Unit IV Redox Titrations

1.
1. CERIMETRY

PRINCIPLE: Ce(SO4)2 .2(NH4)2. SO4. 2H2O in H2SO4 medium can function as a strong
oxidizing agent and have a high oxidation potential. Sufficient H2SO4 is used to prevent hydrolysis
and precipitation of basic salts. Ceric Ammonium Sulphate is a salt of suitable solubility for the
precipitation of the standard solution has the approximate formula Ce(SO4)2.2(NH4)2. SO4. 2H2O.
But the solution has to be standardized against a solution of As2O3. Since Ceric Ammonium
Sulphate is a strong oxidizing agent we can determine various reducing substances by simple
titration. In the presence of reducing agent it undergoes reduction to the cerous state for ex:

Ce(SO4)2 + 2FeSO4. Ce(SO4)3 + 2Fe(SO4)3

STANDARDIZATION OF 0.1M Ce(SO4)2 :

1. Preparation of 0.1M Ce(SO4)2.2(NH4)2. SO4. 2H2O :Dissolve 64gm of Ceric Ammonium

Sulphate with the aid of gentle heat in a mixture of 30ml of H2SO4 and 500ml of water. cool, filter
the solution if turbid and dilute to 1000ml with water.
2. Standardization of Ceric Ammonium Sulphate : Weigh accurately about 0.2gm of As2O3,
previously dried at 105˚ for 1 hour, and transfer to a 500ml conical flask. Wash down the inner
walls of the flask with 25ml of 8% w/v NaOH solution, swirl to dissolve and add 100ml of water
and mix. Add 30ml of dilute H2SO4 , 0.15ml osmic acid, 0.1 ml ferroin sulfate solution and titration
with Ce(SO4)2.2(NH4)2. SO4. 2H2O solution (0.1M) until the pink color is changed to a very pale
blue color.

IP/ EQUIVALENT FACTOR:

Each ml of 0.1M Ce(SO4)2.2(NH4)2. SO4. 2H2O solution = 0.004946gm of As2O3.

CALCULATION:
Molarity of Ce(SO4)2.2(NH4)2. SO4. 2H2O solution = Wt. taken x Expected M

Titration vol x IP factor

APPLICATIONS:
1. Assay of FeSO4 : FeSO4 .7H2O, molecular weight = 278gm.
CATERGORY: Haematinic
DESCRIPTION: Bluish-green crystals or light-green crystalline powder.
PROCEDURE: Weigh accurately about 0.5gm of substance, dissolve in a mixture of 30ml water
and 20ml 1M H2SO4 solution and titrate with 0.1M Ce(SO4)2.2(NH4)2. SO4. 2H2O using ferroin
sulfate solution as indicator.
IP FACTOR: 1 ml of 0.1M Ce(SO4)2.2(NH4)2. SO4. 2H2O = 0.01519gm of FeSO4.
2. FeSO4 tablets
3. Dried FeSO4
4. Ferrous glauconate tablets
5. Ferrous fumarate tablets
6. TiO2
7. ascorbic acid tablets
8. Paracetamol
Unit IV Redox Titrations
2.

2. IODIMETRY

DEFINITION: Determination involving direct titration with iodine due to oxidizing powder of
iodine in aqueous solution such type of titrations are called iodimetric titrations.

PRINCIPLE: Oxidation and reduction process involving I2 is called in general as iodimetric

titrations. The direct titration with a standard solution of I2 is termed as iodimetric. Solutions of I2
are weak oxidizing agents that are used for the determination of strong oxidizing agents. The most
accurate description of the half reaction for I2 in the application is :

I3- + 2e- 3I- [E˚= 0.536 v]

Where I3 is the tri-iodide ion.

Standard I2 solutions have relatively limited applications compared with the other oxidants because
of their significantly smaller electrode potential. A solution of I2 in aqueous media has an intense
yellow to brown color. Since I2 solution can serve as its own indicator (self- indicator). However in
practice starch solution is used as an indicator for the most accurate end point.

STANDARDIZATION OF 0.05M I2 USING As2O3 :

1. PREPARATION OF 0.05M I2 SOLUTION: Dissolve about 14gm of I2 in a solution of 36gm of

KI in 100ml of water, add 3 drops of HCl and dilute with water to 100ml.

