Aim: To prepare and standardize 0.02 M Potassium Permanganate solution.

Requirements: Conical flask, burette, pipette, volumetric flask, funnel, iodine flask
Reagents: Sodium Thiosulphate(0.1M), Potassium iodide, 1M sulphuric acid, starch solution,
Potassium Permanganate, Sodium oxalate, Distilled water

Theory:
Preparation:
Potassium permanganate is not a primary standard. It is difficult to obtain the substance perfectly
pure and completely free from manganese dioxide. Moreover, ordinary distilled water is likely to
contain reducing substances (traces of organic matter etc) which will react with the potassium
permanganate to form manganese dioxide. The presence of latter is very objectionable because it
catalyzes the auto - decomposition of the permanganate solution on standing:

4 MnO4 - + 2H2O → 4 MnO2 + 3O2 + 4OH-

This reaction is slow in acid solution but very rapid in neutral solution. For these reasons,
solution is rarely made by dissolving weighed amounts of the purified solid in water, it is more
usual to heat a freshly prepared solution to boiling and keep it on the steam bath for an hour or
so, then filter the solution through a non reducing filtering medium, such as purified glass wool
or a sintered - glass filtering crucible (porosity No: 4). Alternatively, the solution may be allowed
to stand for 2-3 days at room temperature before filtration. The glass stopper bottle or flask
should be carefully freed from grease and prior deposits of manganese dioxide (as this may
catalyzed the decomposition) this may be done by rinsing with dichromate - sulphuric acid
cleaning mixture and then thoroughly with distilled water. Acidic and alkaline solutions are less
stable than neutral ones. Permanganate solution should be protected from unnecessary exposure
to light a dark colored bottle is recommended, but bright sunlight slowly decomposes even pure
solutions.

Standardization:
 Using Sodium Thiosulphate as SSS:
It is an iodometric titration, where liberated iodine from the reaction between potassium
permanganate and potassium iodide is titrated with a reducing agent sodium thiosulphate using
starch solution as indicator. Potassium permanganate as an oxidizing agent and potassium iodide
as a reducing agent, whereby iodide ions are oxidized to molecular iodine in acidic medium
provided by sulphuric acid and potassium permanganate is reduced to manganese. During
titration iodine acts as oxidizing agent and gets reduced to iodide and sodium thiosulphate is
oxidized to sodium tetrathionate.

Reactions:

2 KMnO4 + 10 KI + 8 H2SO4 → 5 I2 + 2MnSO4 + K2SO4 + 8 H2O ……………….1

(2 Na2S2O3 + I2 → Na2S4O6 + 2 NaI) * 5 ...……………..2

Factor:

2 KMnO4 = 5 I2

5 I2 = 2 KMnO4

I2 = 2/5 KMnO4 …..A

Now, from reaction 2

I2 = 2 Na2S2O3 …..B

Comparing A & B,

2 Na2S2O3 = 1 I2 = 2/5 KMnO4

2 Na2S2O3 = 2/5 KMnO4

1 Na2S2O3 = 1/5 KMnO4

1000ml of 1M Na2S2O3 = 1/5(Mol.wt. KMnO4)

= 1/5 (158.03)

1000ml of 1M Na2S2O3 = 31.606g of KMnO4

1ml of 0.1M Na2S2O3 = 0.003161g of KMnO4

 Using sodium oxalate as PSC:

It is oxidation reduction reactions in which potassium permanganate acts as an oxidizing agent,

oxidizes sodium oxalate to carbon dioxide and gets reduced to manganese under acidic
conditions. Titration is carried out at 60-70 ̊ C.

Precautions: Sufficient quantity of acid must present, otherwise formation of a brown color
observe during titration. Similar brown coloration can also be observed at too high temperature
or use of dirty flask. To avoid such anomalies always rinse the flask with solution of Hydrogen
peroxide and dilute sulphuric acid before performing titration.

Reactions:
2 KMnO4 + 3 H2SO4 → K2SO4+ 2 MnSO4 + 3 H2O + 5 [O]
{C2O4Na2 + H2SO4 + [O] → 2 CO2 + H2O + Na2SO4 } * 5

2 KMnO4 + 5 C2O4Na2 + 8 H2SO4→ K2SO4 + 5 Na2SO4 + 2 MnSO4+ 8 H2O + 10 CO2

Factor: 2 KMnO4 = 5 C2O4Na2

KMnO4 = 5/2 C2O4Na2

= 5/2 ( Mol.wt. C2O4Na2)

1000ml of 1M KMnO4 = 5/2 *134.0

=335g of C2O4Na2

1ml of 0.02M KMnO4 = 0.0067g C2O4Na2

Procedure:
Preparation of 0.02 M Potassium Permanganate:
Weigh accurately 3.2g of potassium permanganate; transfer it into 1000 ml volumetric flask.
Dissolve it in sufficient water and make up to volume up to graduation mark with distilled water.
Heat the solution on water bath for one hour. Allow to stand for 2 days and filter through glass
wool. Store in clean, glass - stopper bottle and keep in the dark or in diffuse light except when in
use alternatively, store in dark brown glass bottle; Standardize the solution.

