UNIT

REDOX
8
REACTIONS
OBJECTIVES
Building on..... Assessing..... Preparing for Competition.....
 Understanding Text 1  Quick Memory Test with  Topicwise MCQs 63
 Conceptual Questions 42 Answers 57  Competitive Examination Qs
CHAPTER SUMMARY & QUICK  HOTS & Advance Level  AIPMT & Other State Boards’
CHAPTER ROUND UP 44 Questions with Answers 58 Medical Entrance 65
NCERT FILE REVISION EXERCISES 60  JEE (Main) & Other State Boards’
 Hints & Answers for Engineering Entrance 66
 In-text Qs & Exercises with
Solutions 46 Revision Exercises 62
 JEE (Advance) for IIT Entrance 69
 NCERT Exemplar Problems with  NCERT Exemplar Problems
UNIT PRACTICE TEST 79
Answers & Solutions (Subjective) 54 (Objective Questions) 72
 Hints & Explanations for Difficult
Questions 74

The oxidation and reduction reactions or redox reactions are very

common in our daily life. A large number of phenomena both
physical as well as chemical and biological are concerned with
redox reactions. Chemical reactions like burning of coal,
sulphur, cooking gas, rusting of iron, generation of electricity,
digestion of food, etc are examples of redox reactions. Many
industrial processes such as electroplating, production of
caustic soda, potassium permanganate, extraction of metals
like sodium, iron and aluminium, etc are also common
examples of redox reactions. In fact, redox reactions keep
us alive. They help to capture the energy of the sun by the
photosynthesis process by plants which is used by us.
Recently, environmental issues such as hydrogen economy
i.e., use of liquid hydrogen as fuel and development of ozone
hole are considered as redox phenomena.
In the present unit, we shall classify the reactions into
two classes, oxidation and reduction reactions and discuss
electrochemical cells.
OXIDATION AND REDUCTION REACTIONS
Classical Concepts of Oxidation and Reduction
Oxidation
According to classical (earlier) views, oxidation is defined as
the addition of oxygen or any other electronegative element or removal of hydrogen or any other
electropositive element.
For example, the oxidation reactions are :
(i) C + O2 ⎯⎯→ CO2 ⎫
2Mg + O2 ⎯⎯→ 2MgO ⎬⎭
Addition of oxygen
(ii)
Addition of
(iii) Zn + S ⎯⎯→ ZnS ⎫ electronegative
⎬
(iv) Mg + Cl2 ⎯⎯→ MgCl2 ⎭ element 8/1
 8/2 MODERN'S abc + OF CHEMISTRY–XI

The above reactions involve addition of oxygen or electronegative element (S and Cl2) and therefore, are
oxidation reactions.
(v) 2H2S + O2 ⎯⎯→ 2H2O + 2S ⎫ Removal of
⎬ hydrogen
(vi) MnO2+ 4HCl ⎯⎯→ MnCl2 + Cl2 + 2H2O ⎭
(vii) 2KI + Cl2 ⎯⎯→ 2KCl + I2 ⎫ Removal of
⎬ electropositive
(viii) 2K4 [ Fe(CN)6] + H2O2 ⎯⎯→ 2K3 [Fe(CN)6] + 2KOH ⎭ element

These reactions involve removal of hydrogen or In these examples, reactions involve removal of
some electropositive element (potassium) and, oxygen or electronegative element (chlorine) and
therefore, are oxidation reactions. therefore, are reduction reactions.
In these reactions, the substances shown coloured The substances shown coloured have undergone
have undergone oxidation. reduction.
Oxidising Agent or Oxidant Reducing Agent
A substance which gives oxygen or removes
A substance which provides hydrogen or
hydrogen is called an oxidising agent or
removes oxygen is called a reducing agent or
oxidant.
reductant.
For example, in examples (i) and (ii), O2 is an
oxidising agent because it causes the oxidation of For example, in examples (i) and (ii), H2 and
C and Mg. Similarly, in reactions (iii) and (iv) S H2S act as reducing agents because these cause
and Cl2 act as oxidising agents because they add reduction of Cl 2 and Br 2. Similarly, in reactions
electronegative element to Zn and Mg. Similarly, (iii) and (iv), Fe and SnCl2 act as reducting agents
Cl2 and MnO2 act as oxidising agents in reactions because these add electropositive elements Fe and
(v) and (vi) because they remove hydrogen while, Cl2 Hg. Similarly, in reactions (v) and (vi), H2 and CO act
and H2O2 act as oxidising agents in reactions (vii) and as reducing agents because these remove oxygen
(viii) because they remove electropositive element from CuO and Fe 2O 3, respectively. In reactions
(potassium). (vii) and (viii), H2 and Na act as reducing agents
because these remove electronegative element (Cl)
Reduction
from FeCl3 and SiCl4.
According to classical concept, reduction is
defined as Oxidation-Reduction Reactions are
the addition of hydrogen or any other Complementary : go side by side
electropositive element or removal of oxygen Oxidation-reduction reactions are complementary
or any other electronegative element. reactions. Whenever any substance is oxidised,
For example, the reduction reactions are : another substance is always reduced at the same time
(i) Cl2 + H2 ⎯→ 2HCl ⎫ and vice versa. In other words, the oxidation reduction
⎬ Addition of hydrogen reactions always occur simultaneously i.e., they always
(ii) Br2 + H2S ⎯→ 2HBr + S ⎭
Addition of go hand in hand or side by side. For example, consider
(iii) 2FeCl3 + Fe ⎯→ 3FeCl2 ⎫ electro- the reaction :
(iv) 2HgCl2 + SnCl2⎯→Hg2Cl2 + SnCl4
⎬ positive
⎭ element 2HgCl2 + SnCl2 ⎯⎯→ Hg2Cl2 + SnCl4
In the above examples, reactions (i) and (ii) involve In this reaction, stannous chloride (SnCl2) has
addition of hydrogen and reactions (iii) and (iv) involve been oxidised to stannic chloride (SnCl4) because
addition of electropositive elements (Fe and Hg) and of addition of electronegative element chlorine to
therefore, are reduction reactions. Similarly, it. At the same time HgCl 2 is reduced to Hg 2Cl 2
(v) CuO + H2 ⎯⎯→ Cu + H2O ⎫ because of the addition of mercury to mercuric
Removal of
⎬ oxygen chloride. Thus, SnCl2 is oxidised by HgCl2 and HgCl2
(vi) Fe2O3 + 3CO ⎯⎯→2Fe + 3CO2 ⎭ is reduced by SnCl2. Hence, HgCl2 acts as an oxidising
(vii) 2FeCl3+ H2 ⎯⎯→2FeCl2 + 2HCl ⎫ Removal of agent and SnCl2 acts as a reducing agent in this
⎬ electronegative reaction.
(viii) SiCl4 + 4Na –⎯→ Si + 4NaCl ⎭ element
REDOX REACTIONS 8/3

