Page 1
235 redox reactions
Chemistry deals with varieties of matter and change
of one kind of matter into the other. Transformation of
matter from one kind into another occurs through the
various types of reactions. One important category of such
reactions is Redox Reactions. A number of phenomena,
both physical as well as biological, are concerned with
redox reactions. These reactions find extensive use in
pharmaceutical, biological, industrial, metallurgical and
agricultural areas. The importance of these reactions is
apparent from the fact that burning of different types of
fuels for obtaining energy for domestic, transport and
other commercial purposes, electrochemical processes
for extraction of highly reactive metals and non-metals,
manufacturing of chemical compounds like caustic
soda, operation of dry and wet batteries and corrosion of
metals fall within the purview of redox processes. Of late,
environmental issues like Hydrogen Economy (use of
liquid hydrogen as fuel) and development of ‘Ozone Hole’
have started figuring under redox phenomenon.
7.1 CLASSICAL IDEA OF REDOX REACTIONS –
OXIDATION AND REDUCTION REACTIONS
Originally, the term oxidation was used to describe the
addition of oxygen to an element or a compound. Because
of the presence of dioxygen in the atmosphere (~20%),
many elements combine with it and this is the principal
reason why they commonly occur on the earth in the
form of their oxides. The following reactions represent
oxidation processes according to the limited definition of
oxidation:
2 Mg (s) + O
2
(g) ? 2 MgO (s) (7.1)
S (s) + O
2
(g) ? SO
2
(g) (7.2)
After studying this unit you will be
able to
• identify redox reactions as a class
of reactions in which oxidation
and reduction reactions occur
simultaneously;
• define the terms oxidation,
reduction, oxidant (oxidising
agent) and reductant (reducing
agent);
• explain mechanism of redox
reactions by electron transfer
process;
• use the concept of oxidation
number to identify oxidant and
reductant in a reaction;
• classify redox reaction into
combination (synthesis),
decomposition, displacement
and disproportionation
reactions;
• suggest a comparative order
among various reductants and
oxidants;
• balance chemical equations
using (i) oxidation number
(ii) half reaction method;
• learn the concept of redox
reactions in terms of electrode
processes.
UNIT 7
REDOX REACTIONS
Where there is oxidation, there is always reduction –
Chemistry is essentially a study of redox systems.
Unit 7.indd 235 10/10/2022 10:37:02 AM
2024-25
Page 2
235 redox reactions
Chemistry deals with varieties of matter and change
of one kind of matter into the other. Transformation of
matter from one kind into another occurs through the
various types of reactions. One important category of such
reactions is Redox Reactions. A number of phenomena,
both physical as well as biological, are concerned with
redox reactions. These reactions find extensive use in
pharmaceutical, biological, industrial, metallurgical and
agricultural areas. The importance of these reactions is
apparent from the fact that burning of different types of
fuels for obtaining energy for domestic, transport and
other commercial purposes, electrochemical processes
for extraction of highly reactive metals and non-metals,
manufacturing of chemical compounds like caustic
soda, operation of dry and wet batteries and corrosion of
metals fall within the purview of redox processes. Of late,
environmental issues like Hydrogen Economy (use of
liquid hydrogen as fuel) and development of ‘Ozone Hole’
have started figuring under redox phenomenon.
7.1 CLASSICAL IDEA OF REDOX REACTIONS –
OXIDATION AND REDUCTION REACTIONS
Originally, the term oxidation was used to describe the
addition of oxygen to an element or a compound. Because
of the presence of dioxygen in the atmosphere (~20%),
many elements combine with it and this is the principal
reason why they commonly occur on the earth in the
form of their oxides. The following reactions represent
oxidation processes according to the limited definition of
oxidation:
2 Mg (s) + O
2
(g) ? 2 MgO (s) (7.1)
S (s) + O
2
(g) ? SO
2
(g) (7.2)
After studying this unit you will be
able to
• identify redox reactions as a class
of reactions in which oxidation
and reduction reactions occur
simultaneously;
• define the terms oxidation,
reduction, oxidant (oxidising
agent) and reductant (reducing
agent);
• explain mechanism of redox
reactions by electron transfer
process;
• use the concept of oxidation
number to identify oxidant and
reductant in a reaction;
• classify redox reaction into
combination (synthesis),
decomposition, displacement
and disproportionation
reactions;
• suggest a comparative order
among various reductants and
oxidants;
• balance chemical equations
using (i) oxidation number
(ii) half reaction method;
• learn the concept of redox
reactions in terms of electrode
processes.
UNIT 7
REDOX REACTIONS
Where there is oxidation, there is always reduction –
Chemistry is essentially a study of redox systems.
Unit 7.indd 235 10/10/2022 10:37:02 AM
2024-25
236 chemistry In reactions (7.1) and (7.2), the elements
magnesium and sulphur are oxidised on
account of addition of oxygen to them.
Similarly, methane is oxidised owing to the
addition of oxygen to it.
CH
4
(g) + 2O
2
(g) ? CO
2
(g) + 2H
2
O (l) (7.3)
A careful examination of reaction (7.3) in
which hydrogen has been replaced by oxygen
prompted chemists to reinterpret oxidation
in terms of removal of hydrogen from it and,
therefore, the scope of term oxidation was
broadened to include the removal of hydrogen
from a substance. The following illustration is
another reaction where removal of hydrogen
can also be cited as an oxidation reaction.
