Oxidation-Reduction Titration

1. Oxidation: Oxidation is the loss of electrons during a reaction by a molecule, atom or

ion.
2. Reduction: Reduction occurs when there is a gain of electrons or the oxidation state
of an atom, molecule, or ion decreases.
An example of a reaction is that between hydrogen and fluorine gas to form
hydrofluoric acid:
H2 + F2 → 2HF
In this reaction, hydrogen is being oxidized and fluorine is being reduced. The
reaction may be better understood if it is written in terms of two half-reactions.
H2 → 2H+ + 2e-
F2 + 2e-→ 2F-
3. Redox reaction: Redox reactions are oxidation-reduction chemical reactions in which
the reactants undergo a change in their oxidation states. The term ‘redox’ is a short
form of reduction-oxidation. The oxidation and reduction reactions always occur
simultaneously in redox reactions,

4. Oxidizing agents: Electron-accepting species which tend to undergo a reduction in

redox reactions are called oxidizing agents. They oxidize other reagents.
Examples: O2, O3, F2, Br2, H2SO4, H2O2, Halogens etc.
5. Reducing agents: A reducing agent, or reductant, loses electrons and is oxidized in a
chemical reaction. A reducing agent is typically in one of its lower possible oxidation
states, and is known as the electron donor. They reduce other substances (reactants)
Examples: H2, CO, Fe, Zn, Li, oxalic acid, formic acid, alkali metals etc.
 Titration: A titration is a common laboratory method of quantitative chemical
analysis where a solution of a known concentration is used to determine the
concentration of an unknown solution. The concentration of the solution which is
known is called ‘titrant’ and the concentration of the solution which has to be
determined is called ‘titrand’.

TITRATION

Acid-Base Precipitation Complexometric Redox

 Oxidation-Reduction Titration: Oxidation reduction titration is carried out on

the basis of oxidation-reduction reactions, where the transfer of electron between the
reactant (titrand) and titrant takes place.
 Criteria for reaction in redox titration:
i. Reaction should be rapid
ii. Reaction should go to the completion
iii. Reaction should be stoichiometric
iv. Reaction should provide easy detection of end point
 Redox Indicator: Electrode potential is the parameter which changes during the
course of titration and the magnitude change is maximum in the vicinity of
equivalence point. So indicator used in redox titration must change color due to
sudden change in the electrode potential of the system at the equivalence point. Such
indicators are known as redox indicator.
 Types of Redox Titration: There are different types of redox titrations, and
these are commonly named after the reagent being used.
i. Permanganometry: Permanganometry is a type of redox titration that
uses potassium permanganate as an oxidizing agent. Titrations with potassium
permanganate do not need an indicator because KMnO4 already acts as an
indicator! In a titration of iron(III) with permanganate, chemists use
 phosphoric acid to mask the color of iron(III) so that it does not interfere with
the color change at the end-point of the titration.
MnO4- + 8H+ + 5e- → Mn2+ + 4H2O
Limitations: It is difficult to get potassium permanganate in pure form and
completely free from manganese dioxide.
ii. Dichrometry: Dichrometry uses potassium dichromate (K2Cr2O7) as an
oxidizing agent. In this type of redox titration, a redox indicator (for example,
barium diphenylamine sulphonate) is used to tell us the end-point of the
titration. K2Cr2O7 has weak oxidizing power as compare to KMnO 4. But it is
available in pure form, thermally stable and less expensive. K 2Cr2O7 reduces
rapidly at ordinary temperature in acidic medium to form green chromium salt.
COD can be determined by dichrometry.
Cr2O7- + 14H+ + 6e- → 2Cr3+ + 7H2O
iii. Cerimetry: Ceric ammonium sulphate, Ce(NH4)4(SO4)4.2H2O is used as
oxidizing agent and it is a very powerful oxidizing agent. Ceric solution has
bright yellow color but on reduction cerous salt is colorless.
Ce4+ + e- → Ce3+
iv. Bromatometry: Potassium bromate KBrO3 as an oxidizing agent, mainly
used for determination of inorganic reducers. Bromatometry is done by two
methods- Direct and Indirect method. Direct method titration is carried out in
presence of HCl with bromate solution. In indirect method, excess bromine is
added and then excess of bromine is determined iodometrically. That is by
adding excess of KI and liberated iodine is determined by Na2S2O4 solution.
BrO3- + 6H+ + 6e- → Br- + 3H2O
v. Iodimetry: Determination of iodine is done in iodimetry. Iodine is a 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. Iodimetric titrations are usually
performed in neutral or slightly basic/acidic solutions.
I2 + Reducing agent → 2I

vi. Iodometry: In iodometry iodine is liberated in analyte solution through

oxidation of iodine and liberated iodine is titrated with strong reductant.
K2Cr2O7 + KI + H2SO4 → Cr2(SO4)3 + 4K2SO4 + 7H2O + 3I2
Na2S2O3 + I2 → Na2S4O6 + 2I
 Application of Redox Titration: Redox titremetry is used to analyse a wide range
of inorganic analytes. Some common applications are discussed below:
Redox titration in real life applications:
i. In the production of some important chemicals i.e., caustic soda, chlorine, Nitric acid
etc.
ii. In sanitizing water and bleaching materials.
iii. In electroplating.
iv. Many metals are separated from their ores with the help of redox reactions.
Redox Titration in Pharmacy: Redox titration is used in pharmaceutical analysis to
determine the purity of drugs.
Redox Titration in Industry:
i. Content analysis, wherein redox (oxidation-reduction) reactions are used to establish the
purity of raw materials.
ii. We can also find application of redox titration in polymer.
Redox Titration in Public Health and Environmental Analyses: In the determination of
dissolved oxygen in natural water such as lakes and rivers.
Redox Titration in Food:
i. It allows food manufacturers to determine the quantity of a reactant in a sample.
ii. It can be used to discover the amount of salt or sugar in a product or the concentration
of vitamin C or E, which has an effect on product color.
Redox Titration in Dentistry: During teeth whitening procedure, it is the hydrogen peroxide
that becomes oxidized and breaks the double chemical bonds of the chromogens, scattering
their molecules. Because stains result from accumulations of chromogens, once scattered they
appear lighter in color.
Redox Reaction in Electrochemistry: The battery used for generating DC current uses
redox reaction to produce electrical energy.
Redox Titration in Metallurgy: It is used in metallurgical processes for extracting metals
from ores and combustion of fuel. One of the titration methods used in hydrometallurgy is an
oxidation-reduction (redox) titration.

Advantages of redox titration:

1. It's usually inexpensive and requires little equipment which is generally available in
the lab
2. It does not need particular or expensive chemicals
3. Does not require high expertise, has a simple operating procedure
4. The analysis can be automated, with very precise results
5. Provides quick results
Disadvantages of redox titration:
1. It is a destructive technique that frequently consumes large amounts of the substance
being analyzed
2. It requires reactions to take place in a liquid phase
3. It produces large volumes of chemical waste