UNIT IV – REDOX TITRATION
REDOX TITRATION
OXIDATION:
Oxidation is defined as loss of electrons (LEO).
Fe2+ → Fe3+ + e–
Addition of oxygen:
C + O2 → CO2 (oxidation of carbon)
Addition of electronegative element:
Fe + S → FeS (oxidation of Iron)
Removal of hydrogen:
H2S + Br2 → 2 HBr + S (oxidation of sulphide)
An oxidising agent : Oxidises another substance by taking electrons from it is also
called the oxidant and Gains electrons, and therefore becomes reduced.
Ex: Potassium permanganate, Iodine, Ferric chloride
REDUCTION:
Reduction is defined as gain of electrons (GER).
Ce4+ + e– → Ce3+
Addition of hydrogen:
N2 + 3 H2 → 2NH3 ( reduction of nitrogen)
Addition of electropositive element:
SnCl2 + 2HgCl2 → SnCl4 + Hg2Cl2 ( reduction of mercuric chloride)
Removal of oxygen
ZnO + C → Zn + CO (reduction of zinc oxide)
A reducing agent: Reduces another substance by donating electrons to it. Is also
called the reductant and Loses electrons, and therefore becomes oxidized
Ex: Arsenic tri oxide, Ferrous sulphate, Sodium thio sulphate
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UNIT IV – REDOX TITRATION
OXIDATION-REDUCTION REACTION:
Oxidation-reduction reaction is a process involving the transfer of electrons
from one element or ion to another resulting in the change of the valency
of reacting atoms or ions.
The valency of an element represents the number of electrons in which, the
atoms take on or give up, on reacting with other elements to form the
compound.
Depending on the compound, the valency of some elements varies
e.g. Iron can be bivalent or trivalent (in FeCl2, FeCl3, respectively), the
manganese can have valencies from 2 to 7 (MnO, MnO2, Mn2O3, Mn2O7).
REDOX TITRATION:
Redox titration is based on an oxidation-reduction reaction between the
titrant and the analyte.
It involves gain or loss of electron between oxidation and reduction occurs
simultaneously on redox system.
During redox titration or redox reaction, transfer of electrons from one
element to another will occur, hence one substance is oxidised and get
reduced at a time.
REDOX SYSTEM:
A system or solution containing an oxidant (oxidising agent) and its reduced
form is called as redox system.
For Ex: a solution containing Fe3+ ion and Fe2+ ion
The redox potential of this redox system can be measured by dipping a set
of indicator and reference electrode in to it.
The mobility of electron from one element to another element during
redox reaction will acquires certain potential which is called redox
potential.
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UNIT IV – REDOX TITRATION
It is given by following equation,
𝑅𝑇 𝑎𝑜𝑥𝑖
𝐸𝑟𝑒𝑑𝑜𝑥 = 𝐸 𝑜 + . log 𝑒
𝑛𝐹 𝑎𝑟𝑒𝑑
E redox = Redox potential of redox system
Eº = Potential of standard electrode
R = Gas constant
T = Absolute temperature
n = Number of electrons gained by oxidant
REDOX POTENTIAL:
The redox potential is defined as the potential at which there is
equal concentration of oxidized and reduced form.
This redox potential differs for every pair of oxidized or reduced
form.
For Example:
Ferric/Ferrous - Redox potential is +0.77 v
Dichromate/Chromate - Redox potential is -1.36 v
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UNIT IV – REDOX TITRATION
REDOX INDICATORS:
1. Self Indicator
The titrant itself shows change in colour at the endpoint of the redox
titration is called self indictor.
For this titration do not need any indicator for end point detection.
For Ex:Potassium permanganate is the titrant in permanganometry
titration, it shows appearance of pink colour as the end point without any
indicator.
2. External indicator
In external indicator method, few drops of the titration mixture is removed
periodically from the flask and placed on a white tile and then mixed with
drop of indicator to show the colour change at end point.
But this method is not widely used due to more chances of error.
Ex: Ferrous ion gives deep prussian blue colour with potassium ferric
cyanide
3. Internal indicator:
Few drops of indiator are added to the sample solution which shows the
endpoint by changing its colour.
They have characteristic colour in oxidized and reduced state.