2 H
2
S(g) + O
2
(g) ? 2 S (s) + 2 H
2
O (l) (7.4)
As knowledge of chemists grew, it was
natural to extend the term oxidation for
reactions similar to (7.1 to 7.4), which do
not involve oxygen but other electronegative
elements. The oxidation of magnesium with
fluorine, chlorine and sulphur etc. occurs
according to the following reactions :
Mg (s) + F
2
(g) ? MgF
2
(s) (7.5)
Mg (s) + Cl
2
(g) ? MgCl
2
(s) (7.6)
Mg (s) + S (s) ? MgS (s) (7.7)
Incorporating the reactions (7.5 to
7.7) within the fold of oxidation reactions
encouraged chemists to consider not only
the removal of hydrogen as oxidation, but
also the removal of electropositive elements
as oxidation. Thus the reaction :
2K
4
[Fe(CN)
6
](aq) + H
2
O
2
(aq) ?2K
3
[Fe(CN)
6
](aq)
+ 2 KOH (aq)
is interpreted as oxidation due to the removal
of electropositive element potassium from
potassium ferrocyanide before it changes to
potassium ferricyanide. To summarise, the
term “oxidation” is defined as the addition
of oxygen/electronegative element to
a substance or removal of hydrogen/
electropositive element from a substance.
In the beginning, reduction was considered
as removal of oxygen from a compound.
However, the term reduction has been
broadened these days to include removal
of oxygen/electronegative element from
a substance or addition of hydrogen/
electropositive element to a substance.
According to the definition given above,
the following are the examples of reduction
processes:
2 HgO (s) 2 Hg (l) + O
2
(g) (7.8)
(removal of oxygen from mercuric oxide )
2 FeCl
3
(aq) + H
2
(g) ?2 FeCl
2
(aq) + 2 HCl(aq)
(7.9)
(removal of electronegative element, chlorine
from ferric chloride)
CH
2
= CH
2
(g) + H
2
(g) ? H
3
C – CH
3
(g) (7.10)
(addition of hydrogen)
2HgCl
2
(aq) + SnCl
2
(aq) ? Hg
2
Cl
2
(s)+SnCl
4
(aq)
(7.11)
(addition of mercury to mercuric chloride)
In reaction (7.11) simultaneous oxidation
of stannous chloride to stannic chloride is
also occurring because of the addition of
electronegative element chlorine to it. It was
soon realised that oxidation and reduction
always occur simultaneously (as will be
apparent by re-examining all the equations
given above), hence, the word “redox” was
coined for this class of chemical reactions.
Problem 7.1
In the reactions given below, identify
the species undergoing oxidation and
reduction:
(i) H
2
S (g) + Cl
2
(g) ? 2 HCl (g) + S (s)
(ii) 3Fe
3
O
4
(s) + 8 Al (s) ? 9 Fe (s)
+ 4Al
2
O
3
(s)
(iii) 2 Na (s) + H
2
(g) ? 2 NaH (s)
Solution
(i) H
2
S is oxidised because a more
electronegative element, chlorine is added
to hydrogen (or a more electropositive
element, hydrogen has been removed
from S). Chlorine is reduced due to
addition of hydrogen to it.
(ii) Aluminium is oxidised because
oxygen is added to it. Ferrous ferric oxide
Unit 7.indd 236 10/10/2022 10:37:03 AM
2024-25
Page 3
235 redox reactions
Chemistry deals with varieties of matter and change
of one kind of matter into the other. Transformation of
matter from one kind into another occurs through the
various types of reactions. One important category of such
reactions is Redox Reactions. A number of phenomena,
both physical as well as biological, are concerned with
redox reactions. These reactions find extensive use in
pharmaceutical, biological, industrial, metallurgical and
agricultural areas. The importance of these reactions is
apparent from the fact that burning of different types of
fuels for obtaining energy for domestic, transport and
other commercial purposes, electrochemical processes
for extraction of highly reactive metals and non-metals,
manufacturing of chemical compounds like caustic
soda, operation of dry and wet batteries and corrosion of
metals fall within the purview of redox processes. Of late,
environmental issues like Hydrogen Economy (use of
liquid hydrogen as fuel) and development of ‘Ozone Hole’
have started figuring under redox phenomenon.
7.1 CLASSICAL IDEA OF REDOX REACTIONS –
OXIDATION AND REDUCTION REACTIONS
Originally, the term oxidation was used to describe the
addition of oxygen to an element or a compound. Because
of the presence of dioxygen in the atmosphere (~20%),
many elements combine with it and this is the principal
reason why they commonly occur on the earth in the
form of their oxides. The following reactions represent
oxidation processes according to the limited definition of
oxidation:
2 Mg (s) + O
2
(g) ? 2 MgO (s) (7.1)
S (s) + O
2
(g) ? SO
2
(g) (7.2)
After studying this unit you will be
able to
• identify redox reactions as a class
of reactions in which oxidation
and reduction reactions occur
simultaneously;
• define the terms oxidation,
reduction, oxidant (oxidising
agent) and reductant (reducing
agent);
• explain mechanism of redox
reactions by electron transfer
process;
• use the concept of oxidation
number to identify oxidant and
reductant in a reaction;
• classify redox reaction into
combination (synthesis),
decomposition, displacement
and disproportionation
reactions;
• suggest a comparative order
among various reductants and
oxidants;
• balance chemical equations
using (i) oxidation number
(ii) half reaction method;
• learn the concept of redox
reactions in terms of electrode
processes.
UNIT 7
REDOX REACTIONS
Where there is oxidation, there is always reduction –
Chemistry is essentially a study of redox systems.
Unit 7.indd 235 10/10/2022 10:37:02 AM
2024-25
236 chemistry In reactions (7.1) and (7.2), the elements
magnesium and sulphur are oxidised on
account of addition of oxygen to them.
Similarly, methane is oxidised owing to the
addition of oxygen to it.
