Volumetric Analysis / Quantitative analysis

Experiment No. 7

Estimation of KMnO4 solution using standard 0.05M (M/20) Ferrous

Ammonium Sulphate (Mohr’s salt) solution
Aim : 1. To prepare 0.05M Mohr’s salt solution.
2. To calculate the molarity and strength of given KMnO4 solution by titrating it
against Mohr’s salt solution
Theory:
Ferrous ammonium sulphate (Mohr’s salt) acts as a reducing agent. The oxidation
number of iron in Mohr’s salt is +2. Iron is oxidised during the reaction and its
oxidation number changes from +2 to +3.
Potassium permanganate acts as oxidising agent. MnO4− is reduced to Mn2+.
Potassium permanganate acts as a self indicator. Initially colour of potassium
permanganate is discharged due to its reduction by Mohr’s salt. After complete
consumption of ferrous ions, the end point is indicated by the appearance of a pale
pink colour produced by the addition of a little excess of unreacted potassium
permanganate.

Chemical Equation:
Reduction half reaction: 2KMnO4 + 3H2SO4 → K2SO4 + 2MnSO4 + 3H2O + 5[O]
Oxidation half reaction: [2FeSO4 (NH4)2SO4.6H2O + H2SO4 + 5[O] →
Fe2(SO4)3 + 2(NH4)2SO4 + 13H2O] x 5
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Overall reaction: 2KMnO4 + 10FeSO4(NH4)2SO4.6H2O+8H2O →
K2SO4+ 2MnSO4+ 5Fe2(SO4)3+ 10(NH4)2SO4+ 68H2O
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Ionic equation:
Oxidation half reaction: [Fe2+ → Fe3+ + e–] x 5
Reduction half reaction: MnO4– + 8H+ + 5e– → Mn2+ + 4H2O
---------------------------------------------------------------
Overall ionic equation: MnO4– + 8H+ + 5Fe2+ → Mn2+ + 5Fe3+ + 4H2O
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Procedure:
1. Mohr’s salt[FeSO4(NH4)2SO4.6H2O] being a primary standard; its solution can be
prepared by direct weighing. Take a square piece of paper, weigh it accurately and tare
its weight. Now put crystalline Mohr’s salt in the paper and weigh till the weight of
Mohr’s salt is 4.9g.
2. Add 10 ml of dil.H2SO4 to 250ml volumetric flask through a glass funnel kept over
it. H2SO4 is added to prevent the hydrolysis of Mohr’s salt.
Transfer the weighed Mohr’s salt from the paper to a glass funnel placed above 250ml
volumetric flask. Give fine spray of water from wash bottle to the funnel so that
everything comes down to the volumetric flask.
3.Dissolve the Mohr’s salt by shaking the volumetric flask when the salt dissolves
completely add distilled water up to just a little below the mark on the flask. Now add
the last drops of water carefully until the lower meniscus just touches the graduated
mark. Close the measuring flask and shake to get a uniformly concentrated solution.
4. Rinsed and filled the clean burette with potassium permanganate solution upto 0.0
mark without any air bubble.
5. Taken 20 mL of 0.05 M Mohr’s salt solution in a clean conical flask using
measuring cylinder and added full test tube dil. H2SO4 to it.
6. Titrated the Mohr’s salt solution against potassium permanganate solution with
constant swirling of conical flask until a permanent pale pink colour is obtained.
7. Repeated the titration for concordant titre value and tabulated the readings.
8. Molarity and strength of given KMnO4 soluttion is calculated.

Scheme of Titration:
Conical flask: 20mL Mohr’s salt solution + 1 test tube dil.H2SO4 solution.
Burette: KMnO4 solution.
Indicator: KMnO4 self-indicator.
End point: Colorless to permanent pale pink.

Tabular Column:

Trial Volume of Mohr’s Burette reading (ml) Volume of

No. salt Solution (mL) Initial Final KMnO4 Used (mL)

1. 20 0 9.7 9.7
2. 20 0 9.8 9.8
3. 20 0 9.8 9.8

Concordant titre Value: 9.8 mL

Calculation:
To prepare Mohr’s salt solution:
Mass of Mohr’s salt = Molarity X Molar mass of Mohr′s salt X Volume of Solution (mL)
1000
= 1 𝑿 𝟑𝟗𝟐 𝑿 𝟐𝟓𝟎
20X𝟏𝟎𝟎𝟎
= 4.9g
Molarity and strength of KMnO4 solution (𝐚𝟏𝐌𝟏𝐕𝟏)𝐌𝐨𝐡𝐫′𝐬 𝐬𝐚𝐥𝐭= (𝐚𝟐𝐌𝟐𝐕𝟐)𝐊𝐌𝐧𝐎𝟒
𝒂𝟏= The number of electrons lost per formula unit of Mohr’s salt = 1
𝑴𝟏= Molarity of Mohr’s salt solution = 1/20M OR 0.05M
𝑽𝟏= Volume of Mohr’s salt solution = 20 mL
𝒂𝟐= The number of electrons gained per formula unit of KMnO4 = 5
𝑴𝟐= Molarity of KMnO4 solution = ?
𝑽𝟐= Volume of KMnO4 solution = ________ mL (titre value)

Strength of KMnO4 solution = Molarity X Molar mass of KMnO4

= ______ X 158.03
= _______ gL−1
Result: (i) Molarity of KMnO4 solution is _______M.
(ii) Strength of KMnO4 solution is _______gL−1

PRECAUTIONS:
1. Weighing should be accurate.
2. Add 10 ml of conc H2SO4 to prevent hydrolysis of Mohr’s Salt solution.
3. While titrating, the funnel should not be placed at the top of the burette.
4. For preparing standard solution, apparatus should be clean.
5. Standard solution should be prepared in distilled water.
6. Last drops in the measuring flask must be added accurately.