Thus, oxidation and reduction reactions are Na ⎯⎯→ Na++ e–

collectively called redox reactions. Some more Mg ⎯⎯→ Mg + 2e–
2+

examples of redox reactions are given below : Sn2+ ⎯⎯→ Sn4+ + 2e–
Oxidation Fe2+ ⎯⎯→ Fe3+ + e–

⎯
→
(ii) Loss of electrons resulting in decrease of
2H2 + O2 ⎯⎯→ 2H2O negative charge.

⎯⎯⎯→
(R.A.) (O.A.) MnO42– ⎯⎯→ MnO4– + e–
Reduction
[Fe(CN)6]4– ⎯⎯→ [Fe(CN)6]3– + e–
2Cl− ⎯⎯→ Cl2 + 2e–
Oxidation
S2– ⎯⎯→ S + 2e–
⎯⎯→
Fe2O3 + 2Al ⎯⎯→ Al2O3 + 2Fe Reduction . According to electronic concept,
reduction is

⎯⎯⎯→
(O.A.) (R.A.)
a process which involves gain of electrons by
Reduction an atom or group of atoms.
Oxidation
Due to gain of electrons there is increase of
⎯⎯→ negative charge or decrease of positive charge of an
atom or ion undergoing reduction. For example,
H2S + 2FeCl3 ⎯⎯→ 2FeCl2 + 2HCl + S
(i) Gain of electrons resulting in decrease of
⎯⎯→

(R.A.) (O.A.)
positive charge.
Reduction Fe3+ + e– ⎯⎯→ Fe2+
Sn4+ + 2e– ⎯⎯→ Sn2+
Oxidation Sb5+ + 2e– ⎯⎯→ Sb3+
↓
(ii) Gain of electrons resulting in increase of
H2S + Cl2 ⎯⎯→ 2HCl + S
↓ negative charge.
(R.A.) (O.A.) Cl2+ 2e– ⎯⎯→ 2Cl–
Reduction S + 2e– ⎯⎯→ S2–
ΜnO4− + e– ⎯⎯→ MnO42−
Oxidation
↓ [Fe(CN)6]3– + e– ⎯⎯→ [Fe(CN)6]4–
MnO2 + 4HCl ⎯⎯→ MnCl2 + Cl2 + H2O
OXIDATION-REDUCTION REACTIONS
(O.A.) (R.A.)
↑ AS ELECTRONS TRANSFER REACTIONS
Reduction As already learnt, oxidation process involves loss
of electrons whereas reduction process involves gain
Here O.A. and R.A. stand for oxidising agent of electrons. During transfer of electrons in a reaction,
and reducing agent respectively. the species which loses electrons is said to be oxidised
and the species which gains electrons is said to be
Electronic Concept of Oxidation and Reduction
reduced. Since there cannot be a net loss or gain of
Oxidation and reduction reactions are now used
electrons in a chemical reaction, this means that all
in a much broader and general sense. These are
chemical changes involving the loss and gain of
defined in terms of electron transfer between the
reactants, known as electronic concept of oxidation and electrons occur simultaneously i.e. one species loses
reduction. electrons in oxidation while the other gains electrons
during the reduction. Thus, both these changes take
Oxidation. According to electronic concept,
place side by side i.e., oxidation takes place at the
oxidation is
cost of reduction and vice versa.
a process which involves loss of electrons by an
atom or group of atoms. In other words, oxidation and reduction reactions
As a result of loss of electrons, there is increase in go hand in hand. This may be illustrated by the
positive charge or decrease in negative charge of the following reactions:
atom or ion undergoing oxidation. 4Na(s) + O2(g) ⎯⎯→ 2Na2O(s)
For example, 2Na(s) + Cl2(g) ⎯⎯→ 2NaCl(s)
(i) Loss of electrons resulting in increase in positive 2Na(s) + S(s) ⎯⎯→ Na2S(s)
charge.
 8/4 MODERN'S abc + OF CHEMISTRY–XI

