CHEMISTRY LABORATORY [CHEM 102]

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EXPERIMENT NO. : 06 DATE:

STANDARDIZATION OF POTASSIUM
NAME OF THE PERMANGANATE (KMnO4) SOLUTION WITH
EXPERIMENT STANDARD SODIUM OXALATE (Na2C2O4)
SOLUTION
Theory

Permanganate solution is usually standardized with sodium oxalate because of its stability,
anhydration and easy availability in a pure form. Sodium oxalate solutions are not stable
when stored in glass vessels, since the glass is attacked. Hence these solutions should be
used soon after they have been made. The oxalate-permanganate reaction is relatively
complex. In this reaction, Sodium oxalate acts as reducing agent(reductant) while potassium
permanganate acts as oxidizing agent(oxidant). The reactions are:
MnO4- + 8H+ + 5 e - = Mn2+ + 4 H2O [reduction half reaction]
C2O42- = 2CO2 + 2 e - [oxidation half reaction]
The overall reaction in acid solution is given by,
2KMnO4 (aq) + 8H2SO4 (aq) + 5 Na2C2O4 (aq) = 2MnSO4 (aq) + 8H2O (l) + 10CO2 (g) +
5Na2SO4 (aq) + K2SO4 (aq)
In this reaction, sodium oxalate is oxidized by potassium permanganate and converted into
CO2 and H2O. At about 600- 700C, KMnO4 is readily reduced into MnSO4. At initial state, the
direct reaction is slow since no Mn 2+ exists in the solution. Consequently, the first few drops
of permanganate added to the acidified oxalate solution are not decolorized immediately. But
2-
when a small amount of Mn 2+ (MnSO4 Mn2+ + SO4 ) is formed in the solution, rate of the
reaction is increased instantly. They react with permanganate to form intermediate oxidation
states of manganese. These states, in turn, react rapidly with oxalate to give the products.
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So it can be said that MnSO4 acts as an auto catalyst. When pink color KMnO 4 is added from
burette into Na2C2O4, MnSO4 (light pink and almost colorless at dilute solution) along with
colorless K2SO4 is produced. As a result, the solution will be colorless. So the appearance of
light pink color KMnO4 in the solution indicates the end point since the whole amount of
Na2C2O4 are completely oxidized by KMnO4.
PREPARATION OF 100ML 0.1M STANDARD SODIUM OXALATE SOLUTION
Molecular weight of Na2C2O4 = 134 gm

1000ml of 1M Na2C2O4 solution contain 134 gm Na2C2O4

134  100  0.1

100 ml of 0.1M Na2C2O4 solution contain gm
1000

= 1.34 gm

Amount of Na2C2O4 taken = . . . . . . . . . gm

Weight taken (gm)

Molarity of the prepared solution = × 0.1M
Weight to be taken (1.34gm)

= × 0.1M
1.34gm

= ………… M

Transfer . . .. …. . gm of anhydrous Na2C2O4 in a 100ml volumetric flask, then dissolve it with

distilled water and make it up to the mark.

PROCEDURE
1. Pipette out 10ml 0.1M standard sodium oxalate solution in a conical flask.

2. Add about 50ml 1M sulfuric acid solution to it.

3. Heat the solution up to 60oC to 70oC.

4. Continue to add permanganate solution from the burette at a moderate rate and shake
the clear solution continuously. As the color disappears more slowly, slow down the addition

of permanganate solution drop wise until one drop gives a light permanent pink color.
This is the end point of titration.

5. Calculate the concentration of the supplied potassium permanganate solution.

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TABLE: STANDARDIZATION OF SUPPLIED POTASSIUM PERMANGANATE

SOLUTION BY THE PREPARED STANDARD SODIUM OXALATE SOLUTION.

Volume of Burette reading

No. of
Na2C2O4
observation
solution
(ml) Initial (ml) Final (ml) Difference (ml) Mean (ml)

CALCULATION

We know, 5 × VKMnO4 × S KMnO4 = 2 × V Na C O

2 2 4 × S Na C O
2 2 4

RESULT

The strength of the supplied potassium permanganate solution is ….................... M.

ERROR
The accurate result is …………M.

