Analytica Chimica Acta

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Standardization of potassium permanganate by titration of sodium oxalate in presence

of perchloric acid and manganese(II) sulfate

Potassium permanganate solutions are conveniently standardized against

sodium oxalate, a reagent that may be obtained with reductimetric value of 99.95°/o
(U.S. National Bureau of Standards, sample 40h).
Permanganate and oxalate ions react in acidic solution as follows:
2 M n O 2 + 5 H2C204+6 H + ~ 2 Mn 2 + + 10 C O 2 ~-8 H 2 0
In the absence of manganese(II) ion, the reaction is very slow. When the first portion
of permanganate is added to the oxalate solution, the color takes some time to dis-
appear; a further addition of permanganate is followed by a more rapid decoloriza-
tion. The reaction is catalyzed by one of its products, the manganese(II) ion.
The reaction mechanism is complex and involves several steps. Permanganate
and oxalate ions do not react directly; the two species can coexist for quite a long
time in the absence of even traces of lower oxidation states of manganese a. When
manganese(II) and oxalate ions are initially present in excess, the reaction involves
the processes
M n O 2 + 4 M n 2+ + 5 n C 2 0 2 - -I-8 H + --* 5 Mn(CzO4)~n3-2n)+ + 4 H 2 0
2 Mn(C204)(, 3 - 2,)+ __, 2 Mn 2 + + (2n - 1) C 2 0 2 - + 2 C 02
where n may be 1, 2 or 3. The first reaction takes place almost instantaneously, but
not the second. These processes each take place in several steps 2. The reduction of
manganese(VII) by manganese(II) to manganese(III) is initiated by the step:
M n O 2 + M n C 2 0 4 ~ M n O 2- + M n C 2 0 2
If manganese(II) ion is present in significant concentration, the following steps are :
Mn(VI) + Mn(II) ~ 2 Mn(IV) and Mn(IV) + Mn(II) ~ 2 Mn(III)
The manganese(III) subsequently reacts according to the sequence:
Mn(C204)(~3-2")+ ~ M n 2+ + ( n - 1)C2 O 2 - -~C02-~- C O 2

Mn(C204)~ 3-2")+ + C 0 2 -- Mn 2+ + n C 2 0 2 - + C 0 2
At very low concentrations of oxalate, permanganate can also react by the step :
M n 0 2 + M n C 2 0 2 --, M n O 2- +Mn(IV)
In the presence of air, oxygen competes with manganese(III) for the C 0 2 species,
leading to the following induced chain:

C O 2 ~- 0 2 --~ 0 2 C 0 2

0 2 C 0 2 + M n 2+ + 2 H + --, Mn(III) + H 2 0 2 + C O 2

In the titration of an oxalate solution with permanganate, parallel reactions

may take place, affecting the stoichiometry of the oxidation of oxalate by per-

Anal. Chim. Acta, 58 (1972)