All these reactions are redox reactions because in the number of electrons gained during reduction half
each of these reactions sodium is oxidised due to reaction, the two half reactions are multiplied by
addition of either oxygen or more electronegative suitable integers so that when the two half equations
elements such as chlorine or sulphur to sodium. are added, the electrons get cancelled out in the final
Simultaneously oxygen, chlorine and sulphur are redox reaction. For example,
reduced because electropositive element sodium has Na (s) ⎯→ Na+ + e– ] × 4
been added to each of these. We have also learnt in Oxidation half reaction
chemical bonding that sodium oxide, sodium chloride O2(g) + 4e ⎯→ 2O2–
–
and sodium sulphide are ionic compounds and may be Reduction half reaction
written as :
Sodium oxide : (Na +) 2 O 2– , Sodium chloride : 4Na(s) + O2(g) ⎯→ 2(Na+)2O2– or 2Na2O
Na Cl–, Sodium sulphide : (Na+)2 S2–.
+ Overall redox reaction
These ionic charges suggest that the above redox Similarly, we may write other reactions as :
reactions may also be written as : Na (s) ⎯→ Na+ + e– ] × 2
Loss of 4e– : oxidation Oxidation half reaction
Cl2(g) + 2e ⎯→ 2Cl–
–

4Na(s) + O2(g) ⎯⎯→ 2(Na+)2 O2– (s) Reduction half reaction

2Na(s) + Cl2(g) ⎯→ 2Na+Cl–(s) or 2NaCl

Gain of 4e– : reduction Overall redox reaction
Loss of 2e– : oxidation Na (s) ⎯→ Na+ + e– ] × 2
Oxidation half reaction
S(s) + 2e ⎯→ S
– 2–
2Na(s) + Cl2(g) ⎯⎯→ 2Na+ Cl– (s)
Reduction half reaction

Gain of 2e– : reduction 2Na(s) + S(s) ⎯→ (Na+)2 S2–(s) or Na2S(s)

Loss of 2e– : oxidation Overall redox reaction

In all the above reactions, electrons are transferred

2Na(s) + S(s) ⎯⎯→ (Na+)2 S2– (s) from sodium to O2, Cl 2 and S. Thus, oxidation-
reduction i.e., redox reactions are regarded as
electron transfer reactions. Moreover, we observe
Gain of 2e– : reduction
that O2, Cl2 and S have gained electrons only if there
For the sake of convenience, each of the above
is another substance which can donate electrons. This
redox reaction may be considered as the sum of two
means that reduction can occur only if oxidation is
half reactions; one involving loss of electrons i.e.
occurring side by side and vice versa. In these
oxidation and the other involving gain of electrons
reactions, sodium loses electrons and has been oxidised
i.e. reduction as
to sodium ion, Na+. This is brought about by the
Na(s) ⎯⎯→ Na+ + e–
acceptance of electrons by oxygen, chlorine or sulphur,
Oxidation half reaction which get reduced. Thus, oxygen, chlorine and sulphur
O2 + 4e– ⎯⎯→ 2O2– bring about the oxidation and are called oxidising
Reduction half reaction agents or oxidants.
These two half reactions are called oxidation half Thus, according to electronic concept,
reaction and reduction half reaction respectively. The
oxidising agent is a substance which can accept
sum of the half reactions give the overall reaction. It
one or more electrons.
may be noted that the overall reaction is so written
that the electrons are balanced i.e., the number of Similarly, in the above example, oxygen, chlorine
electrons lost and gained become equal. This means and sulphur are reduced to oxide ion (O2−), chloride ion
that the two half reactions are simply added if the (Cl–) and sulphide ion (S2–) respectively. This has been
number of electrons lost during oxidation half reaction possible by furnishing electrons by sodium. Thus,
is equal to the number of electrons gained during sodium is a reducing agent or reductant. Thus,
reduction half reaction. But if the number of electrons reducing agent is a substance which can give
lost during oxidation half reaction are different from one or more electrons.
REDOX REACTIONS 8/5

TO SUM UP the bottom of the beaker.