CH
4
(g) + 2O
2
(g) ? CO
2
(g) + 2H
2
O (l) (7.3)
A careful examination of reaction (7.3) in
which hydrogen has been replaced by oxygen
prompted chemists to reinterpret oxidation
in terms of removal of hydrogen from it and,
therefore, the scope of term oxidation was
broadened to include the removal of hydrogen
from a substance. The following illustration is
another reaction where removal of hydrogen
can also be cited as an oxidation reaction.
2 H
2
S(g) + O
2
(g) ? 2 S (s) + 2 H
2
O (l) (7.4)
As knowledge of chemists grew, it was
natural to extend the term oxidation for
reactions similar to (7.1 to 7.4), which do
not involve oxygen but other electronegative
elements. The oxidation of magnesium with
fluorine, chlorine and sulphur etc. occurs
according to the following reactions :
Mg (s) + F
2
(g) ? MgF
2
(s) (7.5)
Mg (s) + Cl
2
(g) ? MgCl
2
(s) (7.6)
Mg (s) + S (s) ? MgS (s) (7.7)
Incorporating the reactions (7.5 to
7.7) within the fold of oxidation reactions
encouraged chemists to consider not only
the removal of hydrogen as oxidation, but
also the removal of electropositive elements
as oxidation. Thus the reaction :
2K
4
[Fe(CN)
6
](aq) + H
2
O
2
(aq) ?2K
3
[Fe(CN)
6
](aq)
+ 2 KOH (aq)
is interpreted as oxidation due to the removal
of electropositive element potassium from
potassium ferrocyanide before it changes to
potassium ferricyanide. To summarise, the
term “oxidation” is defined as the addition
of oxygen/electronegative element to
a substance or removal of hydrogen/
electropositive element from a substance.
In the beginning, reduction was considered
as removal of oxygen from a compound.
However, the term reduction has been
broadened these days to include removal
of oxygen/electronegative element from
a substance or addition of hydrogen/
electropositive element to a substance.
According to the definition given above,
the following are the examples of reduction
processes:
2 HgO (s) 2 Hg (l) + O
2
(g) (7.8)
(removal of oxygen from mercuric oxide )
2 FeCl
3
(aq) + H
2
(g) ?2 FeCl
2
(aq) + 2 HCl(aq)
(7.9)
(removal of electronegative element, chlorine
from ferric chloride)
CH
2
= CH
2
(g) + H
2
(g) ? H
3
C – CH
3
(g) (7.10)
(addition of hydrogen)
2HgCl
2
(aq) + SnCl
2
(aq) ? Hg
2
Cl
2
(s)+SnCl
4
(aq)
(7.11)
(addition of mercury to mercuric chloride)
In reaction (7.11) simultaneous oxidation
of stannous chloride to stannic chloride is
also occurring because of the addition of
electronegative element chlorine to it. It was
soon realised that oxidation and reduction
always occur simultaneously (as will be
apparent by re-examining all the equations
given above), hence, the word “redox” was
coined for this class of chemical reactions.
Problem 7.1
In the reactions given below, identify
the species undergoing oxidation and
reduction:
(i) H
2
S (g) + Cl
2
(g) ? 2 HCl (g) + S (s)
(ii) 3Fe
3
O
4
(s) + 8 Al (s) ? 9 Fe (s)
+ 4Al
2
O
3
(s)
(iii) 2 Na (s) + H
2
(g) ? 2 NaH (s)
Solution
(i) H
2
S is oxidised because a more
electronegative element, chlorine is added
to hydrogen (or a more electropositive
element, hydrogen has been removed
from S). Chlorine is reduced due to
addition of hydrogen to it.
(ii) Aluminium is oxidised because
oxygen is added to it. Ferrous ferric oxide
Unit 7.indd 236 10/10/2022 10:37:03 AM
2024-25
237 redox reactions
(Fe
3
O
4
) is reduced because oxygen has
been removed from it.
(iii) With the careful application of the
concept of electronegativity only we
may infer that sodium is oxidised and
hydrogen is reduced.
Reaction (iii) chosen here prompts us to
think in terms of another way to define
redox reactions.
7.2 REDOX REACTIONS IN TERMS OF
ELECTRON TRANSFER REACTIONS
We have already learnt that the reactions
2Na(s) + Cl
2
(g) ? 2NaCl (s) (7.12)
4Na(s) + O
2
(g) ? 2Na
2
O(s) (7.13)
2Na(s) + S(s) ? Na
2
S(s) (7.14)
are redox reactions because in each of these
reactions sodium is oxidised due to the addition
of either oxygen or more electronegative
element to sodium. Simultaneously, chlorine,
oxygen and sulphur are reduced because to
each of these, the electropositive element
sodium has been added. From our knowledge
of chemical bonding we also know that sodium
chloride, sodium oxide and sodium sulphide
are ionic compounds and perhaps better
written as Na
+
Cl
–
(s), (Na
+
)
2
O
2–
(s), and (Na
+
)
2
S
2–
(s). Development of charges on the species
produced suggests us to rewrite the reactions
(7.12 to 7.14) in the following manner :
For convenience, each of the above
processes can be considered as two separate
steps, one involving the loss of electrons
and the other the gain of electrons. As an
illustration, we may further elaborate one of
these, say, the formation of sodium chloride.
2 Na(s) ? 2 Na
+
(g)
+ 2e
–
Cl
2
(g) + 2e
–
? 2 Cl
–
(g)
Each of the above steps is called a half
reaction, which explicitly shows involvement
of electrons. Sum of the half reactions gives
the overall reaction :
2 Na(s) + Cl
2
(g) ? 2 Na
+
Cl
–
(s) or 2 NaCl (s)
Reactions 7.12 to 7.14 suggest that half
reactions that involve loss of electrons are
called oxidation reactions. Similarly, the
half reactions that involve gain of electrons
are called reduction reactions. It may not
be out of context to mention here that the
new way of defining oxidation and reduction
has been achieved only by establishing a
correlation between the behaviour of species
as per the classical idea and their interplay
in electron-transfer change. In reactions (7.12
to 7.14) sodium, which is oxidised, acts as
a reducing agent because it donates electron
to each of the elements interacting with it and
thus helps in reducing them. Chlorine, oxygen
and sulphur are reduced and act as oxidising
agents because these accept electrons from
sodium. To summarise, we may mention that
Oxidation : Loss of electron(s) by any species.
