Oxidation of phenolates and phenylenediamines by 2-alkanonyl radicals produced from 1,2-dihydroxy- and 1-hydroxy-2-alkoxyalkyl radicals. [Pulsed irradiation]
Journal Article
·
· J. Phys. Chem.; (United States)
Using pulse radiolysis with optical detection it is shown that the formylmethyl radical CH/sub 2/CHO reacts with phenolated XC/sub 6/H/sub 4//sup -/(X = H, alkyl, OCH/sub 3/, OH) by one electron oxidation to yield XC/sub 6/H/sub 4/O. With parasubstituted phenolates the rate constants for formation of XC/sub 6/H/sub 4/O increase with increasing electron-donating power of X (Hammett p=7.9). For X = OH (hydroquinone anion) the rate constant for the electron transfer reaction is 2.2 x 110/sup 9/M/sup -1/s/sup -1/. Replacement of H in CH/sub 2/CHO by alkyl or hydroxyalkyl groups leads to a decrease in the rate constants for oxidation of the hydroquinone anion. CH/sub 2/CHO is also able to oxidize o- and p- phenylenediamine and N,N'-tetramethyl-p-phenylenediamine (k = 7.3 x 10/sup 7/, 4.0 x 10/sup 8/, and 2.0 x 10/sup 9/M/sup -1/s/sup -1/, respectively). The 2-alkanonyl radicals were produced by elimination of OH/sup -/ or alkoxide from ionized 1,2-dihydroxyalkyl or 1-hydroxy-2-alkoxyalkyl radicals, respectively. For cyclic 1-hydroxy-2-alkoxyalkyl radicals elimination of alkoxide results in ring opening. The rate constants for elimination of OH/sup -/ from ionized 1,2-dihydroxyalkyl radicals R/sub 1/C(O/sup -/)CH(OH)R/sub 2/ are between 3 x 10/sup 6/s/sup -1/ (for R/sub 1/ = R/sub 2/ = H and R/sub 1/, R/sub 2/ = H, hydroxyalkyl) and greater than or equal to 8 x 10/sup 6/s/sup -1/ (for R/sub 1/ = R/sub 2/ = CH/sub 3/). 1 figure, 3 tables.
- Research Organization:
- Univ. of Notre Dame, Indiana
- OSTI ID:
- 6478438
- Journal Information:
- J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 83:5; ISSN JPCHA
- Country of Publication:
- United States
- Language:
- English
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Journal Article
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Wed Sep 10 00:00:00 EDT 1986
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OSTI ID:6952925
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Fri Dec 31 23:00:00 EST 1982
· J. Phys. Chem.; (United States)
·
OSTI ID:5939263
Reduction and alkylation of cobalt(II) tetrakis(4-sulfonatophenyl)porphyrin in aqueous solutions. A kinetic spectrophotometric study
Journal Article
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Thu Apr 28 00:00:00 EDT 1983
· J. Phys. Chem.; (United States)
·
OSTI ID:5340229
Related Subjects
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
400600* -- Radiation Chemistry
AMINES
CHEMICAL RADIATION EFFECTS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CHEMISTRY
COMPARATIVE EVALUATIONS
DATA
DATA FORMS
DECOMPOSITION
ELECTRON TRANSFER
EXPERIMENTAL DATA
HYDROXY COMPOUNDS
INFORMATION
IRRADIATION
ISOLATED VALUES
KINETICS
MEASURING INSTRUMENTS
MEDIUM TEMPERATURE
NUMERICAL DATA
OPTICAL SPECTROMETERS
ORGANIC COMPOUNDS
PH VALUE
PHENOLATES
PULSED IRRADIATION
RADIATION CHEMISTRY
RADIATION EFFECTS
RADICALS
RADIOLYSIS
REACTION KINETICS
SPECTROMETERS
TEMPERATURE DEPENDENCE
400600* -- Radiation Chemistry
AMINES
CHEMICAL RADIATION EFFECTS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CHEMISTRY
COMPARATIVE EVALUATIONS
DATA
DATA FORMS
DECOMPOSITION
ELECTRON TRANSFER
EXPERIMENTAL DATA
HYDROXY COMPOUNDS
INFORMATION
IRRADIATION
ISOLATED VALUES
KINETICS
MEASURING INSTRUMENTS
MEDIUM TEMPERATURE
NUMERICAL DATA
OPTICAL SPECTROMETERS
ORGANIC COMPOUNDS
PH VALUE
PHENOLATES
PULSED IRRADIATION
RADIATION CHEMISTRY
RADIATION EFFECTS
RADICALS
RADIOLYSIS
REACTION KINETICS
SPECTROMETERS
TEMPERATURE DEPENDENCE