Ex: Ferroin sulphate (1,10- Phenanthroline)
Red colour in reduced form and blue colour in oxidized form
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UNIT IV – REDOX TITRATION
TYPES OF REDOX TITRATION
1. Permanganometry
2. Ceriometry
3. Iodimetry
4. Iodometry
5. Bromatometry
6. Dichrometry
7. Titrations with potassium iodate
1. PERMANGANOMETRY
Principle:
Potassium permanganate is used as a titrant in permanganometry. It is a
very powerful oxidising agent and also used as a self indicator due to its intense
colour. This method is used for the determination of amount of reducing
substances.
During the titration, sample substance is oxidized and at the same time, the
titrant (KMnO4) itself is reduced. It shows the conversion of MnO4¯ ion
(permangnate ion) in to Mn²+ ion (manganese ion) in acid solution which shows
marked colour change at end point.
Ex: ferrous sulphate is oxidised in the presence of slphuric acid by KMnO4 and the
reaction is represented by the equation,
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UNIT IV – REDOX TITRATION
Ionic equation,
During the titration, the permanganate ion (pink colour) is reduced to
manganese ion (colourless). After the completion of this reaction (after the end
point), addition of a drop of KMnO4 will produce pink colour to the reaction
mixture, because there is no Ferrous ion to reduce the permanganate ion to
manganese ion.
So the appearance of permanent pink colour is taken as an endpoint in
permanganomtry titration.
PREPARATION AND STANDARDISATION OF 0.1M POTASSIUM PERMANGANATE:
Principle:
• It is based on redox titration, oxidation and reduction reaction occurs
simultaneously.
• Oxalic acid is used as primary standard and potassium permanganate is the
titrant and also used as self-indicator.
• Potassium permanganate is a strong oxidising agent and in the presence of
sulfuric acid it acts as a powerful oxidising agent.
• When potassium permanganate is standardized against oxalic acid,
KMnO4 itself gets reduced to MnSO4 (Mn2+ - manganese) ion with
evaluation of nascent oxygen. This liberated oxygen oxidizes the oxalic acid
to carbon-di-oxide.
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UNIT IV – REDOX TITRATION
• Here potassium permanganate itself acts as self-indicator and the endpoint
is appearance of pale pink colour in which the colour should be permanent
after shaking for 30 seconds.
Oxalic acid reacts with potassium permanganate in the following way,
Procedure:
Molecular Formula: KMnO4
Molecular Weight: 158.03
Preparation of 0.1M Potassium Permanganate
Dissolve 16gm of potassium permanganate in 1000ml of water, heat on a
water bath for one hour, allow to stand for 2 days and filter through glass wool.
Standardisation of 0.1M Potassium Permanganate
Weigh accurately about 0.63gm of oxalic acid and transfer into 1000ml of
volumetric flask, then dissolve it by adding the water upto the level. Pipette out
about 10ml of this solution into a clean 250ml conical flask and add 2.5ml of
[Link] acid.
Warm the solution at 60ºC and titrate it against 0.1 M potassium
permanganate until the appearance of pale pink colour in which the colour should
be permanent after shaking for 30 seconds.
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UNIT IV – REDOX TITRATION
APPLICATIONS OF PERMANGANOMETRY:
Assay of Hydrogen peroxide
Assay of Potassium bromide
Assay of ferrous sulphate
Assay of dibasic calcium phosphate
Assay of oxalic acid
Determination of calcium as calcium oxalate
Malic acid content in Cherry juice.
Assay of Etamsylate (Haemoatatic agent)
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UNIT IV – REDOX TITRATION
2. CERIOMETRY
Principle:
Cerric ammonium sulphate is strong oxidising agent in dilute sulphuric acid
medium and considerably more stable than standard Potassium permanganate
solution. Cerric ion (oxidised state) is bright yellow in colour. During the titration,
it is reduced by the analyte in to cerrous ion (colourless) up to the equivalent
point.
After the completion of this redox reaction, the addition of excess of titrant
(Cerric ammonium sulphate) makes the solution to yellow colour. So the
appearance of yellow colour is considred as end point and hence, Cerric
ammonium sulphate acts as self indicator.