Reduction : Gain of electron(s) by any species.
Oxidising agent : Acceptor of electron(s).
Reducing agent : Donor of electron(s).
Problem 7.2 Justify that the reaction:
2 Na(s) + H
2
(g) ? 2 NaH (s) is a redox
change.
Solution
Since in the above reaction the compound
formed is an ionic compound, which may
also be represented as Na
+
H
–
(s), this
suggests that one half reaction in this
process is :
2 Na (s) ? 2 Na
+
(g) + 2e
–
Unit 7.indd 237 10/10/2022 10:37:03 AM
2024-25
Page 4
235 redox reactions
Chemistry deals with varieties of matter and change
of one kind of matter into the other. Transformation of
matter from one kind into another occurs through the
various types of reactions. One important category of such
reactions is Redox Reactions. A number of phenomena,
both physical as well as biological, are concerned with
redox reactions. These reactions find extensive use in
pharmaceutical, biological, industrial, metallurgical and
agricultural areas. The importance of these reactions is
apparent from the fact that burning of different types of
fuels for obtaining energy for domestic, transport and
other commercial purposes, electrochemical processes
for extraction of highly reactive metals and non-metals,
manufacturing of chemical compounds like caustic
soda, operation of dry and wet batteries and corrosion of
metals fall within the purview of redox processes. Of late,
environmental issues like Hydrogen Economy (use of
liquid hydrogen as fuel) and development of ‘Ozone Hole’
have started figuring under redox phenomenon.
7.1 CLASSICAL IDEA OF REDOX REACTIONS –
OXIDATION AND REDUCTION REACTIONS
Originally, the term oxidation was used to describe the
addition of oxygen to an element or a compound. Because
of the presence of dioxygen in the atmosphere (~20%),
many elements combine with it and this is the principal
reason why they commonly occur on the earth in the
form of their oxides. The following reactions represent
oxidation processes according to the limited definition of
oxidation:
2 Mg (s) + O
2
(g) ? 2 MgO (s) (7.1)
S (s) + O
2
(g) ? SO
2
(g) (7.2)
After studying this unit you will be
able to
• identify redox reactions as a class
of reactions in which oxidation
and reduction reactions occur
simultaneously;
• define the terms oxidation,
reduction, oxidant (oxidising
agent) and reductant (reducing
agent);
• explain mechanism of redox
reactions by electron transfer
process;
• use the concept of oxidation
number to identify oxidant and
reductant in a reaction;
• classify redox reaction into
combination (synthesis),
decomposition, displacement
and disproportionation
reactions;
• suggest a comparative order
among various reductants and
oxidants;
• balance chemical equations
using (i) oxidation number
(ii) half reaction method;
• learn the concept of redox
reactions in terms of electrode
processes.
UNIT 7
REDOX REACTIONS
Where there is oxidation, there is always reduction –
Chemistry is essentially a study of redox systems.
Unit 7.indd 235 10/10/2022 10:37:02 AM
2024-25
236 chemistry In reactions (7.1) and (7.2), the elements
magnesium and sulphur are oxidised on
account of addition of oxygen to them.
Similarly, methane is oxidised owing to the
addition of oxygen to it.
CH
4
(g) + 2O
2
(g) ? CO
2
(g) + 2H
2
O (l) (7.3)
A careful examination of reaction (7.3) in
which hydrogen has been replaced by oxygen
prompted chemists to reinterpret oxidation
in terms of removal of hydrogen from it and,
therefore, the scope of term oxidation was
broadened to include the removal of hydrogen
from a substance. The following illustration is
another reaction where removal of hydrogen
can also be cited as an oxidation reaction.
2 H
2
S(g) + O
2
(g) ? 2 S (s) + 2 H
2
O (l) (7.4)
As knowledge of chemists grew, it was
natural to extend the term oxidation for
reactions similar to (7.1 to 7.4), which do
not involve oxygen but other electronegative
elements. The oxidation of magnesium with
fluorine, chlorine and sulphur etc. occurs
according to the following reactions :
Mg (s) + F
2
(g) ? MgF
2
(s) (7.5)
Mg (s) + Cl
2
(g) ? MgCl
2
(s) (7.6)
Mg (s) + S (s) ? MgS (s) (7.7)
Incorporating the reactions (7.5 to
7.7) within the fold of oxidation reactions
encouraged chemists to consider not only
the removal of hydrogen as oxidation, but
also the removal of electropositive elements
as oxidation. Thus the reaction :
2K
4
[Fe(CN)
6
](aq) + H
2
O
2
(aq) ?2K
3
[Fe(CN)
6
](aq)
+ 2 KOH (aq)
is interpreted as oxidation due to the removal
of electropositive element potassium from
potassium ferrocyanide before it changes to
potassium ferricyanide. To summarise, the
term “oxidation” is defined as the addition
of oxygen/electronegative element to
a substance or removal of hydrogen/
electropositive element from a substance.
In the beginning, reduction was considered
as removal of oxygen from a compound.
However, the term reduction has been
broadened these days to include removal
of oxygen/electronegative element from
a substance or addition of hydrogen/
electropositive element to a substance.
