Mechanisms of the dismutation of superoxide catalyzed by the copper(II) phenanthroline complex and of the oxidation of the copper(I) phenanthroline complex by oxygen in aqueous solution. [Gamma Radiation]

Journal Article · Wed Dec 14 00:00:00 EST 1983 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00363a012· OSTI ID:6970585

Goldstein, S; Czapski, G

The technique of pulse radiolysis to generate O/sup -//sub 2/ has been used to demonstrate that copper 1,10-phenanthroline ((op)/sub 2/Cu/sup 2 +/)is capable of catalytically dismutating O/sup -//sub 2/ with a ''turnover'' rate constant k/sub cat./ = (5.1+/-0.9) x 10/sup 8/ M-/sup 1/s-/sup 1/. The rate constants of the reduction of (op)/sub 2/Cu/sup 2 +/ and of the oxidation of (op)/sub 2/Cu/sup +/ by O/sup -//sub 2/ have been determined to be (1.93+/-0.07) x 10/sup 9/ and (2.95 +/- 0.3) x 10/sup 8/ M/sup -1/s/sup -1/, respectively. The kinetic results of the oxidation of (op)/sub 2/Cu/sup +/ by molecular oxygen in aqueous solution are interpreted by a mechanism that proceeds via a superoxide intermediate, and the rate constant k/sub -10/ = (5.0 +/- 0.3) x 10/sup 4/ M/sup -1/s/sup -1/ has been determined. The rate constant of the oxidation of (op)/sub 2/Cu/sup +/ by H/sub 2/O/sub 2/ was measured to be k/sub 22/ = (937 +/- 20) M/sup -1/s/sup -1/. 7 figures.

• Research Organization: Hebrew Univ. of Jerusalem, Israel
• DOE Contract Number: AC02-76EV03221
• OSTI ID: 6970585
• Journal Information: J. Am. Chem. Soc.; (United States), Vol. 105:25
• Country of Publication: United States
• Language: English

Related Subjects

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
COPPER COMPLEXES
CATALYTIC EFFECTS
SUPEROXIDE RADICALS
OXIDATION
RADIOINDUCTION
REDUCTION
AQUEOUS SOLUTIONS
CATALYSIS
CHEMICAL RADIATION EFFECTS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
DOSIMETRY
EXPERIMENTAL DATA
FORMATES
GAMMA RADIATION
HYDROGEN PEROXIDE
METABOLISM
MONITORING
OXYGEN
PH VALUE
PHENANTHROLINES
PHOSPHATES
PULSED IRRADIATION
RADIOLYSIS
REACTION INTERMEDIATES
SODIUM COMPOUNDS
SOLVATED ELECTRONS
WATER
ALKALI METAL COMPOUNDS
AROMATICS
AZAARENES
CARBOXYLIC ACID SALTS
CHEMISTRY
COMPLEXES
DATA
DECOMPOSITION
DISPERSIONS
ELECTROMAGNETIC RADIATION
ELECTRONS
ELEMENTARY PARTICLES
ELEMENTS
FERMIONS
HETEROCYCLIC COMPOUNDS
HYDROGEN COMPOUNDS
INFORMATION
IONIZING RADIATIONS
IRRADIATION
KINETICS
LEPTONS
MIXTURES
NONMETALS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
OXYGEN COMPOUNDS
PEROXIDES
PHOSPHORUS COMPOUNDS
RADIATION CHEMISTRY
RADIATION EFFECTS
RADIATIONS
RADICALS
REACTION KINETICS
SOLUTIONS
TRANSITION ELEMENT COMPLEXES
400600* - Radiation Chemistry