Ferrous sulphate can be assayed by titrating with oxidizing agent cerric
ammonium sulphate using ferroin sulphate solution as an indicator. Cerric
ammonium sulphate oxidizes ferrous sulphate in acidic medium preferably in
sulphuric acid medium to ferric sulphate. Ferroin sulphate is an indicator used in
this titration which is a solution of O-Phenanthroline in aqueous solution of
ferrous sulphate, having red colour. After oxidizes the indicator to ferric form
having blue colour will be the end point or just disappearance of red colour.
Ionic equation:
If the sample solution is too dilute, it is necessary to detect the endpoint
with redox indicators, such as Ferrion sulphate, N-Phenyl anthranilic acid.
Ex: Ferroin sulphate (1,10- Phenanthroline)
Red colour in reduced form and blue colour in oxidized form
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UNIT IV – REDOX TITRATION
PREPARATION AND STANDARDISATION OF 0.1M CERRIC AMMONIUM
SULPHATE:
Principle: (Redox titration – Ceriometry)
• In this standardization of ceric ammonium sulphate, arsenic tri oxide is
used as primary standard.
• The principle is based on the oxidation of sodium arsenite (which is formed
from arsenic trioxide with sodium hydroxide solution) to sodium arsenate
by ceric ammonium sulphate. Ferroin sulphate is used as an indicator which
shows sharp colour change from pink or orange to very pale blue.
The reaction between ceric ammonium sulphate solution and arsenic
trioxide is very slow at ordinary temperature. Hence it is necessary to add
trace of osmic acid solution as catalyst to increase the reaction rate.
Procedure:
Molecular Formula: (NH4)Ce(SO4)2.2H2O
Molecular Weight: 632.56
Preparation of 0.1M Cerric Ammonium Sulphate:
Dissolve 65 g of cerric ammonium sulphate with the aid of gentle heat in a
mixture of 30 ml of sulphuric acid and 500 ml of water. Cool, filter the solution if
turbid and dilute to 1000 ml with water.
Standardization of 0.1 M Ceric ammonium sulphate:
Weigh accurately 0.2 g of arsenic trioxide previously dried at 105⁰ C for 1
hour and transferred to a 500ml conical flask. Wash the inner walls of the flask
with 25 ml of 8%w/v solution of sodium hydroxide solution. Dissolve the content
and add 100 ml of water.
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UNIT IV – REDOX TITRATION
Add 30 ml of dilute sulphuric acid, 0.15 ml of osmic acid, 0.1 ml of ferroin
sulphate and titrate with 0.1M ceric ammonium sulphate until the pink colour
changes to pale blue. Each ml of 0.1M ceric ammonium sulphate is equivalent to
0.004946 g of arsenic trioxide.
APPLICATIONS OF CERIMETRY:
Assay of Ferrous sulphate
Assay of Paracetamol
Assay of Ferrous gluconate tablets
Assay of Ferrous sulphate tablets
Assay of Ascorbic acid tablets (Vit.C)
Assay of Iron-dextron injection
Assay of Iron-sorbitol injection
Assay of Menodione
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UNIT IV – REDOX TITRATION
3. IODIMETRY
Principle:
Sample solution is directly titrated with standard Iodine [Link] is
weak oxidising agent and it is used for determination of easily oxidisable
substances. During iodimetric titration, iodine is reduced to form Iodide ion, so
the colour of iodine solution (yellow) will disappear.
After the endpoint, there is no analyte to reduce the Iodine, hence the
addition of drop of iodine will imparts yellow colour to the sample [Link]
appearance of yellow colour is considered as endpoint.
If starch is used as indicator which is added towards the end of the
titration, appearance of blue colour is considered as endpoint.
PREPARATION AND STANDARDISATION OF 0.05M IODINE:
Preparation of 0.05M Iodine:
Dissolve 12.8 gm of iodine along with 20 gm of Potassium iodide in water and
make upto 1 litre with distilled water. Iodine is volatile in nature, so should be
stored in tightly closed, amber coloured container. Iodine is practically insoluble
in water, so KI is added to dissolve the iodine. But, iodine behaves as free iodine
in this solution.
Standardisation of 0.05M Iodine using Arsenic Trioxide:
Principle:
Arsenic trioxide is used as a primary standard for standardizing Iodine
solution. It is slowly soluble in cold water, but readily soluble in NaOH solution to
form sodium arsenite.