According to the definition given above,
the following are the examples of reduction
processes:
2 HgO (s) 2 Hg (l) + O
2
(g) (7.8)
(removal of oxygen from mercuric oxide )
2 FeCl
3
(aq) + H
2
(g) ?2 FeCl
2
(aq) + 2 HCl(aq)
(7.9)
(removal of electronegative element, chlorine
from ferric chloride)
CH
2
= CH
2
(g) + H
2
(g) ? H
3
C – CH
3
(g) (7.10)
(addition of hydrogen)
2HgCl
2
(aq) + SnCl
2
(aq) ? Hg
2
Cl
2
(s)+SnCl
4
(aq)
(7.11)
(addition of mercury to mercuric chloride)
In reaction (7.11) simultaneous oxidation
of stannous chloride to stannic chloride is
also occurring because of the addition of
electronegative element chlorine to it. It was
soon realised that oxidation and reduction
always occur simultaneously (as will be
apparent by re-examining all the equations
given above), hence, the word “redox” was
coined for this class of chemical reactions.
Problem 7.1
In the reactions given below, identify
the species undergoing oxidation and
reduction:
(i) H
2
S (g) + Cl
2
(g) ? 2 HCl (g) + S (s)
(ii) 3Fe
3
O
4
(s) + 8 Al (s) ? 9 Fe (s)
+ 4Al
2
O
3
(s)
(iii) 2 Na (s) + H
2
(g) ? 2 NaH (s)
Solution
(i) H
2
S is oxidised because a more
electronegative element, chlorine is added
to hydrogen (or a more electropositive
element, hydrogen has been removed
from S). Chlorine is reduced due to
addition of hydrogen to it.
(ii) Aluminium is oxidised because
oxygen is added to it. Ferrous ferric oxide
Unit 7.indd 236 10/10/2022 10:37:03 AM
2024-25
237 redox reactions
(Fe
3
O
4
) is reduced because oxygen has
been removed from it.
(iii) With the careful application of the
concept of electronegativity only we
may infer that sodium is oxidised and
hydrogen is reduced.
Reaction (iii) chosen here prompts us to
think in terms of another way to define
redox reactions.
7.2 REDOX REACTIONS IN TERMS OF
ELECTRON TRANSFER REACTIONS
We have already learnt that the reactions
2Na(s) + Cl
2
(g) ? 2NaCl (s) (7.12)
4Na(s) + O
2
(g) ? 2Na
2
O(s) (7.13)
2Na(s) + S(s) ? Na
2
S(s) (7.14)
are redox reactions because in each of these
reactions sodium is oxidised due to the addition
of either oxygen or more electronegative
element to sodium. Simultaneously, chlorine,
oxygen and sulphur are reduced because to
each of these, the electropositive element
sodium has been added. From our knowledge
of chemical bonding we also know that sodium
chloride, sodium oxide and sodium sulphide
are ionic compounds and perhaps better
written as Na
+
Cl
–
(s), (Na
+
)
2
O
2–
(s), and (Na
+
)
2
S
2–
(s). Development of charges on the species
produced suggests us to rewrite the reactions
(7.12 to 7.14) in the following manner :
For convenience, each of the above
processes can be considered as two separate
steps, one involving the loss of electrons
and the other the gain of electrons. As an
illustration, we may further elaborate one of
these, say, the formation of sodium chloride.
2 Na(s) ? 2 Na
+
(g)
+ 2e
–
Cl
2
(g) + 2e
–
? 2 Cl
–
(g)
Each of the above steps is called a half
reaction, which explicitly shows involvement
of electrons. Sum of the half reactions gives
the overall reaction :
2 Na(s) + Cl
2
(g) ? 2 Na
+
Cl
–
(s) or 2 NaCl (s)
Reactions 7.12 to 7.14 suggest that half
reactions that involve loss of electrons are
called oxidation reactions. Similarly, the
half reactions that involve gain of electrons
are called reduction reactions. It may not
be out of context to mention here that the
new way of defining oxidation and reduction
has been achieved only by establishing a
correlation between the behaviour of species
as per the classical idea and their interplay
in electron-transfer change. In reactions (7.12
to 7.14) sodium, which is oxidised, acts as
a reducing agent because it donates electron
to each of the elements interacting with it and
thus helps in reducing them. Chlorine, oxygen
and sulphur are reduced and act as oxidising
agents because these accept electrons from
sodium. To summarise, we may mention that
Oxidation : Loss of electron(s) by any species.
Reduction : Gain of electron(s) by any species.
Oxidising agent : Acceptor of electron(s).
Reducing agent : Donor of electron(s).
Problem 7.2 Justify that the reaction:
2 Na(s) + H
2
(g) ? 2 NaH (s) is a redox
change.
Solution
Since in the above reaction the compound
formed is an ionic compound, which may
also be represented as Na
+
H
–
(s), this
suggests that one half reaction in this
process is :
2 Na (s) ? 2 Na
+
(g) + 2e
–
Unit 7.indd 237 10/10/2022 10:37:03 AM
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238 chemistry and the other half reaction is:
H
2
(g) + 2e
–
? 2 H
–
(g)
This splitting of the reaction under
examination into two half reactions
automatically reveals that here sodium
is oxidised and hydrogen is reduced,
therefore, the complete reaction is a
redox change.
7.2.1 Competitive Electron Transfer
Reactions
Place a strip of metallic zinc in an aqueous
solution of copper nitrate as shown in Fig.
7.1, for about one hour. You may notice
that the strip becomes coated with reddish
metallic copper and the blue colour of the
solution disappears. Formation of Zn
2+
ions
among the products can easily be judged
when the blue colour of the solution due to
Cu
2+
has disappeared. If hydrogen sulphide
gas is passed through the colourless solution
containing Zn
2+
ions, appearance of white zinc
sulphide, ZnS can be seen on making the
solution alkaline with ammonia.