Oxidation is a process in which one or more (iii) The blue colour of the solution gradually fades
electrons are lost. away.
Reduction is a process in which one or more electrons (iv) The reaction is exothermic and proceeds with
are gained. the liberation of heat energy.
Oxidising agent or oxidant is a substance which (v) The solution remains electrically neutral.
can accept one or more electrons. Let us try to explain the above reaction. In aqueous
Reducing agent or reductant is a substance which solution, CuSO4 dissociates into Cu2+ and SO42− ions.
can give one or more electrons. When a strip of zinc is dipped in CuSO4 solution, zinc
In a redox reaction, oxidising agent is reduced by metal loses electrons and gets oxidised whereas Cu2+
accepting electrons and reducing agent is oxidised ions accept electrons and get reduced. Since zinc is
by losing electrons. getting oxidised and converted to Zn2+ ions which go
into the solution, the weight of zinc plate gradually
TYPES OF REDOX REACTIONS decreases. On the other hand, Cu2+ ions present in the
The redox reactions may be classified into two types: solution are accepting the electrons given by zinc and
1. Direct redox reactions. The reactions in which are getting reduced to copper. As a result, copper metal
the oxidation and reduction take place in the same either gets deposited on the zinc plate or gets precipitated
vessel are called direct redox reactions. at the bottom of the beaker [Fig. 1(b)]. Since Cu2+ ions
2. Indirect redox reactions. The reactions in from the solution are changing to Cu(s), the blue colour
which oxidation and reduction take place in different of the solution (which is due to Cu2+ ions) slowly fades.
vessels are called indirect redox reactions. These are The reaction may be written as :
very important reactions because these form the basis Zn(s) + Cu2+ (aq) + SO42– (aq) ⎯⎯→
of electrochemical cells. Cu(s) + Zn2+ (aq) + SO42–
DIRECT REDOX REACTIONS: Formation of Zn2+ ions among the products can
REDOX REACTIONS IN AQUEOUS easily be tested when the blue colour of the solution
SOLUTIONS due to Cu2+ ions has disappeared. If we pass, hydrogen
Redox reactions are very common in our daily life. sulphide (H2S) gas through the solution, formation of
Whenever you use a battery, a redox reaction occurs. white precipitate of zinc sulphide (ZnS) on making
A simple example of an oxidation-reduction reaction the solution alkaline with ammonia indicates the
is the reaction between zinc metal and copper (II) salt presence of Zn2+ ions in the solution.
in aqueous solution : In this reaction, sulphate ions, SO 42– do not
Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s) participate and we may write the reaction as :
Let us study this reaction. Loss of 2e– : Oxidation
Take a strip of zinc metal and clean it with a sand ⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯
⎯

paper. Place this strip in a solution of copper sulphate Zn (s) + Cu2+ (aq) ⎯⎯⎯⎯→ Zn2+ (aq) + Cu (s)
⎯

in a beaker [Fig. 1]. We observe that a spontaneous ⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯

reaction takes place and the following observations Gain of 2e– : Reduction
are made :
(i) Zinc metal starts dissolving and it loses its or Zn(s) + Cu2+ (aq) ⎯⎯→ Zn2+ (aq) + Cu(s)
weight gradually. The reaction is commonly described as zinc having
(ii) The copper metal starts getting either displaced Cu2+ ions from the CuSO4 solution.
deposited on the zinc plate or settles down at

(a) (b) (c)

Fig. 1. Redox reaction occurring in a beaker.
 8/6 MODERN'S abc + OF CHEMISTRY–XI

In this case, zinc acts as a reducing agent while At equilibrium, chemical tests show that both
Cu2+ ions act as oxidising agent. Ni 2+ (aq) and Co 2+ (aq) are present in moderate
In this redox reaction, the transference of electrons concentration. This means that in this case, neither
from Zn metal to Cu2+ ions is occurring directly because the reactants [Co(s) and Ni2+(aq)] nor the products
the two are in direct contact. The energy released appears [Co2+(aq) and Ni(s)] are greatly favoured.
as heat and therefore, it is an exothermic reaction. Thus, we observe that there is a competition of
Let us study the state of equilibrium for the above loss or gain of electrons by metals. This is similar to
reaction. For this purpose, place a rod of copper in zinc the competition between various acids to lose a
sulphate (ZnSO4) solution. You will notice that no proton (H+) in water. This similarity suggests that
visible reaction occurs. If we pass H2S gas through the we can develop a table in which the metals and their
solution, there will be no black precipitate of copper ions are listed on the basis of their tendency to lose
sulphide indicating that no reaction has occurred. In or gain electrons similar to the table in which
other words, the following reaction : various acids are arranged according to their acid
strengths. For example, we have learnt in above
Cu (s) + ZnSO4(aq) ⎯→CuSO4(aq) + Zn(s)
experiments that zinc loses electrons to copper and
does not occur. Thus, we conclude that the state of
copper releases electrons to silver. Therefore, the
equilibrium for the above reaction between zinc and electron releasing tendency of these three metals is
copper sulphate greatly favours the products over the in the order :
reactants.
Zn > Cu > Ag
Similarly, when we dip a copper strip in a silver
nitrate solution, copper gets oxidised and goes into the Similarly, by comparing the relative tendencies of
solution whereas Ag+ ions accept electrons and get other metals, we can build a table to arrange the
metals in their decreasing or increasing order of losing
reduced (Fig. 2). The reaction may be written as :
electrons. This series is called activity series or
Cu(s) + 2Ag+ (aq) ⎯⎯→ 2Ag(s) + Cu2+ (aq)
electrochemical series and is discussed later.
Loss of 2e– : Oxidation
⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯ Some other examples of common redox reactions
⎯

