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Faster Phase
Faster Phase
1,2)
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.