Hydrodyanmic chronocoulometiy is theoretically developed such that the diffusion coefficient (£>) and concen-Research on New Development of Organic Electrochemistry (Nos. 05235214 and 06226222) from the Ministry of Education, Science and Culture, Japan, the Nakatani Electric Measuring Technology Foundation, and the Nissan Science Foundation.
The water-induced disproportionation of the electrogenerated
superoxide ion (O2
-) in acetonitrile,
dimethylformamide, and dimethyl sulfoxide media containing various
concentrations of water as a Brønsted acid
has been examined by UV−vis spectroscopy. Analysis of the
kinetics as a function of O2
- and
water
concentrations and of the measurement time demonstrated that the
disproportionation of O2
- by water
in
these media obeys a common mechanism: O2
-
+ H2O ⇄ HO2
• +
OH- (k
1,
k
-1) HO2
• +
O2
- → HO2
- +
O2
(k
2) (HO2
•,
hydroperoxyl radical; HO2
-, hydrogen peroxide
anion). The solvent dependence of the obtained
kinetic parameters of
(k
1/k
-1)k
2,
k
1 and
k
-1/k
2 is discussed in
terms of the solvation of O2
- and
H2O as well
as the effective acidities of H2O in different aprotic
solvents.
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