Known Value ~ Observed Value

Percentage of error = × 100
Known Value

= × 100 = …………

CAUTION!
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1. HNO3 is unsuitable since nitrate ion is a moderately strong oxidizing agent which may
interfere with the cation of KMnO4.
HCl reacts with KMnO4 as follows, 2MnO4- + 10Cl- +16H+ = 2Mn2+ + 5Cl2 + 8H2O. In the use
of HCl, the rate of reaction has to be increased by using excessive HCl or by making solution
more concentrated or by maintaining high temperature or by using ferric salt. For these
reasons, amount of KMnO4 is excessively needed with respect to theoretical amount during
titration.
Because of the above reasons, HNO3 and HCl are not used during standardization of
potassium Permanganate (KMnO4) solution with standard sodium oxalate (Na 2C2O4) solution
whereas H2SO4 does not react with KMnO4 at dilution.

2. If the solution is brownish due to less H2SO4, then excessive H2SO4 should be added to
the solution.

3. Permanganate is not a primary standard. The strength of the solution, when prepared
with ordinary distilled water, gradually decreases as the permanganate decomposes to
manganese dioxide due to the presence of organic matter in the water. MnO 2 acts as a
catalyst for auto decomposition of permanganate; hence solutions should be kept in dark
bottles.

4. A pure permanganate solution will be kept indefinitely, provided that it is kept free from
dust, organic matter, precipitated manganese dioxide and reducing vapors. In order to guard
against possible error due to decomposition of permanganate the solution should be
standardized just before it is used. If filtered solution of permanganate is to be diluted, it is
best to use water which has been re-distilled from alkaline permanganate.

DISCUSSION
[Write, in brief, about the precautions taken, causes for deviation of the experimental result from the
expected value on the basis of the following major matters. i) washing and rinsing all apparatus ii)
weight measurement iii) Solution preparation iv) maintaining lower meniscus of the surface
level of liquid on the mark in the volumetric flask and eye level at the same plane v)
maintaining lower meniscus of the surface level of liquid on the mark in the burette and eye
level at the same plane vi) rate of dropping vii) detection of color change. These are just
examples. Every day in every lab in the world old mistakes are repeated and new cases are recorded.
Finally, each titration has its own quirks. They are usually related to chemical characteristics of titrant

and other substances involved. Discussion should be written in past-passive form.]

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 ………………………………………..
Signature of the faculty
SOME POINTS ON SOURCES OF ERRORS

TITRATION ERROR
After the reaction between the substance and the standard solution is practically complete, the
indicator should give a clear visual change (either a color change of the formation of turbidity) in the
liquid being titrated. The point at which this occurs is called the end point of the titration. In the ideal
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titration the visible end point will coincide with the stoichiometric or theoretical end point. In practice,
however, a very small difference usually occurs; this represents the titration error.
There are thousands of possible random errors that can't be adjusted for. Some of them are typical
human errors that can be limited by sticking to lab procedures, but as long as there is a human operator
involved, they will be never completely eliminated. Some of possible cases are:
1. Misjudging the color of the indicator near the end point - this is probably the most common
one. Not only color change is sometimes very delicate and slow, but different people have
different sensitivity to colors. This is not the same as being color blind, although these things
are related.
2. Misreading the volume - at any moment, and due to whatever reason. This can be for example
a parallax problem (when someone reads the volume looking at an angle), or error in counting
unmarked graduation marks. When reading the volume on the burette scale it is not uncommon
to read both upper and lower value in different lighting conditions, which can make a
difference.
3. Using contaminated solutions - for example when two different solutions are transferred
using the same pipette and pipette is not rinsed with distilled water in between.
4. Using diluted titrant and diluted titrated solution - if the burette and/or pipette was not
rinsed with transferred solution after being rinsed with distilled water. In effect titrant (or
titrated substance) is slightly diluted.
5. Using solutions of wrong concentration - titrant we use may have different concentration
than expected. This can be due to incorrect standardization, error in copying the concentration,
contamination of the bottle content, titrant decomposition, solution being kept in open bottle
and partially evaporated and so on.
6. Using wrong amount of indicator - in the case of single color indicators amount added can
shift end point.
7. Using dirty glass - if glass was not properly cleaned before use it may be contaminated with
old reagents, which can react with new ones, changing their concentration. Also, dirty glass is
not properly wetted by the solutions and they can form droplets on the glass surface making
exact volume measuring impossible.
8. Rinsing burette and/or pipette with wrong solution - if the burette or pipette is not dry
before use, it has to be rinsed with the solution that will be transferred. Using just distilled
water for rinsing will mean transferred solution is slightly diluted. Obviously it is important
only when transferring sample, titrant or stoichiometric reagents used for back titration. Small
errors in amounts of other substances (buffers, acids used to lower pH in redox titrations,
solutions masking presence of interfering substances and so on) are not that important.
9. Not filling burette properly - if there is an air lock in the burette stopcock it can block the
flow of the titrant, but it can also at some moment flow with the titrant; after that we have no
idea what was the real volume of solution used.
10. Not transferring all solid/liquid when preparing samples - it may happen that part of the
solid was left in the funnel during transferring it into flask, or it was simply lost. It is also not
uncommon to forget to rinse walls of the glassware after solution was transferred - it may
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 happen both to solution pipetted to some vessel, or to titrant that formed droplet on the flask
wall and was not rinsed with distilled water. If the pipette is not clean, some of the solution can
be left inside in form of drops on the glass.
11. Transferring excess volume of liquid - by blowing pipette for example, or by incorrectly
leveling meniscus with the mark on the single volume pipette.
12. Not transferring all the volume - shaken pipette may lose a drop of the solution when it is
being moved between flasks, one may also fill the single volume pipette leveling not the
meniscus, but the upper edge of the solution with pipette mark.
13. Using wrong reagents - sounds stupid, but happens now and then. Too many possibilities to
list, but we have to remember - if the reaction doesn't proceed as expected, it won't hurt to
check if burette is not filled with something different than expected. Or perhaps there is no
indicator in the solution?
14. Titrating at wrong temperature (other than glassware was calibrated for)- This is a very
common problem. Quite often we have no choice other, then to calibrate the glass once again.
This is time consuming and - especially in the student lab - almost impossible without
additional arrangements.
15. Titrating at wrong temperature (other than the method was designed for)- Some
indicators are sensitive to temperature changes. Some reactions need correct temperature range
to keep stoichiometry (avoid side reactions).
16. Losing solution - too vigorous swirling can end in liquid splashing from the titration flask
before the end point had been reached. It may also happen that some titrant lands on the table
instead of inside the flask.
17. Leaking burette - sometimes burettes leak slowly enough to allow titration, but will lose
several tenths of milliliter if left for several minutes after titrant level has been set to zero and
before titration started.