Cu (s) + 2Ag+ (aq) ⎯⎯⎯⎯→ Cu2+ (aq) + 2Ag (s) When a metal reacts with acids, hydrogen is
liberated. For example metals like Zn, Mg, Ni etc.
⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯
can easily displace hydrogen from dil. HCl.
Gain of 2e– : Reduction
Zn + 2HCl ⎯⎯→ZnCl2 + H2
Thus, copper is oxidised to Cu2+ and Ag+ is reduced
This reaction occurs as redox reaction in which
to Ag(s). Therefore, copper acts as an oxidising agent or
metal is oxidised and hydrogen is reduced as :
oxidant while silver acts as a reducing agent or reductant.
Zn ⎯⎯→Zn2+ + 2e– Oxidation
The equilibrium greatly favours the products
Cu2+(aq) and Ag(s). 2H+ + 2Cl– + 2e– ⎯⎯→2Cl– + H2 Reduction
For the purpose of comparison, let us study the Zn + 2H+ + 2Cl– ⎯⎯→Zn2+ + 2Cl– + H2
reaction between cobalt metal and nickel sulphate In electrolytic process also, redox reaction takes
solution. For this, place a rod of cobalt metal in nickel place. For example, during electrolysis of aqueous
sulphate solution. The following reaction occurs : solution of copper chloride, oxidation and reduction
Loses 2e– : Oxidation occur as :
↓  Cu2+ + 2Cl–
CuCl2 
Co(s) + Ni2+(aq) ⎯⎯→ Co2+ (aq) + Ni(s)
At cathode : Cu2+ + 2e– ⎯⎯→Cu(s) Reduction
↑
Gains 2e– : Reduction At anode : 2Cl– ⎯⎯→ Cl2 + 2e– Oxidation

Fig. 2. Redox reaction between AgNO3 and copper.

REDOX REACTIONS 8/7

Potassium permanganate is a strong oxidising Loses electrons : oxidation

agent in the presence of dil. H2SO4. In the presence of
dil. H2SO4, it gives nascent oxygen which oxidises H2S (g) + Cl2(g) ⎯⎯→ 2HCl (g) + S(s)
ferrous ammonium sulphate [FeSO4(NH4)2SO4] to
ferric sulphate as : gains electrons : reduction
2KMnO4 + 3H2SO4 ⎯→K2SO4 + 2MnSO4 +3H2O +5O (ii) Aluminium is oxidised because oxygen is added to
it.
2FeSO4(NH4)2SO4 + H2SO4 + O ⎯→ Ferrous ferric oxide (Fe3O4) is reduced because oxygen
Fe2(SO4)3 + 2(NH4)2SO4 + H2O] × 5 has been removed from it.
In terms of electronic concept :
2KMnO4 + 10FeSO4(NH4)2SO4 + 8H2SO4 ⎯→ loses electrons : oxidation
K2SO4 + 5Fe2(SO4)3 + 2MnSO4 + 10(NH4)2SO4 + 8H2O
The ionic equation for the reaction may be written 3Fe3O4 (s) + 8Al(s) ⎯⎯→ 9Fe(s) + 4Al2O3(s)
as :
MnO4– + 8H+ + 5e– ⎯→Mn2+ + 4H2O gains electrons : reduction

Fe2+ ⎯→Fe3+ + e– ] × 5 (iii) In this case, sodium has been oxidised and hydrogen
has been reduced. This becomes more clear in terms of
5Fe2+ + MnO4– + 8H+ ⎯→ 5Fe3+ + Mn2+ + 4H2O electronic concept :
loses electron : oxidation
Similarly, acidified KMnO4 oxidises oxalic acid
(C2H2O4) solution. In this reaction, acidified KMnO4 + –
2Na(s) + H2(g) ⎯⎯→ 2Na H (s)
liberates nascent oxygen which oxidises oxalic acid to
carbon dioxide as: gains electrons : reduction
2KMnO4 + 3H2SO4 ⎯→K2SO4 + 2MnSO4 + 3H2O + 5O NaH is ionic compound and exists as Na+H–.
C2H2O4 + O ⎯→2CO2 + H2O] × 5  Example 2.
Identify the oxidant and reductant in the following
2KMnO4 + 5C2H2O4 + 3H2SO4 ⎯→
reactions :
K2SO4 + 2MnSO4 + 10CO2 + 8H2O
1
The ionic equation for the reaction may be written (a) Zn (s) + O2 (g) ⎯⎯⎯→ ZnO (s)
2
as : (b) CH4 (g) + 4Cl2 (g) ⎯⎯⎯→ CCl4 (g) + 4HCl (g)
[MnO4– + 8H+ + 5e– ⎯→Mn2+ + 4H2O] × 2 (c) I2 (aq) + 2S2O32– (aq) ⎯⎯⎯→ 2I– (aq) + S4O62– (aq)
C2O42– ⎯→2CO2 + 2e– ] × 5 (d) Zn (s) + 2H+ (aq) ⎯⎯⎯→ Zn2+ (aq) + H2 (g)
2MnO4– + 5C2O42– + 16H+ ⎯→ 2Mn2+ + 10CO2 +8H2O 1
Solution: (a) Zn (s) + O2 (g) ⎯⎯→ ZnO (s)
2
In this reaction, zinc donates electrons to O to give
zinc ions and oxide ions. Thus, Zn acts as reductant
while oxygen acts as oxidant.
 Example 1. (b) CH4 (g) + 4Cl2 (g) ⎯⎯→ CCl4 (g) + 4HCl (g)
Identify the species undergoing oxidation and CH4 is oxidised and acts as reductant while Cl2 is
reduction in the following reaction : reduced and acts as oxidant.
(i) H2S(g) + Cl2(g) ⎯→ 2HCl (g) + S (s) (c) I2 (aq) + 2S2O32– (aq) ⎯⎯→ 2I– (aq) + S4O62– (aq)
I2 gains electrons and is reduced. Therefore, it acts as
(ii) 3Fe3O4(s) + 8Al(s) ⎯→ 9Fe(s) + 4Al2O3(s) oxidant. S2O32– acts as reductant.
(iii) 2Na(s) + H2(g) ⎯→ 2NaH(s) (d) Zn (s) + 2H+ (aq)⎯⎯→Zn2+ (aq) + H2 (g)
Solution: Zinc loses electrons and gets oxidised. Therefore, it
acts as reductant. Hydrogen gets reduced and acts as
(i) H2S is oxidised because a more electronegative
an oxidant.
element, chlorine is added to hydrogen (or a more
electropositive element hydrogen has been removed  Example 3.
from H2S). Justify that the reaction :
Chlorine has been reduced because hydrogen is added 2Na(s) + H2(g) ⎯⎯→ 2NaH (s) is a redox reaction.
to it.
In terms of electronic concept, we can say,
Solution: Sodium hydride is an ionic compound and
it exists as Na+ H–.
 8/8 MODERN'S abc + OF CHEMISTRY–XI

