EXP-5 STANDARDIZATION OF SODIUM THIOSULPHATE SOLUTION WITH

STANDARD POTASSIUM DICHROMATE SOLUTION BY IODOMETRIC METHOD

1. State the fundamental principle of iodimetric and iodometric titration.

Ans. The process by which estimation of a reductant is made by the use of liberated iodine is called
iodometric titration.
In iodimetric titration, pure iodine is used instead of liberated iodine from the titration.

2. Why is starch used as an indicator in titrations involving iodine?

Ans. Iodine in water solutions is usually colored strong enough so that its presence can be detected
visually. However, close to the end point, when the iodine concentration is very low, its yellowish
color is very pale and can be easily overlooked. If we add starch, iodine gets adsorbed on the starch
molecule surface and product of adsorption has strong, blue color.

3. Why is it added at the last stage of titration?

Ans. In the presence of small amounts of iodine adsorption and desorption are fast and reversible.
This is why for the end point detection starch solutions are used. However, when the concentration
of iodine is high, it gets bonded with starch relatively strong, and desorption becomes slow, which
makes detection of the end point relatively difficult. Thus at the end point some absorbed iodine may
remain un-titrated giving erroneous end point. This is why starch is added at the last moment when
iodine concentration is very small.

4. Why does deep-blue coloration appear after adding starch?

Ans. If we add starch, iodine gets adsorbed on the starch molecule surface and product of adsorption
has strong, blue color.

5. Why does light green color appear at end point?

Ans. Due to the presence of Chromium (3+) ion, which gives light green color when in a solution.

6. Why light green color is not appeared before the end point?
Ans. Because all the iodine is not desorpted by thiosulfate and remained un-titrated before the end-
point, so due to the presence of iodine the light green color of Chromium (3+) cannot appear before
end point.

7. Why is the end point detected by the appearance of light green color of chromic ion (Cr3+)?
Ans. Because of the absence of iodine in the solution, the deep color disappears it means the
reaction is complete so the light green color of Chromium (3+) ion indicates the end point.

8. What are the sources of error and steps of elimination against each of the errors?
Ans. The errors and their solution,
Insufficient acidity -Add strong acid (HCL)
Oxidation of HCL –Add weak base (sodium bicarbonate)
Iodine would fly –Keep the conical flask closed by watch glass
Adsorption of iodine decrease –Keep temperature below 30-35 C

9. Why do you add) i) sodium bicarbonate ii) conc. HCl iii) KI?
Ans. i) In order to avoid oxidation of hydrochloric acid by air, a reducing atmosphere should be
provided. This may conveniently be done by adding some solid sodium bicarbonate
ii) The solution should be strongly acidic. Insufficient acidity causes incomplete reduction of
dichromate by iodide ion. So strong acid HCL is added.
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iii) Potassium Iodide is generally used to produce liberated Iodine to run the reaction through
iodometric method.
10. Write down the reactions. Which is oxidant and reductant and why?
Ans. The reactions,

K2Cr2 O7 + 14 H+ + 6 e - = 2Cr3+ + 7 H2O + 2K+ [reduction half reaction]

2 KI = I2 + 2 e - + 2K+ …………× 3 [oxidation half reaction]

K2 Cr2 O7 + 6 KI + 14 H+ = 2Cr3+ + 3I2 + 7 H2O + 8K+

Or, K2 Cr2 O7 + 6 KI + 14 HCl = 2CrCl3 + 3I2 + 7 H2O + 8KCl

2 Na2S2O3 = Na2S4O6 + 2Na+ + 2 e -

I2 + 2e - = 2I-

2Na2S2O3 + I2 = Na2S4O6 + 2NaI

Now, from the above reactions we get,
1 mole K2Cr2O7 ≡ 3 mole I2 ≡ 6 mole Na2S2O3

Here in 7th line, Sodium thiosulphate is the reductant, because it reacts with iodine and oxidizes itself
by gaining 3 oxygen’s and as we know reductants reduces other in a reaction and oxidizes itself so it is
acting as a reductant and iodine is an oxidant.

In 3rd line, Potassium dichromate is an oxidant because it is reducing itself by gaining hydrogen in this
reaction and as we know oxidants oxidizes other in a reaction and reduces itself so potassium
dichromate is acting as an oxidant and potassium iodide is acting as a reductant.

11. Why the titration’s temperature does not exceed 300C- 350C?
Ans. At the elevated temperatures adsorption of the iodine on the starch surface decreases, so
titration should be carried out at the temperature that does not exceed 300C- 350C.

Chem-102 Page 2 of 5
EXP-6 STANDARDIZATION OF POTASSIUM PERMANGANATE (KMNO4) SOLUTION
WITH STANDARD SODIUM OXALATE (NA2C2O4) SOLUTION

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 KMnO4 in the solution becomes permanent which indicates
the end point since the whole amount of Na2C2O4 is completely oxidized by KMnO4.

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]
2-
C2O4 = 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 Na2C2O4 is Reductant as it is
oxidizing itself by losing electron.

Chem-102 Page 3 of 5
EXP-7 ESTIMATION OF IRON (II) BY STANDARD POTASSIUM DICHROMATE
SOLUTION

1. Why the violet-blue coloration is seen at end point?

Ans. Because all iron is being neutralized by potassium dichromate.

