Scientific American Supplement, No. 561, October 2, 1886Various
Science
Scientific American Supplement, No. 561, October 2, 1886
Various
Science -- Periodicals
To test the method, nine determinations were made with quantities of
pure nitrate of potassium varying from 100 to 200 milligrammes. The
maximum difference between the volumes of permanganate actually used
and those calculated was 0.05 c.c., while the main difference was
0.036 c.c. The measurements of the permanganate were made from a
burette which had been carefully calibrated. We also made a number of
determinations, using a solution of manganous sulphate in the place of
the oxalic acid. The advantage of this method lies in the fact that it
is not necessary to dissolve the oxide which is precipitated upon the
glass within the tubes, E, E, since, in the presence of an excess of
permanganate, the reduction by nitric oxide extends only to the
formation of MnO_{2}; also in the fact that the solution of manganous
sulphate is more stable than that of oxalic acid. A solution of the
sulphate having been once carefully standardized, can be used for a
long time to determine the value of permanganate solutions.
The details of the method are as follows: A solution of manganous
sulphate slightly stronger than No. 1 is prepared.
The difference between 100 c.c. of it and 100 c.c. of No. 1 is
ascertained, according to the method of Volhard, by means of solution
No. 3.
The contents of E, E, together with the rinsings from the tubes, are
poured into a capacious flask. 100 c.c. of the manganous sulphate and
a few drops of nitric acid are then added, and the whole boiled.
Finally, the excess of manganous sulphate is determined, in the manner
described by Volhard, by means of solution No. 3. Subtracting from the
total amount of permanganate thus used the quantity required to
equalize the 100 c.c. of solution No. 1 and the 100 c.c. of the
manganous sulphate, we shall have the quantity of permanganate reduced
by the nitric oxide.
It must, however, be remembered that the value of solution No. 3 is
now to be calculated on the basis of the equation KMnO_{2} + NO =
KNO_{3} + MnO_{2}. One molecule of permanganate equals one molecule of
nitric oxide when manganous sulphate is used, since no part of the
permanganate employed in this method is reduced below the superoxide
condition. In other words, solution No. 3 now represents only
three-fifths as much nitric acid as it does when oxalic acid is used.
The results obtained by this method were moderately satisfactory, but
not quite so exact as those obtained when oxalic acid was used. A
series of four determinations gave differences, between the volumes of
permanganate calculated and used, of 0.05 to 0.15 c.c.
The principal objection to the method lies in the difficulty of
determining, in the presence of the brown oxide of manganese, the
exact point at which the oxidation is complete.
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