Redox Titration notes
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REDOX TITRATION
➢ Redox titration refers to a laboratory method to determine the analyte concentration by
carrying out a redox reaction between the analyte and the titrant.
➢ The redox titration often needs a redox indicator or a potentiometer.
➢ Rodex titration depends on an oxidation-reduction reaction that occurs between the
analyte and the titrant.
Principle ( concept) of Redox Titration
Let us discuss the theory of redox titration. Redox reactions consist of both oxidation and
reduction reactions. The primary features of these reactions are as follows:
1. Reduction Reaction…A substance undergoes a reduction in the following ways:
• Addition of hydrogen atom
• Removal of the oxygen atom
• Accepting electrons
• Reduction in the oxidation state of the substance
2. Oxidation Reaction…A substance undergoes oxidation in the following ways:
• Addition of oxygen
• Removal of hydrogen
• Loss or donation of electrons
• An overall increase in the oxidation state of the substance
Hence, we can say that redox titrations consist of a transfer of electrons between the titrant and
the analyte.
An example of this type of redox reaction is reacting the iodine solution with a reducing agent.A
starch indicator is used to determine the endpoint of this redox titration. Here, the diatomic
iodine gets reduced to the iodine ions and the blue coloured iodine solution loses its colour. This
reaction is known as iodometric titration.
An oxidizing agent
is a compound or element that participates in a redox (oxidation-reduction)
reaction and accepts electrons from a different species. An oxidant is a chemical compound that
easily transfers oxygen or another substance atoms in order to gain an electron.
A reducing agent
(also known as a reductant, reducer, or electron donor) is a chemical species
that "donates" an electron to an electron recipient (called the oxidizing agent, oxidant, oxidizer,
or electron acceptor)
Types of Redox Titrations
Redox titrations are named according to the titrant that is used:
• Bromometry uses a bromine (Br2) titrant.
• Cerimetry employs cerium(IV) salts.
• Dichrometry uses potassium dichromate.
• Iodometry uses iodine (I2).
• Permanganometry uses potassium permanganate.
Redox indicator
A redox indicator (also called an oxidation-reduction indicator) is an indicator which undergoes
a definite color change at a specific electrode potential.
The requirement for fast and reversible color change means that the oxidation-
reduction equilibrium for an indicator redox system needs to be established very quickly.
Therefore, only a few classes of organic redox systems can be used for indicator purposes.[1]
There are two common classes of redox indicators:
• metal complexes of phenanthroline and bipyridine. In these systems, the metal changes
oxidation state.
• organic redox systems such as methylene blue. In these systems, a proton participant in
the redox reaction. Therefore, sometimes redox indicators are also divided into two general
groups: independent or dependent on pH.
The most common redox indicator are organic compounds. Redox Indicator example: The
molecule 2,2'- Bipyridine is a redox Indicator. In solution, it changes from light blue to red at an
electrode potential of 0.97 V.
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.
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.
APPLICATIONS:
1. Assay of FeSO4 : FeSO4 .7H2O, molecular weight = 278gm.
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.
APPLICATIONS:
1. Assay of Na2S2O3 (Sodium Hypo Sulphite) by iodimetry:
Mol.wt = 248.17gm. FORMULA: Na2S2O3 . 5H2O
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.
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
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
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
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-
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
