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    The document describes the standardization of potassium permanganate solutions by titrating with sodium oxalate in the presence of perchloric acid and manganese(II) sulfate. The reaction between permanganate and oxalate ions is very slow in the absence of manganese(II) ions, which catalyze the reaction. The reaction mechanism is complex, involving several steps where permanganate, oxalate, and manganese ions in different oxidation states react. In titrating an oxalate solution with permanganate, parallel reactions may occur that affect the stoichiometry of oxalate oxidation by permanganate.

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    First Page PDF

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    The document describes the standardization of potassium permanganate solutions by titrating with sodium oxalate in the presence of perchloric acid and manganese(II) sulfate. The reaction between permanganate and oxalate ions is very slow in the absence of manganese(II) ions, which catalyze the reaction. The reaction mechanism is complex, involving several steps where permanganate, oxalate, and manganese ions in different oxidation states react. In titrating an oxalate solution with permanganate, parallel reactions may occur that affect the stoichiometry of oxalate oxidation by permanganate.

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    The document describes the standardization of potassium permanganate solutions by titrating with sodium oxalate in the presence of perchloric acid and manganese(II) sulfate. The reaction between permanganate and oxalate ions is very slow in the absence of manganese(II) ions, which catalyze the reaction. The reaction mechanism is complex, involving several steps where permanganate, oxalate, and manganese ions in different oxidation states react. In titrating an oxalate solution with permanganate, parallel reactions may occur that affect the stoichiometry of oxalate oxidation by permanganate.

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    26 views1 page

    First Page PDF

    Uploaded by

    Ashry Habashy
    The document describes the standardization of potassium permanganate solutions by titrating with sodium oxalate in the presence of perchloric acid and manganese(II) sulfate. The reaction between permanganate and oxalate ions is very slow in the absence of manganese(II) ions, which catalyze the reaction. The reaction mechanism is complex, involving several steps where permanganate, oxalate, and manganese ions in different oxidation states react. In titrating an oxalate solution with permanganate, parallel reactions may occur that affect the stoichiometry of oxalate oxidation by permanganate.

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    Analytica Chimica Acta

    ElsevierPublishingCompany,Amsterdam 477
    Printedin TheNelherlands

    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)

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