The reaction between metallic zinc and the
aqueous solution of copper nitrate is :
Zn(s) + Cu
2+
(aq) ? Zn
2+
(aq) + Cu(s) (7.15)
In reaction (7.15), zinc has lost electrons
to form Zn
2+
and, therefore, zinc is oxidised.
Evidently, now if zinc is oxidised, releasing
electrons, something must be reduced,
accepting the electrons lost by zinc. Copper
ion is reduced by gaining electrons from the zinc.
Reaction (7.15) may be rewritten as :
At this stage we may investigate the state
of equilibrium for the reaction represented by
equation (7.15). For this purpose, let us place
a strip of metallic copper in a zinc sulphate
solution. No visible reaction is noticed and
attempt to detect the presence of Cu
2+
ions
by passing H
2
S gas through the solution to
produce the black colour of cupric sulphide,
CuS, does not succeed. Cupric sulphide has
such a low solubility that this is an extremely
sensitive test; yet the amount of Cu
2+
formed
cannot be detected. We thus conclude that
the state of equilibrium for the reaction (7.15)
greatly favours the products over the reactants.
Let us extend electron transfer reaction
now to copper metal and silver nitrate solution
in water and arrange a set-up as shown in
Fig. 7.2. The solution develops blue colour
due to the formation of Cu
2+
ions on account
of the reaction:
Fig. 7.1 Redox reaction between zinc and aqueous solution of copper nitrate occurring in a beaker.
(7.16)
Here, Cu(s) is oxidised to Cu
2+
(aq) and
Ag
+
(aq) is reduced to Ag(s). Equilibrium greatly
favours the products Cu
2+
(aq) and Ag(s).
By way of contrast, let us also compare
the reaction of metallic cobalt placed in nickel
sulphate solution. The reaction that occurs
here is :
(7.17)
Unit 7.indd 238 11/11/2022 09:48:49
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Page 5
235 redox reactions
Chemistry deals with varieties of matter and change
of one kind of matter into the other. Transformation of
matter from one kind into another occurs through the
various types of reactions. One important category of such
reactions is Redox Reactions. A number of phenomena,
both physical as well as biological, are concerned with
redox reactions. These reactions find extensive use in
pharmaceutical, biological, industrial, metallurgical and
agricultural areas. The importance of these reactions is
apparent from the fact that burning of different types of
fuels for obtaining energy for domestic, transport and
other commercial purposes, electrochemical processes
for extraction of highly reactive metals and non-metals,
manufacturing of chemical compounds like caustic
soda, operation of dry and wet batteries and corrosion of
metals fall within the purview of redox processes. Of late,
environmental issues like Hydrogen Economy (use of
liquid hydrogen as fuel) and development of ‘Ozone Hole’
have started figuring under redox phenomenon.
7.1 CLASSICAL IDEA OF REDOX REACTIONS –
OXIDATION AND REDUCTION REACTIONS
Originally, the term oxidation was used to describe the
addition of oxygen to an element or a compound. Because
of the presence of dioxygen in the atmosphere (~20%),
many elements combine with it and this is the principal
reason why they commonly occur on the earth in the
form of their oxides. The following reactions represent
oxidation processes according to the limited definition of
oxidation:
2 Mg (s) + O
2
(g) ? 2 MgO (s) (7.1)
S (s) + O
2
(g) ? SO
2
(g) (7.2)
After studying this unit you will be
able to
• identify redox reactions as a class
of reactions in which oxidation
and reduction reactions occur
simultaneously;
• define the terms oxidation,
reduction, oxidant (oxidising
agent) and reductant (reducing
agent);
• explain mechanism of redox
reactions by electron transfer
process;
• use the concept of oxidation
number to identify oxidant and
reductant in a reaction;
• classify redox reaction into
combination (synthesis),
decomposition, displacement
and disproportionation
reactions;
• suggest a comparative order
among various reductants and
oxidants;
• balance chemical equations
using (i) oxidation number
(ii) half reaction method;
• learn the concept of redox
reactions in terms of electrode
processes.
UNIT 7
REDOX REACTIONS
Where there is oxidation, there is always reduction –
Chemistry is essentially a study of redox systems.
Unit 7.indd 235 10/10/2022 10:37:02 AM
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236 chemistry In reactions (7.1) and (7.2), the elements
magnesium and sulphur are oxidised on
account of addition of oxygen to them.
Similarly, methane is oxidised owing to the
addition of oxygen to it.
CH
4
(g) + 2O
2
(g) ? CO
2
(g) + 2H
2
O (l) (7.3)
A careful examination of reaction (7.3) in
which hydrogen has been replaced by oxygen
prompted chemists to reinterpret oxidation
in terms of removal of hydrogen from it and,
therefore, the scope of term oxidation was
broadened to include the removal of hydrogen
from a substance. The following illustration is
another reaction where removal of hydrogen
can also be cited as an oxidation reaction.
2 H
2
S(g) + O
2
(g) ? 2 S (s) + 2 H
2
O (l) (7.4)
As knowledge of chemists grew, it was
natural to extend the term oxidation for
reactions similar to (7.1 to 7.4), which do
not involve oxygen but other electronegative
elements. The oxidation of magnesium with
fluorine, chlorine and sulphur etc. occurs
according to the following reactions :
Mg (s) + F
2
(g) ? MgF
2
(s) (7.5)
Mg (s) + Cl
2
(g) ? MgCl
2
(s) (7.6)
Mg (s) + S (s) ? MgS (s) (7.7)
Incorporating the reactions (7.5 to
7.7) within the fold of oxidation reactions
encouraged chemists to consider not only
the removal of hydrogen as oxidation, but
also the removal of electropositive elements
as oxidation. Thus the reaction :
2K
4
[Fe(CN)
6
](aq) + H
2
O
2
(aq) ?2K
3
[Fe(CN)
6
](aq)
+ 2 KOH (aq)
is interpreted as oxidation due to the removal
of electropositive element potassium from
potassium ferrocyanide before it changes to
potassium ferricyanide. To summarise, the
term “oxidation” is defined as the addition
of oxygen/electronegative element to
a substance or removal of hydrogen/
electropositive element from a substance.
