Abstract
The reactions between AgII and acetic, propionic, n-butyric, isobutyric, and pivalic acids have been investigated kinetically, at 14.0, 22.0, and 30.0 °C, in aqueous perchloric acid media (1.00 ⩽[HClO4]⩽ 4.00M; µ= 4.0M) by a stopped-flow technique. The overall reaction is: 2AgII+ RCO2H → 2AgI+ 2H++ CO2+ products. The reactions are second order and the rate constants increase with decreasing acidity. Alternative mechanisms for acid-dependent pathways are considered. The rate-determining step involves electron exchange with R–CO2H bond rupture. Two pathways were found to operate and their reactivities correlate with the σ* values of the Taft equation. The results are discussed with reference to previous findings concerning AgII oxidation of formic acid.
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