FEBRUARY.

1949

THE REACTION BETWEEN POTASSIUM

PERMANGANATE AND HYDROGEN PEROXIDE

A Special Project in Quantitative Analysis

MAX I. BOWMAN
University of Louisville, Louisville, Kentucky

Tm potassium perman&nate-hydrogen peroxide shown that, using procedures in standard textbooks of

quantitative analysis, this method gives results equiva-
equation is one of several that were described by
Steinbachl as "nonstoichiometric equations" which lent to those given by the thiosulfate method of deter-
could he balanced in several ways. The following mination of peroxides.
general equation will confirm his statement that there Although the equation in which n=5 holds very well
are theoretically an infinite number of solutions to this under the conditions used in analysis it is not valid for
equation, although it does not include all of the possi- all possible conditions. Several investigators have
shown that when Hz02 is added to a large excess of
+
2 K M n 0 ~ nHpOn+ -rq) ++
bilities listed by Steinbach:
4H-SO4 2MnSOI
Or +
XMnOI thc amount of oxygen evolved is greater than
that pmdicted by the accepted equation. Some early
(n 3)HtO (1) experimenters thought fhat this was due to the presence
of some higher oxide of hydrogens but that view is not
in which n may be any odd integer. Even values of n generally held a t present.
may be used provided the invariant coefficients are The increased amount of oxygen could he accounted
doubled. for by allowing n in equation (1) to equal some number
The reaction in which n=5 is the generally accepted less than 5. If n=5, one rnol of H202 will yield one rnol
one. Huckaba and Keyes2 have recentdy shown the of 02,if n=3, one rnol of Hz02 yields one and one-third
accuracy of this method of determining Ha02 as com- mols of 02,and if n=l , one rnol of the peroxide gives
~ a r e dwith the rtasometric method. It can also he three mols of oxygen.
STEINBMA,0.F,.J O ~ AOFLCKEM.EDUC. 21,66 (1944). %EI,WR, J. W., "A Comprehensive Treatise on Inorganic
2 Hucxaen, C. E.,AND F. G. KEYES,J . Am. Chem. Soc., 70, and Theoretical Chemistry," Longmans, Green and Company,
1640 (1948). New York, Vol. I., 1922, p. 245.

Ramsay4 noted also that the quantity of HaOa
needed to react with a given amount of KMn04 was
less than the amount calculated from the accepted
equation in the case in which the Ha02 was added to the
acidified KMn04, but he did not investigate this prob-
lem in detail. The titration aspect has been rather
thoroughly emlored by Rilis and Gomeza? However,'
their work suffers from the fact that they used an in:
sufficient amount of acid in many of their titrations,
alloning the precipitation of oxides of manganese.
They recognized this fact, but stated that vigorous
stirring caused these oxides to go into solution. Our
experience has been that it is difficult if not impossible
to get results which check under these conditions. The
amount of acid needed to suppress the oxides of man-
ganese is roughly ten times as great when the KMn04is
added to the flask &st as when the HsOe is added first.
It is possible to explain this in terms of the mass action
effect. Addimg KMnO4 first will mean that KMnO4
will be in excess a t all times during the titration until
the equivalent point is reached. If alternate reactions
are possible, those would be favored which require rel-
atively more KMn04 for a given amount of HzOZ.
Substitution in equation (1) of a number less than five
will give us equations of this type. Another equation
~ q u i r i n ga higher KMli04/H20~ratio is the following:
We may assume that adding permanganate first would
increase the tendency toward both reaction (2) and
reaction (1) with n < 5. Therefore it should require a
larger amount of acid to suppress reaction (2) when the
titration is carried out with the KMn04ad ' .d first.
Suggestions for Student Work. The student should
prepare approximately 1 N solutions of KMnO4 and
H201. These may be diluted to obtain solutions of
lower normality, such as 0.1 N and 0.025 N.
A. The 0.1 N KMnO4 may be used to compare the
- permanganate method with the thiosulfate method for
determiniig HzOz. The sodium thiosulfate solution is
made up and standardized against the KMnO4. Both
solutions are then used to determine the concentration
of a sample of H20p, following procedures given in
standard textbooks! If the work is carefully done the
results will agree within 1or 2 parts per thousand. The
fact that the thiosulfate is standardized against the
permanganate makes it unnecessary to know the
normality of the permanganate with a high degree of
accurzcy to demonstrate the close agreement of these
two methods in the determination of hydrogen per-
oxide.
B. The minimum amounts of acid needed to prevent
the precipitation of the oxides of manganese may be
determined for various concentrations. A typical pro-
cedure is to add 50 ml. of distilled water to an Erlen- ACKNOWLEDGMENT
-
RAMSAY, W., J. hem. Soc.,79,1324 (1901).
6 Rlfrs, A., AND J. M. GOMEZA, Anales FZs. y gutm., 37,442-58
f,-"*A,.
lOAl>
6 TREADWEL~F. P., AND W. T. HALL,"AnalytimlChemistry,"
John Wiley & Sons,Inc., New York, 1924,6th ed., pp. 53.F576.
JOURNAL OF CHEMICAL EDUCATION
meyer flask, then add concentrated acid from a buret or
Mohr pipet. After the acid solution has cooled to room
temperature 20 ml. of one reagent is added and titrated
with the other. For purposes of uniformity, we used a
rapid rate of titration and only moderate shaking. Our
results are shown in Table 1. ,
TABLE 1
Minimum Amounts of Acid to Sunress Oxides of
Manganese -
-1 N S o l u t i o n s 4 . l N S o l u t i o n s 4 . 0 2 5 N-
Solutions
36 N 18 N 36 N 18 N 36 N
HnSO, HNOa, HBOI, HNOJ. HaSOa,
ml. ml. ml. ml. ml.
HnOl first 1.7 4;5 0.6 1.2 0.3
KMnO~first 14 7 14 3
* With up to 60 ml. of concd. FINO$,oxides of manganese were
still formed.
It may also be of interest to note that with 0.1 N
solutions and below, the normal titration (i. e., with
HzOa added first) may be carried out with the use of
acetic acid as the acidifying medium. However, when
the KMnO, is added first it is impossible to add enough
acetic acid to prevent the formation of the brown
oxides.
C . To show the variation in the stoichiometric
amounts of reagents titrations-are carried out as above
except that the amount of acid used should be a t least
30 per cent in excess of the minimum amount as shown
in Table 1. The volume ratios of HzOzto KMnO4 are
to be determined in both ways; that is, when the
Ha02 is added first and when the KMnO4 is added first.
These ratios will be about 5 to 11 parts per thousand
less in the latter instance, i. e., with the KMnO4 first.
The differential increases somewhat with increased
concentration of solutions. Nitric acid may be used as
well as sulfuric for the lower concentrations of solu-
tions but i t must first be freed from reducing agents by
titration to a slight pink with KMnOd before being
used in the KMn04-HaOz titrations. The fact that
nitric acid gives results similar to those given with sul-
furic acid is evidence against Ramsay's theory that the
abnormalities in this titration might be due to the for-
mation of persulfuric acid.
After the main points had already been ascertained
by the instructor, this project was assigned to two
students in the elementary quantitative analysis course
for confirmation. These students had previously not
shown much interest in the course, but the project
served to increase their interest greatly and one of them
put in many hours outside the regular laboratory
period.
The author wishes to acknowledge the assistance of
these former students, Mr. Luis G. Romero and Mr.
Robert Lee Davis for their assistance in checking part
of this work.