F. Jacobsen et al., OXIDATION OF MANGANESE(II) BY OZONE AND REDUCTION OF MANGANESE(III) BY HYDROGEN-PEROXIDE IN ACIDIC SOLUTION, International journal of chemical kinetics, 30(3), 1998, pp. 207-214
Manganese(II) is oxidized by ozone in acid solution, k = (1.5 +/- 0.2)
x 10(3) M-1 s(-1) in HClO4 and k = (1.8 +/- 0.2) x 10(3) M-1 s(-1) in
H2SO4. The plausible mechanism is an oxygen atom transfer from O-3 to
Mn2+ producing the manganyl ion MnO2+, which subsequently reacts rapi
dly with Mn2+ to form Mn(III). No free OH radicals are involved in the
mechanism. The spectrum of Mn(III) was obtained in the wave length ra
nge 200-310 nm. The activation energy for the initial reaction is 39.5
kJ/mol. Manganese(III) is reduced by hydrogen peroxide to Mn(II) with
k(Mn(III) + H2O2) = 2.8 x 10(3) M-1 s(-1) at pH 0-2. The mechanism of
the reaction involving formation of the manganese(II)-superoxide comp
lex and reaction of H2O2 with Mn(IV) species formed due to reversible
disproportionation of Mn(III), is suggested. (C) 1998 John Wiley & Son
s, Inc.