Standardization of approximate 0.02M Potassium Permanganate. using sodium

thiosulphate Iodometry:
Pipette 10 ml of Potassium Permanganate solution into 250 ml iodine flask, add 2g of potassium
iodide (or 10ml of 20% Potassium iodide solution) and add 10 ml of 1M Sulphuric acid, allow to
stand for 10 minutes in dark place and titrate the liberated iodine against standard solution of
sodium thiosulphate using 3 ml of starch solution, added towards the end of the titration, as
indicator.
Each ml of 0.1 M sodium thiosulphate is equivalent to 0.003161g of KMnO4

Standardization of approximate 0.02 M Potassium permanganate using PSC sodium

oxalate:
Weigh accurately 0.15 g of sodium oxalate, transfer it into 250 ml conical flask, and dissolve in
30 ml of distilled water. Add 5 ml of 1 M sulphuric acid and heat to about 70 ͦ C .Add slowly
from a burette potassium permanganate solution with constant stirring until pale pink color
persist for fifteen seconds is produced.
The temperature at the conclusion of the titration should not be less than 60̊ C.
Each ml of 0.02M potassium permanganate is equivalent to 0.0067g of C2O4Na2

Results:

1. Using sodium thiosulphate as SSC

The exact Molarity of prepared approximately 0.02 M Potassium Permanganate Solution is
…………M Potassium Permanganate.

2. Using Sodium oxalate as PSC

The exact Molarity of prepared approximate 0.02 M Potassium Permanganate Solution is
…………….M Potassium Permanganate.
Preparation of 0.02M Potassium permanganate:
Molecular weight of Potassium permanganate = 158.034 g/mole
Molarity,

𝑤𝑒𝑖𝑔ℎ𝑡 𝑖𝑛 𝑔 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒 1
M = 𝑀𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒 ∗ 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 (𝐿)

weight of solute (g) = 0.02 * 158 * 1

= 3.16  3.2g of Potassium permanganate

Standardization of 0.02M Potassium permanganate:

 Using Sodium Thiosulphate as SSS:
Observations:
Burette: 0.1M sodium thiosulphate
Iodine flask: 10ml of approx 0.02M Potassium permanganate + 2g Potassium iodide + 10ml of
1M sulphuric acid
Indicator: starch solution
End point: yellow to blue to colorless

Observation Table:

Sr. Burette Reading (ml) Average

No. Final Initial Difference (ml)

Burette reading: ………… ml of 0.1 M sodium thiosulphate

Calculations:

Each ml of 0.1 M sodium thiosulphate is equivalent to 0.003161g of KMnO 4

1 ml of 0.1 M sodium thiosulphate  0.003161g of KMnO4

…B.R.…ml of 0.1 M sodium thiosulphate,
=B.R. * 0.003161
=………………...g of KMnO4 per 10ml solution
i.e. 10ml(0.01L) solution contains …………g KMnO4
Now, molarity of KMnO4 solution,

𝑤𝑒𝑖𝑔ℎ𝑡 𝑖𝑛 𝑔 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒 1
𝑀= ∗
𝑀𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 (𝐿)
=……………. * 1
158 0.01
=……………..M Potassium permanganate
  Using sodium oxalate as PSC:
Observations:
Burette: …x……M potassium permanganate
Conical flask: 0.15 g sodium oxalate + 30 ml distilled water + 5ml of 1M sulphuric acid
Indicator: potassium permanganate itself indicator
End point: colorless to pale pink

Observation Table:

Sr. Burette Reading (ml) Average

No. Final Initial Difference (ml)

Burette reading: ………… ml of …x… M potassium permanganate

Calculations:

Each ml of 0.02M potassium permanganate is equivalent to 0.0067g of C 2O4Na2

1 ml of 0.02M potassium permanganate  0.0067g of C2O4Na2

…B.R.…ml of …x… M potassium permanganate = 0.15 g C2O4Na2

…B.R….. * x * 0.0067 = 1 * 0.02 * 0.15

x = 0.02 * 0.15 / B.R * 0.0067
= …… M potassium permanganate

OR

Exact molarity of potassium permanganate,

weight in mg of PSC 1
M= equivalent weight of PSC ∗ burette reading (mL)

= 150 / (335 * B.R)

= ……………..M potassium permanganate