Redox Titration

Oxidation: Oxidation is a reaction in which an atom or ion loses one or more electrons.
Fe2+ - e- Fe3+

Reduction: Reduction is a reaction in which an atom or ion gains one or more electrons.
Fe3+ + e- Fe2+

Oxidizing Agent: Oxidizing agents are the substances which oxidizes the other substances
but reduced itself. They accept electron.

Fe3+ + e- Fe2+

Example: - KMnO4, K2Cr2O7, H2O2, MnO2, O2, O3

Reducing Agent: Reducing agents are the substances which reduce the other substances
and reduced itself. They donate electron.
Example: - H2S, FeSO4, HI, C, H2, Zn

Fe2+ - e- Fe3+

Oxidation number: Oxidation number of an element is the total number of electron, that
an atom either gains or losses in order to form a chemical bond. The oxidation number
of N is 3.
Valency: Valency is defined as the combining capacity of electron if an atom with other
in a molecule. The valency of C is 4.
Oxidation number

Valency

1. Oxidation number of an element is the 1. Oxidation number of an element is the

total number of electron, that an atom

total number of electron, that an atom

either gains or losses in order to form a

either gains or losses in order to form a

chemical bond.

chemical bond.

2. Varies from compound to compound.

2. It is usually fixed.

3. It may be whole number or fractional. 3. Always whole number, never fractional.

4. Represented by +, - sign.

4. Does not represented by +, - sign.

5. Can be zero.

5. Cannot be zero.

6. Ex: - the oxidation number of C is +2

6. Ex: - Valency of C is 4.

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Q. Describe Oxidation and Reduction occurs simultaneously.

Oxidation and reduction occurs simultaneously in a reaction, one substance being
reduced and the other substance being oxidized in the process. Consider a reaction
CuO + H2 Cu + H2O

Here, CuO gets reduced to copper and H2 oxidized to water, that is oxidation reduction
reaction occurs simultaneously in above reaction.

Q. Describe KMnO4 is not primary standard substance.

The reasons are

1. It is not 100% pure.

2. It has some impurities.
3. KMnO4 is a strong oxidizing agent and contains some reducing agents, which is
responsible for the breakdown of KMnO4 and the strength of KMnO4 is reduced.
4KMnO4 + 2H2O 4MnO2 + 3O2 + 4KOH

4. In the presence of MnO2, it act as auto catalyst as a result, the strength of KMnO 4
is reduced.

Q. why KI is used to prepare Iodine solution?

I2 is insoluble in cold water. To make it soluble or increase the solubility, KI is used. I 2 is
then soluble by forming complex with KI.

I2 + KI I3- + K+ ; (H2O H+ + OH-)

Q. Why starch indicator should be used just before the end point?
Starch form complex with I2 which is insoluble in H2O and then showed color. And I2
also become free and showed different color. For that reason starch should be used just
before the end point.
4H+ + O2 + 4I- 2I2 + 2H2O

Starch water insoluble (cold water)

I2 + starch complex Insoluble in H2O; I2 is not free easily.

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Iodimetric Titration: The titration of reducing agent with the direct help of standard
iodine solution is termed as iodimetric titration.
C6H8O6 + I2 C6H6O6 + 2HI

Iodometric Titration: The titration of oxidizing agent with the indirect help of iodine
(iodine salt) is termed as iodometric titration. In this method the free iodine is formed.
2CuSO4 + 4KI Cu2I2 + I2 + 2K2SO4
Na2S2O3 + I2 Na2S4O3 + 2NaI

Iodimetric Titration

Iodometric Titration

1. The titration of reducing agent with the 1. The titration of oxidizing agent with
direct help of standard iodine solution is the indirect help of iodine (iodine salt) is
termed as iodimetric titration.

termed as iodometric titration.

