Sulfite to permanganate mole ratio (no.

1,2)

Kinetic results were consistent with the rate law

Mn O4


Mn O4

2
S O3
d

which gives the stopped-flow traces excellent linear plots of 1/( A A vs. time.

Under pseudo-first order conditions (no .3-6, 11, 13)

2
S O3

0


Mn O4

0




Which also gives very good linear plots of log ( A A vs. time.

At intermediate sulfite to permanganate mole ratios of 1.5 and 6.0 (no. 12, 14-17, and 7-10), the traces
were also plotted according to the integrated rate equation
 2
S O3

0 X


Mn O4

0


Mn O4

0 2 X

2
S O3

0


Mn O4

2
S O3

0







log
 2
S O3

2
S O3


Mn O4
Where X =

Mn O4







The Kinetic behavior observed in the first, faster phase is consistent with the following mechanism:

2+ S O3
2 k 1 Mn O4

+ S O3
MnO4

2+ HSO 3
k 2 Mn O4


+ H S O3

Mn O4

2+ S O3

fast Mn O4

+ S O3
Mn O4

2+ S O3 + H2O
fast Mn O4

+ H S O
3 +O H
Mn O4
2
fast H 2 O+ S O4

+2 O H
S O3
This scheme implies that outersphere one-electron transfer as the rate determining step.

pH 9-13

There is no variation in k obsd with the pH from about 9 to 13, in accordance with the lack of
protonation equilibria involving either reactants.

The mean value of k 1 = k obsd at = 0.1 M is (1.28 0.08) X 105 M-1 s-1. An ionic strength
effect on k 1 is discernible. Plot of log k 1 vs. 1/ 2 yields a slope of 1.8 in the interval between
=0.00.055, which linearity breaks drown above =0.055, and a saturation effect is
observed: i.e., k 1 increases more slowly than required by linearity.

pH 8 SO32-

About pH 8, the observed rate constant starts to increase, owing to the presence of H S O3
2
ion (pK = 6.79), which is expected to be more reactive than ion on electrostatic grounds. From
S O3
6 -1 -1
runs 14-17, the rate constant for H S O3 path was estimated to be k 2= ( 3.0 0.2 ) 10 M s

The oxidation of sulfite ion by Mn O4 is the fastest among kinetically characterized outersphere
2
oxidations of this ion: 2 10 4 M-1 s-1 (by and 3.7 10 4 M-1 s-1 (by copper(III)
Ir Cl
6
tetraglycine) , which are comparable with k 1 of this work.

The oxidation of SO 2 in perchloric acid by manganese(III), chromium (VI), aquairon(III),

chloroiron(III), and chlorocopper(II) involve inner-sphere mechanisms with prior complexation of the
reactants. The rated determining steps in the permanganate oxidation of nitrite ion in acidic media are
the formation of reactive N(III) species. An inner-sphere mechanism has been proposed for the
permanganate-iron(II) reaction in acidic solution.