Redox Titration

INTRODUCTION
This titrimetric method is mainly based upon the change of the oxidation
number or electrons transfer between the reactants, that is, these reactions
are mainly based upon the oxidation-reduction reactions. In oxidation-
reduction titration method, a reducing substance is titrated with standard
solution of an oxidizing agent (e.g., ceric ammonium sulphate) or an
oxidizing substance is titrated with the standard solution of the reducing
agent (e.g., titanous chloride).

PRINCIPLE
The principle involved in the oxidation-reduction titrations is that the
oxidation process involves the loss of electrons whereas the reduction
process involves the gain of electrons.

Oxidant + ne ↔ Reductant

The redox titration is mainly based upon the oxidation of the analyte by the
oxidizing agent and the oxidation and reduction of the reaction is
determined by the indicators or by potentiometric.

The permanganate ion undergoes the following reaction:

MnO4− + 8H+ + 5e− Mn+2 + 4H2O
Purple mangnate ion ↔ Colourless manganese ion

The dichromate ion undergoes the following reaction:

Cr2O7−2 + 14H+ + 6e− 2Cr+3 + 4H2O−
Orange dichromate ion ↔ Green chromium ion
THEORY
The oxidation leads to the increase in the oxidation number and reduction
leads to the decrease in the oxidation number. Oxidation process involves
the loss of electrons while the reduction process involves the gain of
electrons, that is, oxidizing agents undergo reduction and reducing agents
undergo oxidation.

Oxidant + ne− Reductant

Reductant Oxidant + ne−
Ce+4 + Fe+2 Ce+3 + Fe+3
Ce+4 + e− Ce+3 (Reduction)
Fe+2 Fe+3 + e− (Oxidation)

The ability of the compound to accept or lose electrons is expressed by the

standard electrode potential. This helps in the determination of ions which
undergoes oxidation or reduction.

OXIDISING AND REDUCING AGENTS

1. Oxidizing agents: The following are the commonly employed

oxidizing agents in redox titrations:

1. KMnO4 in dilute H2SO4:

MnO4− + 8H+ + 5e− Mn+2 + 4H2O

2. K2Cr2O7 in dilute H2SO4:

Cr2O7−2 + 14H+ + 6e− 2Cr+3 + 4H2O

3. Iodine solution:

I2 + 2e− 2I−
 2. Reducing agents: The following are the commonly employed reducing
agents in the redox titrations:

1. Mohr's salt (FeSO4−(NH4)2SO4−6H2O)

Fe+2 Fe+3 + e−

2. Oxalic acid (H2C2O4−2H2O)

Cr2O7−2 2CO2 + 2e−

3. Sodium thiosulphate (Na2S2O3−5H2O)

2S2O3−2 S4O6−2 + 2e−

FACTORS AFFECTING REDOX TITRATIONS

The only factor that affects the redox titration is pH.

Example: KMnO4 acts as an oxidizing agent in the alkaline medium, neutral
medium, and acidic medium. However, it acts as a strong oxidizing agent in
the acidic medium.

The factors that affect the redox titration curves are as follows:

1. Reactant concentration: The ability of the reactant undergoes

oxidation or reduction.
2. Completeness of the reaction: The incompleteness of the reaction
shows the depression in the titration curve.
REDOX INDICATORS
Redox indicator should be able to possess the sudden change at the
equivalence point during the redox titration. It should be capable of
undergoing the oxidation and reduction.
InOxidation + ne InReduction

Some indicators are specific to the compounds. They react with one of the
reactants in the titration to produce the colour.

Example Starch reacts with the iodine to produce deep blue colour.
:

Potassium thiocyanate (KSCN) reacts with iron to produce red

colour.

There are different types of redox indicators. They are as follows:

1. Based on the addition of the indicator:

I. Self indicators: The titrant itself acts as a self indicator. It

shows the intense colour at the end point.

Examples: Potassium permanganate—end point is pink to

colourless.

Iodine—end point is brown to black colour

Ceric ammonium sulphate—end point is colourless to yellow

colour

II. Internal indicators: These are added to the reaction mixture

during the titration.

