Radox Titration

UNIT IV
REDOX TITRATION
BY
Mrs. Shinde Pooja Nilkanth
SPM`S College Of Pharmacy, Akluj
Introduction
Concept of oxidation and reduction
Oxidation – Oxidation reaction is defined as loss of
electron.
Reduction - Reduction is defind as gain of electron.
Oxidation reduction reaction
Oxidation reduction reaction is chemical process in which
oxidation reduction occurs simultaneously which leads to
change in valency of reacting element.
If one atom undergoes an oxidation process second atom
undergoes to reduction.
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Oxidising agent -
Oxidising agents is defind as substances which
containing an atom or ion which gains an electron and
result in either decrease in positive valency or
increase in negative valency.
It includes halogens and certain compounds
containing metal or non metal in the state of higher
valency.
Example – KMno4, K4Cr2O7
ab
Reducing agent –
Reducing agents is defind as substance which
containing atom or ion that looses electron and result
in either increase in positive valency and decrease in
negative valency.
It includes metal and compounds containing metal or
non metal in state of lower valency.
Example – FeCl2, H2S.
ab
Redox potential –
Oxidising agent accepts electron and get reduced.
Reducing agent donates electron and get oxidised.
Due to transfer of electrons, changes in valency of
atoms or ions takes place which leads to positive
valency of oxidized atom or ions increases and
reduced atom or ion decreases.
Strong oxidising agent having capacity to accept
electron from many weak reducing agents.
ab
Weak oxidising agent have less capacity to accept

electron hence they can oxidise only strong reducing
agents
The way of redox reaction can be forecast by
characteristics of reactant, this characteristic is called as
Redox potential.
Redox potential is measured by measuring potential
difference between two systems by connecting both to
galvanic cell. System consist of oxidising and reduced
form of chemical element.
Equivalent weights of oxidizing and
reducing agents
Equivalent weight of oxidizing and reducing agents
are calculated by number of electron accepts or
donates by an atom or ion during redox reaction.
Examples
Oxidising agents
1. Potassium permanganate (KMnO4)
Permanganate ion in acidic medium form manganous
ion
MnO4 + 8H +5e Mn++ + 4H2O
ab
Equivalent weight of KMnO4 = Molecular weight
5
In neutral medium the product is manganese dioxide.

MnO-4 + 4H +3e MnO2 + 2H2O
Equivalent weight of KMnO4 = Molecular weight
3
Detection of end point
Internal indicator
These indicators shows different colour in oxidized and
reduced form.
Internal indicators shows sudden change in redox
potential near to end point.
Example
1. Ferroin – It has red colour in reduced form and pale
blue colour in oxidized form.
2. 1% solution of diphenylamine in conc. sulphuric acid –
colourless in reduced form and violet colour in
oxidized form.
ab
Self indicators
Some reagents shows change in colour due to redox
reaction and may serve as their own indicator are called as
self indicator and such reactions do not need any indicator
for detection of end point.
Example
1. Potassium permanganate - shows pink colour
2. Iodine - shows brown colour
But this type of indicators has the disadvantage that an
excess of oxidizing agent is always present at the end
point, to reduce error blank determination is required.
ab
External indicator
In this type of indicator few drops of titration solution
separated periodically from flask and mixed with
indicator which shows colour change at the
equivalence point.
Example
Ferrous ions gives deep blue colour in presence of
potassium ferricyanide.
ab
Instrumental method
This method is employed when visual indicator
method fails or has limited accuracy.
End point determined by use of potentiometer or
conductometer.
Types of redox titrations
Redox titration
Permagnometry Cerimetry Iodimetry Iodometry
Dichrometry
Bromatometry
PERMAGNOMETRY
In this method potassium permanganate (KMnO 4) is
used as oxidizing agent and as self indicator.
Potassium permanganate is secondary standard can
also be standardized by using primary standard like
oxalic acid and arsenic trioxide.
Limitation – It is difficult to get potassium
permanganate in pure form and completely free from
manganese dioxide.
ab
Applications –
1. Used for assay of hydrogen peroxide, ferrous
sulphate, ferrous ammonium sulphate.
2. For determination of nitrates and perchlorates
3. Determination of calcium as calcium oxalate.
4. Etamesylats is haemostatic determined
Dichrometry
Potassium dichromate is used as oxidising agent and it

is weak oxidising power as compare to potassium
permanganate.
But has some advantage that is available in pure
form, thermally stable, has definite shelf life and less
expensive.
Potassium dichromate rduced rapidly at ordinary
temperature in acidic medium to form green
chromium salt.
ab
Applications
1. Determination of iron in iron ore
2. Determination of chromium in chromium salt
3. Chemical oxygen demand can be determined by
dichrometry.
Cerimetry
Cerric ammonium sulphate is used as oxidising agent

ad it is powerful oxidising agent.
Cerric solution has bright yellow colour but on
reduction cerous salt is colourless.
Applications
1. Used for assay ferrous fumarate.
2. For determination of copper and molybdate.
3. Following dosage forms are detrmined by using
Cerimetry.
ab
a. Ferrous gluconate (tablets)

b. Ferrous fumarate (tablets)
c. Ferrous succinate (tablets)
d. Ferrous sulphate dried
e. Ferrous sulphate (tablets)
f. Paracetamol
g. Ascorbic acid (tablets)
Iodimetry
Determination of iodine is done in Iodimetry.

Iodine is weak oxidant and easily reduced by stannous
chloride, sodium thiosulphate and arsenic oxide.
Known volume of standard iodine solution is titrated
directly with reluctant by using starch as indicator.
Applications
1. For determination of reductant like stannous
chloride, sulphurous acid, sodium thiosulphate, and
arsenic oxide.
ab
2. Determination of analgine and acetarsol.

3. Assay of ascorbic acid, sodium ascorbate and
sodium thiosulphate.
Iodometry
In Iodometry iodine is liberated in analyte solution

through oxidation of iodine and liberated iodine is
titrated with strong reductant.
Applications
1. Determination of KMnO4, copper sulphate,
hydrogen peroxide, potassium dichromate.
2. Determination of chlorine in hypochlorite.
3. Determination of thyroxine in thyroid gland.
4. Detrmination of ferric ammonium citrate.
Bromatometry
Potassium bromate is used as oxidising agent, mainly used for
determination of inorganic reducers.
Bromatometry done by two methods
a. Direct
b. Indirect
Direct method - titration is carried out in presence of HCl
with bromate solution.
Indirect method – Excess bromine is added then excess of
bromine is determined iodometrically
ab
That is by adding excess of KI and liberated iodine is

determined by sodium thiosulphate solution.
Applications
1. Various metals like aluminium, iron copper, zinc,
cadmium, cobalt. Nickel determined by using
hydroxyquinoline and bromatometry.
2. Determination of phenols.
3. Determination of Hydroxylamine

Radox Titration

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UNIT IV

Weak oxidising agent have less capacity to accept

In neutral medium the product is manganese dioxide.

Permagnometry Cerimetry Iodimetry Iodometry

Potassium dichromate is used as oxidising agent and it

Cerric ammonium sulphate is used as oxidising agent

a. Ferrous gluconate (tablets)

Determination of iodine is done in Iodimetry.

2. Determination of analgine and acetarsol.

In Iodometry iodine is liberated in analyte solution

That is by adding excess of KI and liberated iodine is

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