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UNIT IV – REDOX TITRATION
The excess NaOH is neutralized with HCl acid using methyl orange as
indicator until the yellow colour is changed to pink. Then, the solution is titrated
with Iodine, it may produce hydriodic acid, which can be neutralized by adding
sodium bicarbonate.
This sodium bicarbonate, removes the hydriodic acid as rapidly as it is
formed, causing the reaction to go to completion towards endpoint.
Procedure
Weigh accurately about 0.15 gm of arsenic trioxide previously dried at
105oC for 1 hr. Dissolve it in 20 ml of 1MNaOH by warming if necessary. Dilute
with 40 ml of water and add methyl orange indicator and add [Link] acid
dropwise until the yellow colour is changed to pink. Add 2 gm of sodium
bicarbonate and dilute with 50 ml of water and add 3 ml of starch solution until a
permanent blue colour is produced.
APPLICATIONS OF IODIMETRY:
Used for determination of stannous chloride, sulphurous acid, sodium thio
sulphate.
Used in assay of Analgin, Ascorbic acid and sodium ascorbate
Assay of Dimercaprol
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UNIT IV – REDOX TITRATION
4. IODOMETRY
Principle:
The titration in which the equivalent amount of Iodine is liberated from
potassium iodide (KI) by the reaction with sample and the liberated iodine is
titrated with sodium thio sulphate (Na2S2O3) is called Iodometry method.
In this method, starch is used as indicator which is added towards the end
of the titration. The endpoint is detected by disappearance of blue colour.
Free iodine is liberated as a result of oxidation of Potassium iodide in acid
medium. This liberated Iodine is titrated with sodium thio sulphate (Na 2S2O3)
using starch is used as indicator which is added towards the end of the titration.
The endpoint is detected by disappearance of blue colour.
PREPARATION AND STANDARDISATION OF 0.1M SODIUM THIOSULPHATE:
Principle:
It is standardized by redox titration involving iodometric methods using
potassium bromate as primary standard. Potassium bromate solution is treated
with potassium iodide and hydrochloric acid to liberate iodine. This liberated
iodine is titrated with sodium thiosulphate solution (titrant) using starch solution
as indicator, added towards the end of the titration until the disappearance of
blue colour.
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UNIT IV – REDOX TITRATION
Procedure:
Molecular Formula: Na2S2O3
Molecular Weight: 158.1
Preparation of 0.1M Sodium Thiosulphate:
Dissolve 25gm of sodium thiosulphate and 0.2gm of sodium carbonate in
carbon-di-oxide free water and dilute to 1000ml with water.
Standardization of 0.1M Sodium Thiosulphate
Weigh accurately 0.2 gm of potassium bromate and dissolve in sufficient
water to produce 250 ml. To 50 ml of this solution add 2 gm of potassium iodide
and 3 ml of 2M hydrochloric acid and titrate with sodium thiosulphate solution
using starch solution, added towards the end of the titration as an indicator until
the blue colour is discharged. Each ml of 0.1M sodium thiosulphate is equivalent
to 0.002784 gm of potassium bromate (KBrO3).
APPLICATIONS OF IODOMETRY METHOD:
Determination of potassium permanganate
Determination of potassium iodate
Determination of potassium di chromate
Assay of copper sulphate
Assay of hydrogen peroxide
Assay of mannitol and phenindione
Used in the estimation of Thyroxine level in blood sample
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UNIT IV – REDOX TITRATION
5. BROMATOMETRY
Principle:
Redox titration which employed potassium bromate as a titrant is called
bromatometry. Potassium bromated is a powerful oxidizing agent which is
reduced to bromide in the presence of HCl acid during the titration. Thenit is
oxidized to give free bromine at the end of the titration, hence it produce
appearance of yellow colour as end point.
TYPES :
1. Direct titration
2. Indirect titration
DIRECT TITRATION:
Sample is directly titrated with potassium bromate in acid medium and it
produce free bromine at the end of the titration and appearance of yellow colour
is considered as end point.
After the equivalent point,
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UNIT IV – REDOX TITRATION
INDIRECT TITRATION:
Sample is treated with potassium bromate in presence of acid medium (HCl
acid) to liberate bromine. This liberated bromine is determined iodometrically by
adding excess of potassium iodide to produce free iodine. This liberated iodine is
titrated with .1M Sodium thio sulphate until the disappearance of yellow colour.
