Hydroxyl radical-induced oxidation of 2-methyl-2-propanol in oxygenated aqueous solution. A product and pulse radiolysis study. [Gamma radiation]

Journal Article · Thu Apr 05 00:00:00 EST 1979 · J. Phys. Chem.; (United States)

DOI:https://doi.org/10.1021/j100470a004· OSTI ID:6232412

Schuchmann, M N; von Sonntag, C

The reactions of the 2-methyl-2-hydroxypropylperoxyl radical were investigated by ..gamma.. and pulse radiolysis of aqueous oxygenated solutions of 2-methyl-2-propanol. The products and their G values (in brackets) on ..gamma.. radiolysis of a N/sub 2/O/O/sub 2/(80/20v/v) saturated solution at 20/sup 0/C are formaldehyde (I(1.3)), acetone (II(1.6)), 2-methyl-2-hydroxypropionaldehyde (III(2.0)), 2-methyl-2,3-propanediol (IV(0.5)), an organic peroxide, very likely di(2-methyl-2-hydroxypropyl) peroxide (V(0.7)), and hydrogen perioxide (VI(2.0)). Two major decay processess for the 2-methyl-2-hydroxypropylperoxyl radical are proposed: (i) formation of O/sub 2/ and two 2-methyl-2-hydroxpropyloxyl radicals which either combine (product V), disproportionate (products III and IV) or fragment (products I and 2-hydroxypropyl-(2) radicals), and (ii) formation of VI and III. The 2-hydroxypropyl-(2) radicals add oxygen to give the corresponding peroxyl radicals which rapidly eliminate HO/sub 2/ (product II). The HO/sub 2/ radicals largely disproportionate (products VI and O/sub 2/). At pH 9.4 the rate of the formation of O/sub 2/ . (pK/sub a/(HO/sub 2/) = 4.75) is determined by the bimolecular decay of the primary peroxyl radicals. The rate constant of the latter reaction was obtained pulse conductometrically as 2k = (8+-2) X 10/sup 8/M/sup -1/s/sup -1/. Competition among the different modes of reaction is evident from the effect of deuterium substitutionand temperature on the distribution of product yields.

• Research Organization: Max-Planck-Institut fuer Kohlenforschung, Ruhr, West Germany
• OSTI ID: 6232412
• Journal Information: J. Phys. Chem.; (United States), Vol. 83:7
• Country of Publication: United States
• Language: English

Related Subjects

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
PROPANOLS
RADIOLYSIS
CATALYSIS
EXPERIMENTAL DATA
GAMMA RADIATION
HYDROXYL RADICALS
ISOLATED VALUES
OXIDATION
ALCOHOLS
CHEMICAL RADIATION EFFECTS
CHEMICAL REACTIONS
CHEMISTRY
DATA
DATA FORMS
DECOMPOSITION
ELECTROMAGNETIC RADIATION
HYDROXY COMPOUNDS
INFORMATION
IONIZING RADIATIONS
NUMERICAL DATA
ORGANIC COMPOUNDS
RADIATION CHEMISTRY
RADIATION EFFECTS
RADIATIONS
RADICALS
400600* - Radiation Chemistry