2. Why is it necessary to use sulphuric acid and phosphoric acid?

Ans. Dilute H2SO4 is preferable to use as
I) it reduces the tendency of atmospheric oxidation of Fe (II) into Fe (III) and
ii) to supply necessary amount of H+ in the solution during titration.

A small volume of H3PO4 is also employed with H2SO4 due to two reasons.
i) It helps to obtain a sharp end point. When phosphoric acid is present in the solution, this decreases
the concentration of ferric ions in the solution by forming a colorless complex ion [Fe (HPO4)] + with
the Fe3+ ions formed during the oxidation reaction. For this reason, change in color at the end point is
sharply visualized. Otherwise Fe3+ ions affect the color change of the indicator.
ii) Phosphoric acid reduces the actual oxidation potential of the ferrous-ferric system to a level which
is sufficiently low to permit the indicator to function.
3. Write down the reactions. Which is oxidant and reductant and why?
Ans. The solution may contain only Fe(II). Fe(II) portion is oxidized into Fe(III) using an oxidizing
agent. Usually acidified K2Cr2O7 or KMnO4 are employed.
K2Cr2O7 + 7H2SO4 + 6FeSO4 = K2SO4 + Cr2(SO4)3 + 3Fe2(SO4)3 +7H2O

4. Show that 1 ml 1M K2Cr2O7 ≡ 0.335 gram of Fe2+

Ans. 6 mole Fe2+ ≡ 1mole K2Cr2O7
1000 ml 1M K2Cr2O7  6 mole Fe  335.04 gm
1 ml 1M K2Cr2O7 ≡ 0.335 gram of Fe2+

5. Why diphenylamine is only able to function as an indicator?

Ans. The diphenylamine indicator is used as solution in concentrated sulphuric acid. The first step in
the oxidation of diphenylamine [1] is its irreversible conversion into diphenylbenzidine [2].
2 NH [O] NH NH
[1]
[2]
Diphenylbenzidine [2] is colorless, but the reversibly oxidized diphenylbenzidine is violet [3].

NH NH N N

[3]
[2]

When all ferrous iron is completely oxidized into ferric iron, then violet diphenylbenzidine [3] is
visible. The oxidation potential of the above reversible reaction is 0.76 volt. The standard oxidation-
0 0
reduction potentials ECr O 2 / Cr 3
and EFe 3
/ Fe2
are 1.36 and 0.77 volt respectively. Phosphoric
2 7

acid reduces the actual oxidation potential of the ferrous-ferric system to a level which is sufficiently
low to permit the indicator to function. So diphenylamine is able to function as an indicator in this
reaction.
EXP-8 ESTIMATION OF COPPER BY IODOMETRIC METHOD
Chem-102 Page 4 of 5
1. What is the desirable pH value for the reaction? Why is it important to maintain the pH of the
solution during the reaction between Cu2+ and KI?
Ans. Before the titration, it is necessary to adjust the acidity of the solution since to keep pH of the
solution is important. If pH is too low, the air oxidation of the iodide is a serious source of error
because of catalysis by copper ions. If pH is too high, the reaction between iodide and cupric ions may
be incomplete when the titration is started. Therefore, this experiment gives accurate result when
solution possess a pH 4 - 5.5. But if mineral acid is present in the solution, pH falls below 4. So it
should be neutralized. To do this a weak alkali e.g., NH4OH, Na2CO3 etc. is used.

2. Why do you add i) NH4OH ii) dil. CH3COOH iii) KI iv) ammonium thiocyanate (NH4CNS)?
Ans. i) to keep the pH around 4 to 5.5 we add ammonium hydroxide
ii) When all the mineral acids are neutralized, an addition of slight excess NH4OH will react with a
small portion of CuSO4 resulting in the precipitation of Cu(OH) 2.
CuSO4 + 2NH4OH = Cu(OH) 2 + (NH4)2SO4
The precipitate of Cu(OH) 2 is re-dissolved by adding few drops of acetic acid.
Cu (OH)2 + CH3COOH  (CH3 COO)2Cu + H2O
That’s why acetic acid is added.
KI is used to liberate iodine
iv) When Cu2+ solution is treated with KI to liberate iodine; it yields Cu2I2. This absorbed iodine in
Cu2I2 may not undergo titration against Na2S2O3. Cu2+ has a greater absorption affinity to CNS- than I-.
This is why, NH4SCN preferentially releases absorbed iodine from Cu2I2. As a result, entire liberated
iodine undergoes titration giving exact end point.

3. Write down the reactions. Which is oxidant and reductant and why?
Ans. In this experiment, a solution of a cupric salt at a suitable concentration is treated with an excess
of potassium iodide, iodine is liberated.
2CuSO4 + 4KI = Cu2I2 + I2 + 2K2SO4
Then the liberated iodine is titrated against Na2S2O3 solution.
I2 + 2Na2S2O3 = Na2S4O6 + 2NaI
Sodium thiosulphate is the reductant as it is oxidizing itself by reducing iodine and cupric salt is the
oxidant as it is reducing itself by oxidizing KI.

4. Show that 1 ml 1M Na2S2O3 ≡ 0.06354 gram of Cu2+

Ans. 2mole CuSO4 ≡ 1mole I2 ≡ 2mole Na2S2O3
1000 ml 1M Na2S2O3  1 mole Cu  63.54 g Cu2+
1 ml 1M Na2S2O3 ≡ 0.06354 gram of Cu2+

Chem-102 Page 5 of 5