2. Iodine is directly involved.

2. Iodine is indirectly involved.

3. Refers to titration with standard 3. Refers to titration with a salt of iodine.

solution.
C6H8O6 + I2 C6H6O6 + 2HI

2CuSO4 + 4KI Cu2I2 + I2 + 2K2SO4

Q. Why indicator is not necessary for KMnO4 titration?

KMnO4 is a good example of self-indicating reagent, one drop will impart visible pink
coloration to several 100 milliliters of solution. Even in the presence of slightly colored

ions as iron (III). When the titration is completed at the end point, it becomes colorless.
It indicates the completion of titration. So, in KMnO 4 titration, no indicator is used.
Determination of EQUIVALENT WIGHT OF KMnO4
KMnO4 K+ + MnO4-

MnO4- - e- + 8H+ + 8e- Mn2+ + 2e- + 4H2O

Or, MnO4-+ 8H+ + 7e-+ 2e- Mn2+ + 2e- + 4H2O

Or, MnO4-+ 8H+ + 5e- Mn2+ + 4H2O

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Equivalent weight =

= 31.6

Determination of EQUIVALENT WIGHT OF K2Cr2O7

K2Cr2O7 K+ + Cr2O72 -

Cr2O72 - - 2e- + 14H+ + 14e- 7H2O + 6e- + 2Cr3+

Or, Cr2O72 - + 12e- - 6e- + 14H+ 7H2O + 2Cr3+

Equivalent weight =

Or, Cr2O72 - + 6e- + 14H+ 7H2O + 2Cr3+

= 49

K2Cr2O7 is a strong oxidizing agnet.

It is found in pure form.
Its concentration doesnot change.

As2O3
KMnO4 K+ + MNO4-

Reduction Half reaction,

MnO4-+ 8H+ + 5e- Mn2+ + 4H2O . (i)

As2O3 2As3+ + 3O2-

2As3+ 2As5+ + 4e- .. (ii)

Now, equation (i) 2 and equation (ii) 5

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As2O3 10As3+ 4MnO4- 20e- 20 1000ml 1N

20,000ml 1N KMnO4 126gm As2O3

1ml 1N KMnO4

gm As2O3

1ml 0.1N KMnO4

gm As2O3

= 6.3 10-4 gm As2O3

Fe-Gluconate (Fe2+)
KMnO4 K+ + MNO4-

Reduction Half reaction,

MnO4-+ 8H+ + 5e- Mn2+ + 4H2O . (i)

Fe2+ Fe3+ + e- .. (ii)

Now, equation (i) 1 and equation (ii) 5

Fe-gluconate 5 Fe2+ MnO4- 5e- 5 1000ml 1N

5,000ml 1N KMnO4 446gm Fe-gluconate

1ml 1N KMnO4

1ml 0.1N KMnO4

gm Fe-gluconate

gm Fe-gluconate

= 8.92 10-3 gm Fe-gluconate

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Na-Oxalate
KMnO4 K+ + MNO4-

Reduction Half reaction,

MnO4-+ 8H+ + 5e- Mn2+ + 4H2O . (i)

Now, equation (i) 2 and equation (ii) 5

Na=oxalate 2MnO4- 10e- 10 1000ml 1N

10,000ml 1N KMnO4 126gm Na-oxalate

1ml 1N KMnO4

1ml 0.1N KMnO4

gm Na-oxalate

gm Na-oxalate

= 1.26 10-3 gm Na-oxalate

Ascorbic acid

C6H8O6 2Ce3+ 2e- 2 1000ml 1N

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2,000ml 1N Ce4+ 176gm Ascorbic acid

1ml 1N Ce4+

gm Ascorbic acid

1ml 0.1N Ce4+

gm Ascorbic acid

= 0.0088 gm Ascorbic acid

Paracetamol

2,000ml 1M Ce4+ 176gm paracetamol

1ml 1M Ce4+

1ml 0.1M Ce4+

gm paracetamol

. .
,

gm paracetamol

= 0.00756 gm paracetamol

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Classification of non-aqueous solvents: The non-aqueous solvents are generally 4 types.

1. Protophilic Solvents.
2. Protogenic Solvents.

3. Amphiprotic Solvents.
4. Aprotic Solvents.
Protophilic Solvents: This type of solvents are basic in nature and reacts with acid to
form solvated proton.

HB + Solvent sol. H+ + B-

Example: - Ketone, Pyridine, Amines (Liquid Ammonia)

Protogenic Solvents: The substances which are capable of donating a proton, is known
as protogenic solvents. They are acidic in nature.

Example: - Acetic acid, formic acid, H2SO4, liquid HCl.

Amphiprotic Solvents: Amphiprotic solvents are defined as the solvents which can act
as both proton donors and acceptors.
Example: - Alcohol, Water.
Aprotic Solvents: Aprotic solvents are the solvents that either accept or donate proton.
Example: - Benzene, CCl4, Chloroform.
Characteristics: 1. Neutral in nature.
2. Chemically inert.
3. Do not favor ionization.