Experiment No. 8

Estimation of KMnO4 solution using standard 0.02M (M/50) Oxalic acid

solution
Aim : 1. To prepare 0.02M Oxalic acid solution.
2. To calculate the molarity and strength of given KMnO4 solution by titrating it
against oxalic acid solution
Theory:
Oxalic acid acts as a reducing agent. The oxidation number of Carbon in oxalic acid is
+3. Carbon is oxidised during the reaction and its oxidation number changes from +3
to +4.
Potassium permanganate acts as oxidising agent. MnO4− is reduced to Mn2+. Potassium
permanganate acts as a self indicator. Initially colour of potassium permanganate is
discharged due to its reduction by oxalic acid. After complete consumption of oxalate
ions, the end point is indicated by the appearance of a pale pink colour produced by
the addition of a little excess of unreacted potassium permanganate. during the
titration of oxalic acid against potassium permanganate, warming of oxalic acid
solution (50°–60°C) along with dilute H2SO4 is required.
Chemical Equation:
Reduction Half reaction: - 2KMnO4 + 3H2SO4 → K2SO4 + 2MnSO4 + 3H2O + 5[O]
Oxidation Half reaction: - 5H2C2O4 + 5[O] → 5H2O + 10CO2↑
--------------------------------------------------------------------------------------- --

Overall reaction: - 2KMnO4+3H2SO4+5H2C2O4 → K2SO4+2MnSO4+8H2O+ 10CO2↑

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Ionic equation:
Reduction Half reaction: - [MnO4– + 8H+ + 5e– → Mn2+ + 4H2O] x 2
Oxidation Half reaction: - [C2O42- → 2CO2 + 2e–] x 5
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Overall reaction: - 2MnO4– + 16H+ + 5C2O42- → 2Mn2+ + 10CO2 + 8H2O
-------------------------------------------------------------------------
Procedure:
1. Being a primary standard oxalic acid(C2H2O4.2H2O) can be prepared by direct
weighing. Take a square piece of paper, weigh it accurately and tare its weight. Now
put oxalic acid crystals in the paper and weigh till the weight is 0.63g.
2. Transfer the weighed oxalic acid crystals from the paper to a glass funnel placed
above 250ml volumetric flask. Give fine spray of water from wash bottle to the funnel
so that everything comes down to the volumetric flask.
3.Dissolve oxalic acid by shaking the volumetric flask when the salt dissolves
completely add distilled water up to just a little below the mark on the flask. Now add
the last drops of water carefully until the lower meniscus just touches the graduated
mark. Close the volumetric flask and shake to get a uniformly concentrated solution.
4. Rinsed and filled the clean burette with potassium permanganate solution upto 0.0
mark without any air bubble.
5. Taken 20 mL of 0.02 M oxalic acid solution in a clean conical flask using measuring
cylinder and added full test tube dil. H2SO4 to it. Heated the oxalic acid solution upto
50°– 60°C before titrating.
6. Titrated the oxalic solution against potassium permanganate solution with constant
swirling of conical flask until a permanent pale pink color is obtained
7. Repeated the titration for concordant titre value and tabulated the readings.
8. Molarity and strength of given KMnO4 solution is calculated.

Scheme of Titration:
Conical flask: 20mL oxalic solution + 1 test tube dil.H2SO4 solution and heated
Burette: KMnO4 solution.
Indicator: KMnO4 self-indicator.
End point: Colorless to permanent pale pink.

Tabular Column:
 Trial Volume of Burette reading (ml) Volume of
No. oxalic acid Initial Final KMnO4 Used (mL)
Solution (mL)

1. 20 0 7.7 7.7
2. 20 0 7.9 7.9
3. 20 0 7.9 7.9

Concordant titre Value: _7.9 Ml

Calculation:
To prepare oxalic acid solution:
Mass of oxalic acid = Molarity X Molar mass of oxalic acid X Volume of Solution (mL)
1000
= 𝟎.02 𝑿𝟏𝟐𝟔 𝑿 𝟐𝟓𝟎
𝟏𝟎𝟎𝟎
= 0.63g
Molarity and strength of KMnO4 solution (𝐚𝟏𝐌𝟏𝐕𝟏)𝐨𝐱𝐚𝐥𝐢𝐜 𝐚𝐜𝐢𝐝= (𝐚𝟐𝐌𝟐𝐕𝟐)𝐊𝐌𝐧𝐎𝟒
𝒂𝟏= The number of electrons lost per formula unit of oxalic acid = 2
𝑴𝟏= Molarity of oxalic acid solution = 0.02M
𝑽𝟏= Volume of oxalic acid solution = 20 mL
𝒂𝟐= The number of electrons gained per formula unit of KMnO4 = 5
𝑴𝟐= Molarity of KMnO4 solution = ?
𝑽𝟐= Volume of KMnO4 solution = ______mL (titre value)

2x0.02x20 =________M

5x____

Strength of KMnO4 solution = Molarity X Molar mass of KMnO4

= ______ X 158.03
= _______ gL−1
Result: (i) Molarity of KMnO4 solution is _______M.
(ii) Strength of KMnO4 solution is _______gL−1
PRECAUTIONS:
1. Oxalic acid should not be heated above 700C.
2. For preparing standard solution, apparatus should be clean.
3. Standard solution should be prepared in distilled water.
4. Weighing should be done correctly.
5. Since the lower meniscus of KMnO4 is not visible, read the upper meniscus.
6. Rinse burette and pipette before use.
7. Do not use rubber pinch cork, burette as rubber is an organic matter and gets attached to
KMnO4.