2. STANDARDIZATION OF I2 SOLUTION: Weigh accurately about 0.15gm of As2O3 , previously

dried at 105˚ for 1 hour and dissolve in 20ml of 1M NaOH by warming, if necessary. Dilute with
40ml of water, add 0.1ml of methyl orange solution and add drop wise dilute HCl until the yellow
color is changed to pink. Add 2gm of NaHCO3, dilute with 50ml of water and add 3ml of starch
solution as indicator. Titrate with prepared I2 solution until permanent blue color is produced.

IP/ EQUIVALENT FACTOR:

Each ml of 0.05M I2 solution = 0.004946gm of As2O3.

CALCULATION:

M of I2 solution = wt.of As2O3 x Expected M

Titration vol x IP Factor

APPLICATIONS:
1. Assay of Na2S2O3 (Sodium Hypo Sulphite) by iodimetry:
Mol.wt = 248.17gm. FORMULA: Na2S2O3 . 5H2O

CATEGORY: Antidote for cyanide poisoning.

DESCRIPTION: large colorless crystals or coarse crystalline powder,odorless, deliquesent in
moist air and effloresces in dry air , temperature above 33˚ .
Unit IV Redox Titrations
3.
PRINCIPLE: It is assayed by directly titrating with I2 solution called as iodimetry using starch
solution as Iindicator which is added towards the end of the titration . End point is the appearance of
blue color.

Na2S2O3 + I2 Na2 4O6 + 2NaI

PROCEDURE: Weigh accurately about 0.5gm of sample, dissolve in 20ml water and titrate with
0.05M I2 solution using starch solution as indicator until a blue color is produced.

IP/ EQUIVALENT FACTOR:

Each ml of 0.05M of I2 solution= 0.02482gm of Na2S2O3 solution.

CALCULATION:

% purity = Titration vol x IP factor x Actual Molarity x 100

Wt. taken x Expected Molarity

2. Assay of sodium meta bisulfide by iodimetry.

Unit IV Redox Titrations
4.
3. IODOMETRY:

DEFINITION: The titrations in which the equivalent amount of I2 is liberated from KI by the
sample the liberated I2 is titrated against standard Na2S2O3 solution such a type of indirect
determination of strong oxidizing agents is called iodometry.

PRINCIPLE: The titrations in which the liberated I2 is titrated with a standard solution of Na2S2O3
solution using starch-mucilage as indicator is called iodometric titrations. The indirect iodometric
titration method is termed as iodometry.

Na2S2O3 + I2 Na2S4O6 + 2NaI

STANDARDIZATION OF 0.1M Na2S2O3 :

1. Preparation of 0.1M Na2S2O3 solution : Dissolve 25gm of Na2S2O3 and 0.2gm of Na2CO3 in CO2
free water and dilute to 1000ml with water.
2. STANDARDIZATION OF Na2S2O3 SOLUTION: Dissolve 0.2gm of KBrO3 weighed accurately
in sufficient water to produce 250ml. To 50ml of this solution add 2gm of KI and 3ml of 2M HCl
solution and titrate with Na2S2O3 solution using starch solution as indicator until the blue color
disappears.

IP FACTOR: Each ml of 0.1M Na2S2O3 solution = 0.002784gm of KBrO3.

CALCULATION:

M of Na2S2O3 solution = Wt. of KBrO3 taken x Required Molarity

Titration vol x IP factor

APPLICATIONS:
1. Assay of CuSO4
2. Bleaching powder
3. Phenol
4. Chloramine
5. Detection of chlorate
6. Determination of As2O3
7. Determination of H2O2
8. Determination of H2SO3
9. Benzyl penicillin
10. Ceric sulphate

1. Assay of CuSO4 by iodometry:

PRINCIPLE:The determination of CuSO4 depends on the instability of cupric iodide formed by
reaction between CuSO4 and KI in the presence of CH3COOH.
2CuSO4 + 4KI CH3COOH
2CuI2 + 2K2SO4
Unit IV Redox Titrations
5.
I2 + 2Na2S2O3. Na2S4O6 + 2NaI

The unstable CuI2 is decomposed to cuprous iodide and free iodine.

2CuI 2 2CuI + I2

This reaction is reversible since CuI is slightly soluble, the backward reaction may be promoted.
The liberated I2 can be titrated with standard Na2S2O3 solution using starch-mucilage solution as
indicator.