4. Useful for studying the reaction of acid-base free of solvent effects.

Titration of weak base: When a weak base like pyridine is dissolved in acetic acid
enhanced the basic properties of pyridine. It is possible therefore to titer a solution of
weak base in acetic acid with HClO4 acid and obtain a sharp end point.

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Solvent: Glacial acetic acid, alone or combine with an aprotic solvent.

Other Solvent: Chloroform, Acetone, Acetic anhydride, Chloro benzene, Benzene, Formic acid.
Titrant: Solution of HClO4 in glacial acetic acid.
Indicator: 1. Crystal violet
2. Oracet blue

3. Quinalidine red

HClO4 standardization by PHP:

HClO4 is a strong acid and CH3COOH is a weak acid. When a strong acid reacts with
weak acid, the weak acid act as base. But the strong acid CH 3COOH contains small
amount of water. For that reason we get only 70-72% HClO4 in pure form.
To reduce water from HClO4, acetic anhydride is added to the solution.

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But when acetic anhydride react with HClO4, an explosive product is formed. To reduce
this, at first acetic acid is added instead of water.

N. B: Weak Basic Drug- salt form Halogen Group

Titration of Chloride or Bromide Salt of Base

To titrant a base in the form of chloride or bromide salt, the counter ion has to be removed
prior to the titration. This is achieved by addition of Hg-acetate. The liberate acetate is
then titrated by acetous perchloric acid.

Titration of weak acid

Solvent: Alcohol (example: - Methanol)
Dimethylformamide.
Titrant: Methoxides of the alkali metals (e.g. lithium methoxide) dissolved in a mixture of
benzene and methanol.

Tetrabutyl ammonium hydroxide in Dimethylformamide.

Indicator: Thymol Blue, potentiometric determination.

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Q, why standardization and titration should be carried out at the same temperature in Nonaqueous titration?

Non-aqueous solvents in general have greater co-efficient of expression than water. So,
small temperature differences can cause significant errors unless suitable correction
factors are used.
Therefore, standardization and titration should be carried out as far as possible at the
same temperature. If it is not possible however, the volume of titration may be corrected
by applying following formula:

Vc = v [1+ 0.0011(t1 t2)]

Where,
t1 = temperature at which titrant was measured.
t2 = Temperature at which the titration was carried out.
Vc = Corrected volume of the titration.
v = Volume of titration measured.
Differentiating Solvent: Weak acidic solvent or weak basic solvent, which cannot
complete the reaction is called differentiating solvent. If the acid (HA) is dissolved in
solvent (S), then the following reaction occurs.

HA + S SH+ + A-

If the reaction does not go completely to the right, the solvent is called differentiating
solvent for the acid HA.

Leveling Solvent: Weak acid or base solvent which can complete the reaction is called
levelling solvent.
HX + S HS+ + X-

If the reaction goes to complete on, the solvent is levelling solvent.

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Q. short note on picric acid as aprotic solvent.

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Picric acid gives a colorless solution in benzene, indicating that no dissociation has
occurred.

On adding aniline, the solution becomes yellow. Owing to the formation of picrate ion.

In presence of base (aniline) picric acid act as acid. Aprotic solvents are often added to
suppress the solvolysis of the neutralizing product and sharper the end point. With his
expansions, aprotic solvents do not participate in only acid-base reactions, hence they
serve only as carriers for the reaction.
Q. Write down the Scope of Non-aqueous titration.
1. BP, USP employs non-aqueous titration to determine the purity of the drugs.
2. Most useful tool for the quality control of Pharmaceuticals. E.g. Nasal sprays.
3. Too weakly acidic or basic compounds titrated in this titrimetric method.

4. Used for substances which are insoluble in H 2O, but soluble in non-aqueous solvents.
5. Great application to the Pharmaceutical dosage forms e.g. Sulphonamides.
6. Many weak organic acids of medicinal have analyzed by non-aqueous titration.
Q. Write down the reactions involve in the titration of a weak base in benzene and acetic
acid by perchloric acid in dioxane.

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MD. ASIF HASAN NILOY | Pharmacy 24 Batch (3rd Semester)