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'Oxyl Radicals' in keywords Facet   Publication Year 1984  [X]
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1984[X]
1Author    Heinz-Peter Schuchmann, Clemens Von SonntagRequires cookie*
 Title    Methylperoxyl Radicals: A Study of the y-Radiolysis of Methane in Oxygenated Aqueous Solutions  
 Abstract    A product study has been made of the y-radiolysis of aqueous methane solutions that also contained nitrous oxide and oxygen. Formaldehyde (G = 2.8), hydrogen peroxide (G = 2.1), methanol (G = 1.5), methylhydroperoxide (G = 0.8), formic acid (G = 0.3), and dimethylper-oxide (G = 0.1) were found. In alkaline solutions (pH 8, 10-3 M phosphate buffer), the formal­ dehyde yield rises to G = 3.2, while the formic acid yield falls to almost zero (G = 0.05). The initial precursor of the carbon-containing products is the methylperoxyl radical. The methyl­ peroxyl radicals decay through a short-lived tetroxide along various pathways. The most promi­ nent one leads to formaldehyde, methanol and oxygen. Methoxyl radicals (and oxygen) are also formed and, after rearrangement into hydroxymethyl radicals and their conversion into hy-droxymethylperoxyl radicals, eventually yield formic acid and probably further formaldehyde. A route to formaldehyd and hydrogen peroxide is also envisaged. Methylhydroperoxide is formed in the reaction of methylperoxyl radicals with H 0 2 / 0 27 radicals (from radiolytic H atoms and the unimolecular decay of the hydroxymethylperoxyl radical). 
  Reference    Z. Naturforsch. 39b, 217 (1984); received September 19 1983 
  Published    1984 
  Keywords    Autoxidation, Peroxyl Radicals, Oxyl Radicals, Radical Rearrangements, Radiation Chemistry 
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 TEI-XML for    default:Reihe_B/39/ZNB-1984-39b-0217.pdf 
 Identifier    ZNB-1984-39b-0217 
 Volume    39 
2Author    Alicja Piesiak, M. An, Nien Schuchmann, Henryk Zegota, Clemens Von SonntagRequires cookie*
 Title    ß-Hydroxyethylperoxyl Radicals: A Study of the y-Radiolysis and Pulse Radiolysis of Ethylene in Oxygenated Aqueous Solutions  
 Abstract    Hydroxyl radicals (and H atom s) generated in the radiolysis of N20-co n tain in g w ater add to ethylene forming /3-hydroxyethyl radicals (and ethyl radicals). In the presence of oxygen these are converted into the corresponding peroxyl radicals which decay bim olecularly (2 k — 2 x 108 M ~'s-1) as m easured by pulse radiolysis. The m ajor products (G values in brackets) are glycolaldehyde (3.3), form aldehyde (1.6), ethylene glycol (0.8), acetaldehyde (0.5), organic peroxidic m aterial (0.5), and hydrogen peroxide (2.4) (dose rate 0.26 Gy s-1, pH 5.6). A m aterial balance has been obtained with respect to the primary w ater radicals (6.0) and oxygen uptake (4.8). The products and their yields can be accounted for if in the rate determ ining step atetro x id e is form ed which decomposes via three m ajor pathways leading to; (i) H 20 2 and two m olecules of glycolaldehyde (ca. 45%), (ii) 0 2, glycolaldehyde and ethylene glycol (ca. 30%), and (iii) 0 2, two molecules of form aldehyde and two C H 2OH radicals (ca. 15%). A 1,2-H shift of interm ediate oxyl radicals is unim portant in this system. 
  Reference    Z. Naturforsch. 39b, 1262—1267 (1984); received March 5 1984 
  Published    1984 
  Keywords    Peroxyl Radicals, Oxyl Radicals, Pulse Radiolysis, Ethylene, Reaction Kinetics 
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 TEI-XML for    default:Reihe_B/39/ZNB-1984-39b-1262.pdf 
 Identifier    ZNB-1984-39b-1262 
 Volume    39