Now solve the following problems:

1. Why permanganate solution is usually used against sodium oxalate?
Ans. Permanganate solution is usually standardized with sodium oxalate because of its
stability, anhydration and easy availability in a pure form.

2. Why is indicator not necessary?

Ans. While adding KMnO4 into the conical flask to neutralize Na2C2O4 at last when the
neutralization is done the appearance of light pink color KMnO 4 in the solution becomes
permanent which indicates the end point since the whole amount of Na 2C2O4 is completely
oxidized by KMnO4.

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3. Why HNO3 or HCl is not used during titration of Na2C2O4 with KMnO4?

Ans. HNO3 is unsuitable since nitrate ion is a moderately strong oxidizing agent which may
interfere with the cation of KMnO4 which is acting as an oxidant in this experiment.
HCl reacts with KMnO4 as follows, 2MnO4- + 10Cl- +16H+ = 2Mn2+ + 5Cl2 + 8H2O. In the use
of HCl, the rate of reaction has to be increased by using excessive HCl or by making solution
more concentrated or by maintaining high temperature or by using ferric salt. For these
reasons, amount of KMnO4 is excessively needed with respect to theoretical amount during
titration.
Because of the above reasons, HNO3 and HCl are not used during standardization of
potassium Permanganate (KMnO4) solution with standard sodium oxalate (Na2C2O4) solution.

4. What are the difficulties of using HCl?

Ans. In the use of HCl, the rate of reaction has to be increased by using excessive HCl or by
making solution more concentrated or by maintaining high temperature or by using ferric salt.
These conditions are quite difficult to maintain in any lab.

5. Why is temperature maintained at 60-700 C?

Ans. About 600- 700C is needed to reduce KMnO4 into MnSO4.

6. Write down the reactions involved in the experiment? Which is oxidant and reductant and
why?
Ans. The reactions are,
MnO4- + 8H+ + 5 e - = Mn2+ + 4 H2O [reduction half reaction]
C2O42- = 2CO2 + 2 e - [oxidation half reaction]
The overall reaction in acid solution is given by,
2KMnO4 (aq) + 8H2SO4 (aq) + 5 Na2C2O4 (aq) = 2MnSO4 (aq) + 8H2O (l) + 10CO2 (g) +
5Na2SO4 (aq) + K2SO4 (aq)

Here KMnO4 is Oxidant as it is reducing itself by gaining electron and Na 2C2O4 is Reductant
as it is oxidizing itself by losing electron.

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