Electron transfer reactions of halogenated aliphatic peroxyl radicals

Measurement of absolute rate constants by pulse radiolysis

authored by

John E. Packer, Robin L. Willson, Detlef Bahnemann, Klaus Dieter Asmus

Abstract

The peroxyl radicals Cl₃COO·, Cl₂CHOO·, ClCH₄OO·, CH₃OO; ·OOCCl₂CO ₂^-. ·OOCHClCO₂^-, ·OOCH₂CO₂^-, ·QOCF ₂CO₂^-, and (CH₃)₂C(OH) CH₂OO· have been generated in aqueous alcohol solutions by pulse radiolysis using the Brunei and Hahn-Meitner accelerators. The absolute rate constants of the one-electron transfer reactions of related aliphatic peroxyl radicals with ascorbate, promethazine, phenol, and tyrosine have been found to increase with increasing substitution of chlorine atoms. For the reaction of the radical Cl₃CO₂· and promethazine, at pH 6, k 6.0 ± 0.4 × 10⁸ l mol^-1 s ^-1 has been measured. For the analogous reaction of the radical ClCH₂O₂·, k 3.3 ± 0.2 × 10⁷ l mol^-1 s^-1 has been determined.

External Organisation(s)

Brunel University
Helmholtz-Zentrum Berlin für Materialien und Energie (HZB)

Type

Article

Journal

Journal of the Chemical Society, Perkin Transactions 2

Pages

296-299

No. of pages

4

ISSN

1472-779X

Publication date

1980

Publication status

Published

Peer reviewed

Yes

ASJC Scopus subject areas

General Chemistry

Electronic version(s)

https://doi.org/10.1039/p29800000296 (Access: Unknown)