PROCEDURE: Weigh accurately about 1gm of CuSO4 and dissolve in 50 ml of water, add 3gm of
KI and 5ml CH3COOH and titrate with liberated I2 with 0.1N Na2S2O3 using starch- mucilage as
indicator. Continue the titration until a faint blue color remains, add 2gm of Potassium Thiocyanate.
Stir well and continue the titration until the blue color disappears.

IP FACTOR: Each ml of 0.1N Na2 2O3 = 0.02497gm of CuSO4.

Unit IV Redox Titrations
6.

4. BROMATOMETRY (Potassium-Bromate titration)

PRINCIPLE: Potassium Bromate is a powerful oxidizing agent which is reduced smoothly to

bromide in the presence of HCl and which is then oxidized to give free bromine by bromate
(excess).

BrO3- + 6H+ + 6e- Br- + 3H2O

BrO3- + 5Br- + 6H+ 3Br2 + 3H2O

The equivalent is therefore 1/6 moles, KBrO 3 /6 or 167/6 which is equal to 27.88 . At the end point
of titration free bromine appears.

BrO3- + 5Br- + 6H+ 3Br2 + 3H2O therefore,

KBrO3 + 5Br- +6HCl. 3Br2. + 6KCl + 3H2O

PREPARATION OF 0.016M KBrO 3 SOLUTION: Potassium bromate is usually available in a

high state of purity. The anyalytical reagent product has an assay value of 99.9%. The substance can
be dried at 120-150˚ is anhydrous and the aqueous solution keeps it indefinitely, it can therefore be
employed as a primary standard. Its only disadvantage is that 1/6th of the relative molecular mass is
a Comparatively small quantity.

PREPARATION: Dissolve 2.783gm of KBrO 3 in sufficient quantity of water to produce 1000ml.

APPLICATIONS:
1. Assay of Isoniazid
2. Determination of Hydroxylamine
3. Determination of As/Sb

ASSAY OF ISONIAZID IP : Anti-tubercular drug. This is determined by addition of potassium

bromide and direct titration of potassium bromate in the presence of HCl solution. Bromine is
released as the titration proceeds and reacts with isoniazid as shown below the Azo-dye, methyl red
solution is used as an indicator which decolorises by oxidation at end point.

KBrO3 + 5Br- + 6HCl 3Br2. + 6KCl + 3H2O

PROCEDURE FOR ASSAY: Weigh accurately about 0.25gm in sufficient water to produce
100ml. From this solution take 20ml and add 100ml water, 20ml HCl and 0.2gm of KBr and titrate
slowly with continuous shaking with 0.016M KBrO3 solution using 0.05ml of methyl red solution
as indicator until the red color disappears.

IP FACTOR: Each ml of 0.016M KBrO3 solution = 0.003429gm of Isoniazid (C6H7N3O).

Unit IV Redox Titrations
7.
5. POTASSIUM-IODATE TITRATION:

DEFINITION: Potassium Iodate is a powerful oxidizing agent under suitable conditions, it reacts
quantitatively with both iodides and iodine, arsenides and other reducing agents. Iodate titration can
be performed in presence of alcohol, saturated organic acid and many other kinds of organic matter.

PRINCIPLE: The reaction between potassium iodate and reducing agents such as iodide ions or
As2O3 in solutions of moderate acidity (0.12 -2M HCl) stops at the state when the iodate is reduced
to iodine.

KIO3 + 5KI + 6HCl 3I2 + 6KCl + 3H2O

2KIO3 + 5H3AsO3 +2HCl I2 +5H3AsO4 +H2O +2KCl

STANDARDIZATION OF 0.05M POTASSIUM IODATE

PREPARATION OF 0.05M KIO3 SOLUTION: Dry some AR KIO3 at 120˚ for 1 hour and allow it
to cool in a dessicator. Weigh accurately about 10.7gm of finely powdered KIO3 and dissolve in
water and gently rotate the flask until the salt is completely dissolved, sufficient water is added to
produce 1000ml.

STANDARDIZATION OF KIO3 SOLUTION: To a definite volume of KIO3 solution add excess of

KI and dil.HCl and titrate the liberated I2 with Na2 2O3 solution.