2Na + H2 ⎯⎯→ 2Na+H–(s) atom without electron has a unit positive charge.
The reaction may be split up into two half reactions: Hence, oxidation number of hydrogen in hydrogen
Na(s) ⎯⎯→ Na+ + e– ] × 2 Oxidation chloride is + 1.
H2(g) + 2e– ⎯⎯→ 2H– Reduction The oxidation number is a fictitious charge in case
of covalent species. The oxidation number can have
2Na(s) + H2(g) ⎯⎯→ 2 NaH
positive, zero or negative values depending upon their
In this reaction, Na is oxidised to Na+ and hydrogen is state of combination.
reduced from H2 to 2H– ion. Therefore, it is a redox
Rules for the Determination of Oxidation Number
reaction.
of an Atom
OXIDATION NUMBER The following general rules are used for the
The concept of electron transfer can easily explain calculation of oxidation number of an atom in a
the redox reactions in case of ionic substances. molecule :
However, we cannot easily explain the redox changes 1. The oxidation number of an element in the
in terms of electron transfer in case of covalent free or elementary state or in any of its
compounds. Now-a-days, to understand oxidation- allotropic forms is always zero. For example,
reduction reactions, systematically, scientists assign oxidation numbers of helium in He, hydrogen
an oxidation number or oxidation state to each in H2, oxygen in O2 or O3, iron in Fe, carbon in
chemical species (ionic or covalent) according to a set diamond, helium atom in He, bromine in Br2,
of rules. The concept of oxidation number has been phosphorus in P4, sulphur in S8, are zero.
very useful in balancing of redox reactions. The 2. The oxidation number of an element in a single
oxidation number is defined as (monoatomic) ion is the same as the charge
the charge which an atom of the element has in on the ion. For example, oxidation number of
its ion or appears to have when present in the K+ is +1, of Ca2+ is + 2, of Al3+ is +3. Similarly,
combined state with other atoms. the oxidation numbers of Cl–, SO42– and PO43–
are –1, –2 and –3 respectively.
Oxidation number also gives the charge which
3. In binary compounds of metal and non-metal,
an atom appears to have when all other atoms are
the oxidation number of metal is always
removed from it as ions. During the removal of atoms, positive while that of the non-metal is negative.
the electrons on the atoms are counted according to For example, in NaCl, the oxidation number of
the following two arbitrary rules : sodium is +1 and that of chlorine is –1.
(i) Electrons shared between two like atoms are 4. In compounds formed by the combination of
divided equally between the sharing atoms. In case of non-metallic atoms, the atom with higher
hydrogen molecule, for example, the electron pair is electronegativity is given negative oxidation
equally shared between the two hydrogen atoms. number. For example, in HCl, the oxidation
Therefore, one electron is counted with each hydrogen number of chlorine in HCl is –1 because of its
atom as shown below : high electronegativity.
H.⏐.H Similarly, N is given an oxidation number of –3,
Now, each hydrogen atom is having one electron when it is bonded to less electronegative atom as in
while its nucleus has one proton. Therefore, there is NH3 and NI3, However, it is given an oxidation number
no net charge on each atom of hydrogen. In other of +3 when it is bonded to more electronegative atom
words, oxidation number of hydrogen in hydrogen as in NCl3.
molecule is zero. Note. Rules (3) and (4) are based on the fact that atoms
(ii) Electrons shared between two unlike atoms having high electronegativity have a tendency to form
are counted with more electronegative atom. For negative ions (anions) while atoms having low
example, in hydrogen chloride molecule, chlorine is electronegativity have great tendency to form positive ions
more electronegative than hydrogen. Therefore, the (cations).
shared pair is counted towards chlorine atom as shown 5. In all compounds of hydrogen, the oxidation
below : number of hydrogen is +1 except in hydrides
.. of active metals such as LiH, NaH, KH, MgH2,
H Cl
..
..