In the beginning, reduction was considered
as removal of oxygen from a compound.
However, the term reduction has been
broadened these days to include removal
of oxygen/electronegative element from
a substance or addition of hydrogen/
electropositive element to a substance.
According to the definition given above,
the following are the examples of reduction
processes:
2 HgO (s) 2 Hg (l) + O
2
(g) (7.8)
(removal of oxygen from mercuric oxide )
2 FeCl
3
(aq) + H
2
(g) ?2 FeCl
2
(aq) + 2 HCl(aq)
(7.9)
(removal of electronegative element, chlorine
from ferric chloride)
CH
2
= CH
2
(g) + H
2
(g) ? H
3
C – CH
3
(g) (7.10)
(addition of hydrogen)
2HgCl
2
(aq) + SnCl
2
(aq) ? Hg
2
Cl
2
(s)+SnCl
4
(aq)
(7.11)
(addition of mercury to mercuric chloride)
In reaction (7.11) simultaneous oxidation
of stannous chloride to stannic chloride is
also occurring because of the addition of
electronegative element chlorine to it. It was
soon realised that oxidation and reduction
always occur simultaneously (as will be
apparent by re-examining all the equations
given above), hence, the word “redox” was
coined for this class of chemical reactions.
Problem 7.1
In the reactions given below, identify
the species undergoing oxidation and
reduction:
(i) H
2
S (g) + Cl
2
(g) ? 2 HCl (g) + S (s)
(ii) 3Fe
3
O
4
(s) + 8 Al (s) ? 9 Fe (s)
+ 4Al
2
O
3
(s)
(iii) 2 Na (s) + H
2
(g) ? 2 NaH (s)
Solution
(i) H
2
S is oxidised because a more
electronegative element, chlorine is added
to hydrogen (or a more electropositive
element, hydrogen has been removed
from S). Chlorine is reduced due to
addition of hydrogen to it.
(ii) Aluminium is oxidised because
oxygen is added to it. Ferrous ferric oxide
Unit 7.indd 236 10/10/2022 10:37:03 AM
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237 redox reactions
(Fe
3
O
4
) is reduced because oxygen has
been removed from it.
(iii) With the careful application of the
concept of electronegativity only we
may infer that sodium is oxidised and
hydrogen is reduced.
Reaction (iii) chosen here prompts us to
think in terms of another way to define
redox reactions.
7.2 REDOX REACTIONS IN TERMS OF
ELECTRON TRANSFER REACTIONS
We have already learnt that the reactions
2Na(s) + Cl
2
(g) ? 2NaCl (s) (7.12)
4Na(s) + O
2
(g) ? 2Na
2
O(s) (7.13)
2Na(s) + S(s) ? Na
2
S(s) (7.14)
are redox reactions because in each of these
reactions sodium is oxidised due to the addition
of either oxygen or more electronegative
element to sodium. Simultaneously, chlorine,
oxygen and sulphur are reduced because to
each of these, the electropositive element
sodium has been added. From our knowledge
of chemical bonding we also know that sodium
chloride, sodium oxide and sodium sulphide
are ionic compounds and perhaps better
written as Na
+
Cl
–
(s), (Na
+
)
2
O
2–
(s), and (Na
+
)
2
S
2–
(s). Development of charges on the species
produced suggests us to rewrite the reactions
(7.12 to 7.14) in the following manner :
For convenience, each of the above
processes can be considered as two separate
steps, one involving the loss of electrons
and the other the gain of electrons. As an
illustration, we may further elaborate one of
these, say, the formation of sodium chloride.
2 Na(s) ? 2 Na
+
(g)
+ 2e
–
Cl
2
(g) + 2e
–
? 2 Cl
–
(g)
Each of the above steps is called a half
reaction, which explicitly shows involvement
of electrons. Sum of the half reactions gives
the overall reaction :
2 Na(s) + Cl
2
(g) ? 2 Na
+
Cl
–
(s) or 2 NaCl (s)
Reactions 7.12 to 7.14 suggest that half
reactions that involve loss of electrons are
called oxidation reactions. Similarly, the
half reactions that involve gain of electrons
are called reduction reactions. It may not
be out of context to mention here that the
new way of defining oxidation and reduction
has been achieved only by establishing a
correlation between the behaviour of species
as per the classical idea and their interplay
in electron-transfer change. In reactions (7.12
to 7.14) sodium, which is oxidised, acts as
a reducing agent because it donates electron
to each of the elements interacting with it and
thus helps in reducing them. Chlorine, oxygen
and sulphur are reduced and act as oxidising
agents because these accept electrons from
sodium. To summarise, we may mention that
Oxidation : Loss of electron(s) by any species.
Reduction : Gain of electron(s) by any species.
Oxidising agent : Acceptor of electron(s).
Reducing agent : Donor of electron(s).
Problem 7.2 Justify that the reaction:
2 Na(s) + H
2
(g) ? 2 NaH (s) is a redox
change.
Solution
Since in the above reaction the compound
formed is an ionic compound, which may
also be represented as Na
+
H
–
(s), this
suggests that one half reaction in this
process is :
2 Na (s) ? 2 Na
+
(g) + 2e
–
Unit 7.indd 237 10/10/2022 10:37:03 AM
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238 chemistry and the other half reaction is:
H
2
(g) + 2e
–
? 2 H
–
(g)
This splitting of the reaction under
examination into two half reactions
automatically reveals that here sodium
is oxidised and hydrogen is reduced,
therefore, the complete reaction is a
redox change.
