Reactions of aliphatic free radicals with copper cations in aqueous solutions. Part 3. - Reactions with cuprous ions: A pulse radiolysis study

Mira Freiberg, William A. Mulac, Klaus H. Schmidt, Dan Meyerstein

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59 Scopus citations

Abstract

Helium-saturated solutions containing copper sulphate and an aliphatic alcohol (methanol, ethanol or propan-2-ol) were pulse irradiated. The kinetics of the reactions thus initiated were followed by the spectrophotometric and conductometric techniques. The results indicate that all three radicals, ·CR1R2OH, react with Cuaq2+ to yield Cuaq+ + CR1 R2O + H3O+. ·CH2OH radicals react with Cuaq2+ according to Cuaq+ + ·CH2OH ⇄ CuII-CH2OH+, K ≈ 5 × 103 dm3 mol-1. The corresponding equilibrium constants for CuII-CH(CH3)OH+ and CuII-C(CH3)2OH+ are too low to be measured and the corresponding intermediates are not observed. Cuaq+ reacts with the β radicals, ·CH2CH2OH and ·CH2CH(CH3)OH, according to Cuaq2+ + ·CH2CR1R2OH → CuII-CH2CR1R2OH+. The latter intermediates decompose via acid catalysed reactions to yield Cuaq2+ + H2C=CR1R2 + H2O.

Original languageEnglish
Pages (from-to)1838-1848
Number of pages11
JournalPhysical Chemistry Chemical Physics
Volume76
DOIs
StatePublished - 1 Dec 1980

ASJC Scopus subject areas

  • Chemistry (all)

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