.. CaH2, etc., where hydrogen has the oxidation

number of –1.
As a result of this, chlorine gets one extra electron 6. The oxidation number of oxygen is –2 in most
and acquires a unit negative charge. Hence, oxidation of the compounds. However, there are two
number of chlorine is – 1. On the other hand, hydrogen exceptions. The first exception is peroxides
REDOX REACTIONS 8/9

and superoxides in which oxygen atoms are

directly linked to each other. In peroxides (e.g.,
H2O2, Na2O2), each oxygen atom is assigned  Example 4.
an oxidation number of –1 and in superoxides Calculate the oxidation number of sulphur in the
(e.g., KO2, RbO2) each oxygen atom is assigned following molecules/ions :
an oxidation number of –1/2. The second
(a) H2S (b) H2SO3 (c) SO42–
exception is found in compounds in which
(d) Na2S2O3 (e) S2O72– (f) H2SO4
oxygen is bonded to fluorine. For example,
(g) S2O42–
in OF 2 (oxygen difluoride) the oxidation
number of oxygen is +2 and in O2F2(dioxygen Solution: (a) H2S. The oxidation number of hydrogen
is +1. Let the oxidation number of sulphur be x.
difluoride) the oxidation number of each
oxygen is +1. This is because of the fact that +1 x
fluorine being most electronegative element H2 S
known has always an oxidation number of –1. (1 × 2) (x)
1×2+x=0 ∴ x = –2
7. The most electronegative element, fluorine has
oxidation number –1. For other halogens, the Oxidation number of S in H2S is –2.
oxidation number is generally –1, but there (b) H 2 SO 3. Oxidation number of hydrogen is +1
are exceptions when these are bonded to a and that of oxygen is –2. Let the oxidation number
more electronegative halogen atom or oxygen. of S be x.
For example, in HI, the oxidation number of I +1 x –2
is –1 but in IF5, it is +5 and in IF7, it is +7. H2 S O3
8. For neutral molecule, the sum of the (+1 × 2) x (–2 × 3)
oxidation numbers of all the atoms is equal to (+1 × 2) + x + (–2 × 3) = 0
zero. For example, in NH3 the sum of the or +2 + x – 6 = 0
oxidation numbers of nitrogen atom and 3 or x = +4
hydrogen atoms is equal to zero.
Oxidation number of S in H2SO3 is + 4.
For a polyatomic ion, the sum of the oxidation
(c) SO42–. The oxidation number of oxygen is –2 and
numbers of all the atoms is equal to charge on let the oxidation number of S be x.
the ion. For example, in SO42– ion, the sum of
the oxidation numbers of sulphur atom and 4
LM x OP
−2 2 −

NS O 4 PQ
oxygen atoms must be equal to –2.
It may be noted that oxidation number is also
frequently called as oxidation state. For example, in x (–2 × 4)
H2O, the oxidation state of hydrogen is +1 and the x + (–2 × 4) = –2 or x = –2 + 8
oxidation state of oxygen is –2. Similarly, in CO2, the or x = +6
oxidation number of carbon is +4, which is also its Oxidation number of S in SO42– is +6.
oxidation state and the oxidation number of oxygen is (d) Na2S2O3. The oxidation number of Na is +1 and
–2, which is also its oxidation state. This means that that of oxygen is –2. Let the oxidation number of S be
oxidation number gives the oxidation state of an x.
element in a compound. +1 x –2
Procedure for calculation of oxidation numbers. Na2 S2 O3
By applying the above rules, we can calculate the (+1 × 2) (x × 2) (–2 × 3)
oxidation numbers of elements in the molecules/ions (+1 × 2) + (x × 2) + (–2 × 3) = 0
by the following steps : + 2 + 2x – 6 = 0 or 2x = 4
x = +2
(i) Write down the formula of the given molecule/ion
leaving some space between the atoms. Oxidation number of S in Na2S2O3 is +2.
(ii) Write oxidation number on the top of each atom. (e) S2O72–. The oxidation number of oxygen is –2 and
In case of the atom whose oxidation number has to let the oxidation number of sulphur be x.
be calculated write x.
LM x −2 OP 2−

NS Q
(iii) Beneath the formula, write down the total oxidation
numbers of each element. For this purpose, 2 O7
multiply the oxidation numbers of each atom with (x × 2) (–2 × 7)
the number of atoms of that kind in the molecule/ x × 2 + (–2 × 7) = –2
ion. Write the product in a bracket.
2x = –2 + 14
(iv) Equate the sum of the oxidation numbers to zero ∴ x = 6
for neutral molecule and equal to charge on the ion.
Oxidation number of S in S2O72– is + 6.
(v) Solve for the value of x.
 8/10 MODERN'S abc + OF CHEMISTRY–XI