PREPARATION AND STANDARDIZATION OF 0.0167M POTASSIUM BROMATE:
Preparation:
About 2.783 gmof potassium bromated is dissolved in water to produce
1000 ml. (1 mole bromine is equivqlent to 1/6 mole of potassium bromate 1/6 =
0.0167).
Standardization:
About 30 ml of potassium bromate solution is taken in conical flak, 3gm of
potassium iodide and 3 ml of HCl acid are added. Kept aside for 5 mts to liberate
free iodine. This liberated iodine is titrated with 0.1M sodium thio sulphate until
the appearance of yellow colour. Each ml of 0.1M sodium thio sulphate is
equivalent to 0.002784 gm of potassium bromate.
APPLICATIONS:
1. Assay of Isoniazid
2. Assay of Hydroxylamine HCl
3. Determination of Arsenic and Antimony metals.
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UNIT IV – REDOX TITRATION
6. DICHROMETRY
Principle:
The titration involving potassium dichromate as titrant is known as
dichrometry. Potassium dichromate is less powerful oxidizing agent as compared
to potassium permanganate. The medium is maintained acidic by the use of dilute
sulphuric acid and this method is mainly used for the estimation of ferrous salts
and iodides.
During the titration, potassium dichromate is reduced rapidly at room
temperature in acid medium to form chromium ion (Cr3+). At the same time, the
sample (ferrous ion) is oxidized to ferric ion.
Diphenylamine, diphenyl benzidine and dihenyl sulphonate are used as
indicators. At the end point, all these three shows the colour changes from green
to violet (purple).
PRPARATION AND STANDARDIZATION OF 0.1N POTASSIUM DICHROMATE:
Preparation:
About 4.9 gm of Potassium dichromate is powdered and dried in desicator
for 4 hrs, dissolved in water to produce 1000 ml.
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UNIT IV – REDOX TITRATION
Standardization:
Principle:
Ferrous ammonium sulphate is used as primary standrard. When it is
titrated with 0.1N Potassium dichromate, ferrous ion is oxidized to ferric ion and
dichromate ion ( ) is reduced to green colour chromium in (Cr3+) in acid
medium. Diphenylamine is used as indicator and the colour changes from green
to purple is considered as endpoint.
Procedure:
Specified quantity of ferrous ammonium sulphate is weighed and
transferred into conical flask, dissolved it in 5M H 2SO4. Then it is titrated with
0.1N Potassium dichromate using Diphenylamine is used as indicator and the
colour changes from green to purple is considered as endpoint. Equivalent weight
factor is 0.039213 gm.
APPLICATIONS:
1. Determination of percentage of Iron in Iron ore.
2. Estimationof percentage content of Iron in iron wire.
3. Determination of concentration of ferrous ion in Iron syrup and ferric alum.
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UNIT IV – REDOX TITRATION
7. TITRATIONS WITH POTASSIUM IODATE
Principle :
Potassium iodate is a powerful oxidizing agent, under suitable conditions,
any reducing sample substances (like Potassium iodate, sodium arsenite, arsenic
acid) are treated with potassium iodate in presence of acid medium and liberates
free iodine. This liberated iodine is back titrated with sodium thio sulphate. End
point is detected by disappearance of yellow colour or disappearance of blue
colour if starch is used as indicator.
PREPARATION AND STANDARDIZATION OF 0.1M POTASSIUM IODATE:
Preparation:
About 10.7 gm of powdered potassium iodate is weighed and dissolved in 1
liter of water.
Standardization:
About 25 ml of 0.1M potassium iodate is taken in conical flask, 2 gm
potassium iodide and 10ml of 1M hydrochloric acid are added, to liberate free
iodine. The liberated iodine is titrated with 0.1M sodium thio sulphate using
starch as indicator. End point is disappearance of blue colour.
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UNIT IV – REDOX TITRATION
APPLICATIONS:
1. Assay of Potassium iodate.
2. Assay of weak or aqueous iodine solution.
3. Determination of mercury in mercuric chloride solution.
4. Assay of Hydralazine HCl injection
5. Assay of Benzalkonium chloride
6. Assay of Sodium iodide
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