APPLICATIONS:
1. Potassium iodide(KI)
2. Weak I2 solution
3. Aqueous I2 solution
4. Sodium diatrizoate
5. Iodized oil fuel injection
6. Determination of Hg(HgCl2)
7. Hydralazine HCl and injection IP

USP:
1. Benzalkonium chloride
2. Iodine tincture
3. Sodium Iodide

ASSAY OF POTASSIUM IODATE:

PRINCIPLE: if the concentration of HCl is less the reaction between KIO3 and KI stops,when the
iodide has been reduced to free iodine.

IO3- + 5I- + 6H+ 3I2 + 3H2O

PROCEDURE: weigh accurately about 0.35gm of KIO3 dissolved in about 10ml of water, add
35ml HCl and 5ml of chloroform. Titrate with 0.05M KIO3 until the purple color of I2 disappears
from the chloroform. Add the last portion of iodate solution drop wise and agitate vigorously and
Unit IV Redox Titrations
8.
continuously. Allow to stand for 5 mins, if any color develops in huge in chloroform layer continue
the titration until the chloroform layer, continue the titration until the chloroform is decolorised.
IP FACTOR: Each ml of 0.05M KIO3 solution = 0.0166ml of KI.

6. DICHROMETRY(Potassium Dichromate titration)

Primary standard used: Ammonium iron(II) sulphate

Indicator used: N-phenyl anthranilic acid

PRINCIPLE: As an oxidant, dichromate has advantages over permanganate but it is less powerful,
it's use is much more limited. It is obtainable in a state of high purity and can be used as primary
standard solutions of dichromate in water are state indefinite. The half reaction for dichromate is:

CrO7- + 14H+ + 6e- 2Cr+3 + 7H2O

The most important application of dichromate is in its reaction with iron (II) in which it is often
preferred to permanganate.

Cr2O7-2 + 6Fe+2 + 14H+. 2Cr+3 + 6Fe+3 + 7H2O

PREPARATION AND STANDARDIZATION OF 0.1M K2Cr2O7 :

PREPARATION OF 0.1M K2Cr2O7 : Weigh accurately 29.46gm of K2Cr2O7 and dissolve in 1000ml
of water to get 0.1N solution. To prepare 1N dissolve 49.03gm of K2Cr2O7 in 1000ml of water.

STANDARDIZATION: To 50ml of 0.1N Ferrous Ammonium Sulphate add 20ml H2SO4 and 1.5ml
of N-phenyl anthranilic acid. Titrate the excess of iron(II) salt with K2Cr2O7 solution until the water
changes from green to restore red color.

END POINT: Appearance of Pink/Red color.

REACTION:

2Cr+3 + 3S2O5-2 + 7H2O. Cr2O7- + 6HSO4- + 8H+

2S2O8-2 + 2H2O O2 + Fe+3 + 4HSO4-

CALCULATION:

M1V1 =M2V2

M1 = Molarity of K2Cr2O7
V1 = Volume ofK2Cr2O7 consumed (burette reading)
M2 = Molarity of ammonium iron(II) sulfate
V2 = Volume of ammonium iron(II) sulfate
Unit IV Redox Titrations
9.
APPLICATIONS:
1.Determine the % of Fe in sample of Fe wire
2. Determine ferrous and ferric ions in a solution
3. Determine ferric ion % in solution of ferric
alum
4. Determine the % of Fe in Fe ore such as
haematite
DETERMINATION OF IRON USING k2Cr2O7:
PRINCIPLE: As an oxidant dichromate has advantages over permanganate but it is less powerful
its use is much more limited. It is obtained in the state of high purity and can be used as primary
standard solution of dichromate in water are stable ingredients.
The half reaction of dichromate is:

Cr2O7- + 14H++ 6e- 2Cr+3 + 7H2O

The most important application of dichromate is in its reaction with iron(II) in which it is often
preferred to permanganate.

Cr2O72- +6Fe+2 + 14H+ 2Cr+3 + 6Fe+3 + 7H2O

METHOD:
Prepare a standard dichromate solution by dissolving an accurately weighed sample of 0.4gm in
water and make up the volume upto 1000ml in volumetric flask. Into the flask or beaker weigh out
accurately duplicate portions about 0.7gm of iron provided (in 100ml) add 30ml of dil. H2SO4 and
1000ml of water. 7ml of 85% H3PO4 and 5 drops of diphenylamine sulfonate indicator. Titrate with
dichromate solution and a purple color is appeared. Calculate the % of iron in solid state.