OH radical induced oxidation of ethanol in oxygenated aqueous solutions. Part 1.—Formation of acetic acid
- 1 January 1975
- 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. 71, 1099-1105
- https://doi.org/10.1039/f19757101099
Abstract
γ-Irradiation of ethanol (10–2 mol dm3) in aqueous N2O + O2(4 : 1) saturated solution (pH = 6.8) at 0°C leads to the following products (G-values): acetaldehyde (4.0), acetic acid (1.5), glycolaldehyde (0.2), ethylene glycol (0.2), and hydrogen peroxide (1.9). The G-values of acetaldehyde and acetic acid were determined as a function of ethanol concentration, pH, temperature and dose rate. G(acetic acid) decreases with increasing temperature and pH, and increases with dose rate. The ethanol concentration in the range of 10–3 to 1 mol dm–3 has no influence on the G-value. The sum of G(acetic acid) and G(acetaldehyde) is always about 6. At pH = 6.8 a long lived peroxidic intermediate A is observed with a half life of approximately 800 s at 0°C. A is assumed to be 1-hydroxyethyl hydroperoxide (ethanol hydroperoxide). The only source of acetic acid is the proton catalysed decomposition of A at pH > 3. At low dose rate, A is formed with low yield because the 1-hydroxyethylperoxyl radical decomposes into acetaldehyde and H2O2 without forming A.Keywords
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