7.2.1 Competitive Electron Transfer
Reactions
Place a strip of metallic zinc in an aqueous
solution of copper nitrate as shown in Fig.
7.1, for about one hour. You may notice
that the strip becomes coated with reddish
metallic copper and the blue colour of the
solution disappears. Formation of Zn
2+
ions
among the products can easily be judged
when the blue colour of the solution due to
Cu
2+
has disappeared. If hydrogen sulphide
gas is passed through the colourless solution
containing Zn
2+
ions, appearance of white zinc
sulphide, ZnS can be seen on making the
solution alkaline with ammonia.
The reaction between metallic zinc and the
aqueous solution of copper nitrate is :
Zn(s) + Cu
2+
(aq) ? Zn
2+
(aq) + Cu(s) (7.15)
In reaction (7.15), zinc has lost electrons
to form Zn
2+
and, therefore, zinc is oxidised.
Evidently, now if zinc is oxidised, releasing
electrons, something must be reduced,
accepting the electrons lost by zinc. Copper
ion is reduced by gaining electrons from the zinc.
Reaction (7.15) may be rewritten as :
At this stage we may investigate the state
of equilibrium for the reaction represented by
equation (7.15). For this purpose, let us place
a strip of metallic copper in a zinc sulphate
solution. No visible reaction is noticed and
attempt to detect the presence of Cu
2+
ions
by passing H
2
S gas through the solution to
produce the black colour of cupric sulphide,
CuS, does not succeed. Cupric sulphide has
such a low solubility that this is an extremely
sensitive test; yet the amount of Cu
2+
formed
cannot be detected. We thus conclude that
the state of equilibrium for the reaction (7.15)
greatly favours the products over the reactants.
Let us extend electron transfer reaction
now to copper metal and silver nitrate solution
in water and arrange a set-up as shown in
Fig. 7.2. The solution develops blue colour
due to the formation of Cu
2+
ions on account
of the reaction:
Fig. 7.1 Redox reaction between zinc and aqueous solution of copper nitrate occurring in a beaker.
(7.16)
Here, Cu(s) is oxidised to Cu
2+
(aq) and
Ag
+
(aq) is reduced to Ag(s). Equilibrium greatly
favours the products Cu
2+
(aq) and Ag(s).
By way of contrast, let us also compare
the reaction of metallic cobalt placed in nickel
sulphate solution. The reaction that occurs
here is :
(7.17)
Unit 7.indd 238 11/11/2022 09:48:49
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239 redox reactions
Fig. 7.2 Redox reaction between copper and aqueous solution of silver nitrate occurring in a beaker.
At equilibrium, chemical tests reveal that both
Ni
2+
(aq) and Co
2+
(aq)
are present at moderate
concentrations. In this case, neither the
reactants [Co(s) and Ni
2+
(aq)] nor the products
[Co
2+
(aq) and Ni (s)] are greatly favoured.
This competition for release of electrons
incidently reminds us of the competition for
release of protons among acids. The similarity
suggests that we might develop a table in
which metals and their ions are listed on the
basis of their tendency to release electrons
just as we do in the case of acids to indicate
the strength of the acids. As a matter of fact
we have already made certain comparisons.
By comparison we have come to know that
zinc releases electrons to copper and copper
releases electrons to silver and, therefore,
the electron releasing tendency of the metals
is in the order: Zn>Cu>Ag. We would love to
make our list more vast and design a metal
activity series or electrochemical series.
The competition for electrons between various
metals helps us to design a class of cells,
named as Galvanic cells in which the chemical
reactions become the source of electrical
energy. We would study more about these
cells in Class XII.
7.3 OXIDATION NUMBER
A less obvious example of electron transfer is
realised when hydrogen combines with oxygen
to form water by the reaction:
2H
2
(g) + O
2
(g) ? 2H
2
O (l) (7.18)
Though not simple in its approach, yet
we can visualise the H atom as going from a
neutral (zero) state in H
2
to a positive state in
H
2
O, the O atom goes from a zero state in O
2
to a dinegative state in H
2
O. It is assumed that
there is an electron transfer from H to O and
consequently H
2
is oxidised and O
2
is reduced.
However, as we shall see later, the charge
transfer is only partial and is perhaps better
described as an electron shift rather than a
complete loss of electron by H and gain by
O. What has been said here with respect
to equation (7.18) may be true for a good
number of other reactions involving covalent
compounds. Two such examples of this class
of the reactions are:
H
2
(s) + Cl
2
(g) ? 2HCl(g) (7.19)
and,
CH
4
(g) + 4Cl
2
(g) ? CCl
4
(l) + 4HCl(g) (7.20)
In order to keep track of electron shifts
in chemical reactions involving formation
of covalent compounds, a more practical
method of using oxidation number has
been developed. In this method, it is always
assumed that there is a complete transfer
of electron from a less electronegative atom
to a more electonegative atom. For example,
we rewrite equations (7.18 to 7.20) to show
charge on each of the atoms forming part of
the reaction :
0 0 +1 –2
2H
2
(g) + O
2
(g) ? 2H
2
O (l) (7.21)
0 0 +1 –1
H
2
(s) + Cl
2
(g) ? 2HCl(g) (7.22)
–4+1 0 +4 –1 +1 –1
CH
4
(g) + 4Cl
2
(g) ? CCl
4
(l) +4HCl(g) (7.23)
It may be emphasised that the assumption
of electron transfer is made for book-keeping
purpose only and it will become obvious at
a later stage in this unit that it leads to the
simple description of redox reactions.
Oxidation number denotes the oxidation
state of an element in a compound
ascertained according to a set of rules
formulated on the basis that electron pair
Unit 7.indd 239 11/10/2022 15:18:03
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