Examples:  Phenanthroline
 blue

 Methylene blue,
etc.

3. External indicators: These are used externally by means of grooved tile

and then mixed with the indicator solutions.
 Example: Ferrous ions in dichromate solution show the Prussian blue
colour with potassium ferricyanide solution.

 Based on the nature of the indicator:

1. Metal organic complexes:

Example: Phenanthroline shows the colour change from blue to red.

2. Free organic complexes:

Example: Methylene blue shows the colour change from blue to

colourless.

 Based on the dependence on the pH:

1. pH independent indicators:

 Examples:  2,2’-bipyridine shows the colour change from

colourless to yellow.

  5,6-dimethylphenanthroline shows the colour change

from yellow-green to red.
2.pH dependent indicators:
  Examples:  Safrannin T shows the colour change from red-violet
to colourless.

  Neutral red shows the colour change from red to

colourless.
 Based on the instrument used for the endpoint detection: This method
is mainly based upon the conductivity determinations and potential
determinations at the end point. In this method, platinum electrode is used
as the indicator electrode and the glass electrode is used as the reference
electrode.
 Example: conductometry determinations.

TYPES OF REDOX TITRATIONS

1. Based on the titrant used:

1. Permanganate titration: The reducing substances are
determined directly by the potassium permanganate and the
oxidizing substances are determined indirectly.

Example: 2KMnO4 +10FeSO4 + 8H2SO4 5Fe2(SO4)3 + K2SO4 +

2MnSO4 +8H2O

2. Dichromate titration: The solution which is prepared from the

potassium dichromate is stable and acts as strong oxidizing
agent.

Example: 2K2Cr2O7 +6FeSO4 +7H2SO4 3Fe2(SO4)3 +K2SO4

+Cr2(SO4)3 +7H2O

3. Iodine titration:
 Direct method: Iodine is used as the titrating agent.
 Indirect method: The liberated iodine is back titrated with
the sodium thiosulphate.
 2. Based on the method:
1. Direct titration: Some substances are initially coloured and the
indicator solution is not necessary for the end point
determination.

Example: Azo dyes and quinones are titrated by this method.

2. Back titration: An excess volume of the titrant solution is added

to the sample solution and then the excess titrant is back
titrated with the other titrant solution.

Example: Chloramphenicol is titrated by this method.

PROCEDURE FOLLOWED FOR REDOX TITRATION

Reaction with Potassium Permanganate Solution (Oxidizing Agent)

This is the powerful oxidizing agent which is introduced by F. Margueritte.
The reaction mechanism is as follows:
MnO4− + H+ + 5e− Mn+2 + 4H2O

1. Preparation of the permanganate solution: The accurate amount of

the potassium permanganate is weighed on a watch glass and then it
is transferred into the beaker. Then this is dissolved in the three-
fourth portion of the distilled water and the mouth of the beaker is
covered with the appropriate stopper. The resulting solution is boiled
for 15-30 minutes and is allowed for cooling to room temperature.
The solution is filtered through a cotton plug and is made to desired
volume by adding distilled water.
2. Standardization of the potassium permanganate solution: The
standardization of the potassium permanganate solution is done by
the arsenic oxide solution or by sodium oxalate solution.
3. Applications of the potassium permanganate:
1. Used in the analysis of metallic peroxides: To the 100 ml of
distilled water concentrated sulphuric acid and boric acid is
added and then the mixture is cooled in the ice bath and then
the sample solution is added. The appropriate quantities are
taken and titrated with the standard permanganate solution.

2MnO4− + 5NO2 + 6H+ 2Mn+2 + 5O3− + 8H2O

2. Used in the determination of the nitrites: Commercial

potassium nitrite is weighed accurately and dissolved in the
cold water and is made to the desired volume with the distilled
water. Then the desired volume of the standard potassium
permanganate solution is taken and then appropriate volume of
the sulphuric acid is added. Then the nitrite solution is taken in
the burette and the permanganate solution is titrated until it
decolourizes.

2MnO4− + 5NO2 + 6H+ 2Mn+2 + 5NO3− + 3H2O