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Title: Hydroxyl radical induced oxidation of diethyl ether in oxygenated aqueous solution. A product and pulse radiolysis study. [Gamma radiation]

Abstract

The reactions of peroxyl radicals derived from diethyl ether were investigated by product analyses and pulse-radiolytic techniques. The products and their G values (in brackets) in the ..gamma.. radiolysis of diethyl ether (10/sup -3/ M) in N/sub 2/O/O/sub 2/-saturated aqueous solutions at 0.43 W kg/sup -1/ are acetaldehyde (0.6), ethanol (0.6), ethyl acetate (2.8), ethyl formate (0.7), formaldehyde (0.4), hydrogen peroxide (2.1), 1-ethoxyethyl hydroperoxide (1.2), and 2-ethoxyacetaldehyde (approx. 0.5). Except for the latter, all products have the 1-ethoxyethylperoxy radical (I) as a precursor. It is formed as the major radical by OH abstraction of the ..cap alpha..-H atom (96%) followed by O/sub 2/ addition. Besides other bimolecular decay processes of I which are also discussed, there is an important route leading to 1-ethoxyethyloxyl radicals and O/sub 2/: 2I ..-->.. 2CH/sub 3/CH(O)OEt + O/sub 2/. The oxyl radical rearranges in aqueous solutions to the 1-ethoxy-1-hydroxyethyl radical: CH/sub 3/CH(O)OEt ..-->.. CH/sub 3/C(OH)OEt. The latter adds oxygen to give the corresponding peroxyl radical, which eliminates HO/sub 2/. in a fast spontaneous reaction to give ethyl acetate: CH/sub 3/C(OH)OEt + O/sub 2/ - HO/sub 2/. ..-->.. CH/sub 3/COOEt. Evidence for the formation of HO/sub 2/. (O/sub 2//sup -/. in neutral and basic solutions) accordingmore » to the above reaction sequence was provided by pulse-spectrometric and pulse-conductometric measurements. 1-Ethoxyethyl hydroperoxide is thought to result from the reduction of I by O/sub 2//sup -/.. At much lower dose rates (0.0048 W kg/sup -1/) an intramolecular H abstraction competes with the bimolecular decay of I. This process leads to a different product distribution and to the formation of acidic products.« less

Authors:
;
Publication Date:
Research Org.:
Max-Planck-Institut fuer Strahlenchemie, Ruhr, Germany
OSTI Identifier:
6846999
Resource Type:
Journal Article
Journal Name:
J. Phys. Chem.; (United States)
Additional Journal Information:
Journal Volume: 86:11
Country of Publication:
United States
Language:
English
Subject:
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY; ACETALDEHYDE; G VALUE; ACETIC ACID ESTERS; CARBOXYLIC ACID ESTERS; ETHANOL; ETHYL ETHER; OXIDATION; RADIOLYSIS; FORMALDEHYDE; HYDROGEN PEROXIDE; PEROXIDES; AQUEOUS SOLUTIONS; CHEMICAL REACTION KINETICS; EXPERIMENTAL DATA; GAMMA RADIATION; HYDROXYL RADICALS; NITROUS OXIDE; OXYGEN; PEROXY RADICALS; PH VALUE; PULSED IRRADIATION; RADIATION DOSES; REACTION INTERMEDIATES; ALCOHOLS; ALDEHYDES; CHALCOGENIDES; CHEMICAL RADIATION EFFECTS; CHEMICAL REACTIONS; CHEMISTRY; DATA; DECOMPOSITION; DISPERSIONS; DOSES; ELECTROMAGNETIC RADIATION; ELEMENTS; ESTERS; ETHERS; HYDROGEN COMPOUNDS; HYDROXY COMPOUNDS; INFORMATION; IONIZING RADIATIONS; IRRADIATION; KINETICS; MIXTURES; NITROGEN COMPOUNDS; NITROGEN OXIDES; NONMETALS; NUMERICAL DATA; ORGANIC COMPOUNDS; ORGANIC OXYGEN COMPOUNDS; OXIDES; OXYGEN COMPOUNDS; RADIATION CHEMISTRY; RADIATION EFFECTS; RADIATIONS; RADICALS; REACTION KINETICS; SOLUTIONS; 400600* - Radiation Chemistry

Citation Formats

Schuchmann, M N, and von Sonntag, C. Hydroxyl radical induced oxidation of diethyl ether in oxygenated aqueous solution. A product and pulse radiolysis study. [Gamma radiation]. United States: N. p., 1982. Web. doi:10.1021/j100208a017.
Schuchmann, M N, & von Sonntag, C. Hydroxyl radical induced oxidation of diethyl ether in oxygenated aqueous solution. A product and pulse radiolysis study. [Gamma radiation]. United States. https://doi.org/10.1021/j100208a017
Schuchmann, M N, and von Sonntag, C. 1982. "Hydroxyl radical induced oxidation of diethyl ether in oxygenated aqueous solution. A product and pulse radiolysis study. [Gamma radiation]". United States. https://doi.org/10.1021/j100208a017.
@article{osti_6846999,
title = {Hydroxyl radical induced oxidation of diethyl ether in oxygenated aqueous solution. A product and pulse radiolysis study. [Gamma radiation]},
author = {Schuchmann, M N and von Sonntag, C},
abstractNote = {The reactions of peroxyl radicals derived from diethyl ether were investigated by product analyses and pulse-radiolytic techniques. The products and their G values (in brackets) in the ..gamma.. radiolysis of diethyl ether (10/sup -3/ M) in N/sub 2/O/O/sub 2/-saturated aqueous solutions at 0.43 W kg/sup -1/ are acetaldehyde (0.6), ethanol (0.6), ethyl acetate (2.8), ethyl formate (0.7), formaldehyde (0.4), hydrogen peroxide (2.1), 1-ethoxyethyl hydroperoxide (1.2), and 2-ethoxyacetaldehyde (approx. 0.5). Except for the latter, all products have the 1-ethoxyethylperoxy radical (I) as a precursor. It is formed as the major radical by OH abstraction of the ..cap alpha..-H atom (96%) followed by O/sub 2/ addition. Besides other bimolecular decay processes of I which are also discussed, there is an important route leading to 1-ethoxyethyloxyl radicals and O/sub 2/: 2I ..-->.. 2CH/sub 3/CH(O)OEt + O/sub 2/. The oxyl radical rearranges in aqueous solutions to the 1-ethoxy-1-hydroxyethyl radical: CH/sub 3/CH(O)OEt ..-->.. CH/sub 3/C(OH)OEt. The latter adds oxygen to give the corresponding peroxyl radical, which eliminates HO/sub 2/. in a fast spontaneous reaction to give ethyl acetate: CH/sub 3/C(OH)OEt + O/sub 2/ - HO/sub 2/. ..-->.. CH/sub 3/COOEt. Evidence for the formation of HO/sub 2/. (O/sub 2//sup -/. in neutral and basic solutions) according to the above reaction sequence was provided by pulse-spectrometric and pulse-conductometric measurements. 1-Ethoxyethyl hydroperoxide is thought to result from the reduction of I by O/sub 2//sup -/.. At much lower dose rates (0.0048 W kg/sup -1/) an intramolecular H abstraction competes with the bimolecular decay of I. This process leads to a different product distribution and to the formation of acidic products.},
doi = {10.1021/j100208a017},
url = {https://www.osti.gov/biblio/6846999}, journal = {J. Phys. Chem.; (United States)},
number = ,
volume = 86:11,
place = {United States},
year = {Thu May 27 00:00:00 EDT 1982},
month = {Thu May 27 00:00:00 EDT 1982}
}