The reaction between manganese dioxide and potassium permanganateHopkins, Arthur John
Science
The reaction between manganese dioxide and potassium permanganate
Hopkins, Arthur John
Manganese; Thesis (Ph. D.)
It has also been found that the manganese dioxide prepared by the
reduction of permanganate by manganese sulphate is much less stable
than was supposed at the time this work was begun. The dioxide
prepared in this way begins immediately to lose oxygen spontaneously
but recovers the same in the presence of an excess of potassium
permanganate. In the light of these facts it is easy to understand
why lower results were obtained when the oxygen was determined
immediately after the disappearance of the color of the permanganate
and before the suspended oxide had subsided. It appears that the
manganese oxide employed in these experiments was not, as was supposed
at the time, the dioxide but one containing a smaller proportion of
oxygen. If such is the case the first action of the permanganate upon
it would be to replace the oxygen which had been lost. The reduction of
the remaining permanganate would then probably be in accordance with
the equation,
2 KMnO₄ + 3 MnO₂ = 2 K₂O + 5 MnO₂ + 1½ O₂
At the time when the permanganate color disappears, all of the
manganese is in the dioxide condition and the further evolution of
oxygen, which is shown by the preceding experiments to take place
during the subsidence of the suspended oxides, is due to a partial
reduction of this manganese. Therefore the relation of the reduction
of the manganese oxide below the MnO₂ condition before the treatment
with permanganate to the reduction which follows the disappearance
of the permanganate color will determine whether the oxygen evolved
shall be more or less than one and one half atoms to each molecule of
permanganate.
Neither variations in the quantities of nitric acid used (from two to
three molecules in No. III) nor the very slight variations in the amount
of manganese dioxide used, seem to affect appreciably the amount of
oxygen obtained.
It appears that the action of manganese dioxide on potassium
permanganate is the same as that of lead superoxide[7] in the presence
of very dilute nitric acid. Both reduce it to manganese dioxide with
the evolution of one and one half atoms of oxygen to each molecule of
the permanganate.
[7] Allen’s thesis.
The evolution of oxygen from flask No. I containing manganese dioxide
and nitric acid is very slight. From flask No. II containing potassium
permanganate and one equivalent nitric acid, it is also slight but
usually greater than from flask No. I. The differences are much greater
in the case of those determinations in which the heating of the flask
was continued for three hours and in this fact is to be found further
evidence of the reducing action of manganese dioxide on potassium
permanganate.
The possibility of a reaction analogous to that between potassium
permanganate and lead dioxide in the presence of strong nitric acid
seems to be excluded by the fact that the higher oxides of manganese
may be prepared in the presence of concentrated nitric acid.
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