SP - 3383

EP - 3385

JO - Journal of Physical Chemistry

JF - Journal of Physical Chemistry

IS - 12

ER -

Halogenated alkylperoxyl radicals as oxidants: Effects of solvents and of substituents on rates of electron transfer

Abstract

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Cite this