Reactions of aliphatic free radicals with copper cations in aqueous solutions. Part 3.—Reactions with cuprous ions: a pulse radiolysis study
- 1 January 1980
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases
- Vol. 76, 1838-1848
- https://doi.org/10.1039/f19807601838
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 Cu2+ aq to yield Cu+ aq+ CR1 R2O + H3O+. ·CH2OH radicals react with Cu+ aq according to Cu+ aq+·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. Cu+ aq reacts with the β radicals, ·CH2CH2OH and ·CH2CH(CH3)OH, according to Cu+ aq+·CH2CR1R2OH → CuII—CH2CR1R2OH+. The latter intermediates decompose via acid catalysed reactions to yield Cu2+ aq+ H2CCR1R2+ H2O.Keywords
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