(f ) H2SO4. The oxidation number of hydrogen is +1 and

(iv) N in (NH4)2SO4. Let the oxidation no. of N be x.
that of oxygen is –2. Let the oxidation number of S be x
+1
H2
x
S
–2
O4
(N H ) SO
x +1
4 2
2−
4
2x + 2 (+1 × 4) + (–2) = 0
(+1 × 2) x (–2 × 4) 2x + 6 = 0
(+1 × 2 ) + x + (–2 × 4) = 0 6
∴ 2x = –6 or x = − = –3
or +2 + x – 8 = 0 2
or x=+6
Oxidation number of S in H2SO4 is + 6. KEY NOTE
(g) S2O42–. The oxidation number of oxygen is –2 and PARADOX OF FRACTIONAL OXIDATION
let the oxidation number of sulphur be x.
NUMBER
LM x −2 OP 2–
 For some compounds, the general rules give fractional
NS 2 O4 Q oxidation number to some atoms. For example, the
8
(x × 2) ( –2 × 4) oxidation number of Fe in Fe3O4 comes out to be + .
x × 2 + (– 2 × 4) = –2 3
2 x – 8 = – 2 ∴ x = +3 This is strange because electrons are never shared or
∴ Oxidation number of S in S2O42– is +3. transferred in fractions.
Actually, this fractional oxidation number is the
 Example 5. average oxidation number of the element in the
What is the oxidation number of the underlined compound. This can be explained by the fact that Fe3O4
atoms in each of the following molecules/ions ? contains Fe atoms of both + 2 and + 3 oxidation number.
(a) ClO3– (b) BrF3 (c) CH4 (d) C6H12O6 (e) Na2 B4O7 It is a stoichiometric mixture of ferrous (FeO) and ferric
(Fe2O3) oxides combined as FeO . Fe2O3. Therefore, the
(f) Na4[Fe(CN)6] (g) N2H4. oxidation number found in such cases is average
Solution: Suppose x be the oxidation number of the oxidation number.
underlined atom : Similarly, Mn3O4 is regarded as a mixture of MnO
(a) ClO3– x + (–2 × 3) = –1 and MnO 2 having the composition 2MnO·MnO 2 .
x – 6 = –1 or x = +5 Therefore, the oxidation number of Mn in MnO is +2
and that in MnO2 is +4. Hence, average comes out to be
(b) BrF3 x + (–1 × 3) = 0 [2(+2) + 1(+4)]/3 = 8/3.
x – 3 = 0 or x = +3 Red lead, Pb3O4 is regarded as a mixture with
(c) CH4 x + (1 × 4) = 0 composition of 2PbO·PbO2. In PbO, the oxidation number
x + 4 = 0 or x = –4 of Pb is +2 while in PbO2, the oxidation number of Pb is
(d) C6H12O6 6 × x + 1 × 12 + (–2 × 6) = 0 +4. The average value is [2(+2) + 1(+4)]/3 = 8/3.
6x + 12 – 12 = 0 or x = 0 Similarly, in ferriferrocyanide, Fe 4[Fe(CN) 6 ] 3
molecule, there are four iron atoms with oxidation
(e) Na2B4O7 (+1 × 2) + (x × 4) + (–2 × 7) = 0
number + 3 and three iron atoms with oxidation number
+2 + 4x – 14 = 0 or x = +3 + 2. The oxidation number of iron in this molecule is the
(f) Na4[Fe(CN)6] (+1 ×4) + x + (–1 × 6) = 0 average of all these atoms equal to 18/7 (strange number).
+4 + x – 6 = or x = +2 Thus, the average oxidation number indicates average of
(g) N2H4 2 × x + (1 × 4) = 0 atoms in different bonding situations in a compound.
2 x + 4 = 0 or x = –2  In some compounds, the knowledge of chemical
 Example 6. bonds or structures is essential to calculate
oxidation numbers. For example,
Calculate the oxidation number of (i) Fe in (a) Caro’s acid, H2SO5 (peroxymonosulphuric acid)
Fe 3 O 4 (ii) S in Na 2 S 4 O 6 (iii) Pb in Pb 3 O 4 The O.N. can be calculated as
(iv) N in (NH 4 ) 2 SO 4 . 2 × (+1) + x + 5(–2) = 0, x = +8
Solution: But this is wrong because the maximum oxidation
(i) Fe in Fe3O4. Let the oxidation number of Fe be x. number of S cannot be more than +6 because it
has only six electrons in its valence shell. In this
x –2 3x – 8 = 0
structure, two oxygen atoms are bonded by a
Fe3 O4 3x = 8 peroxide bond as
(x × 3) (–2 × 4) x = 8/3 = 2.67
(ii) S in Na2S4O6. Let the oxidation number of S be x.
O
+1 x –2 2 + 4x – 12 = 0 H O S O O H
Na2 S4 O6 4x = 10
10
O
(+1 × 2) (x × 4) (–2 × 6) = 2.5 x = In the peroxide bond each O atom has –1 oxidation
4
(iii) Pb in Pb3O4. Let the oxidation no. of Pb be x. state
x –2 3x – 8 = 0 H2S(O2)O3
Pb3 O4 3x = 8 2(+1) + x + 2(–1) + 3(–2) = 0 or x–6=0
∴ x = +6
8
(x × 3) (–2 × 4) or x=
3
= 2.67 ∴ O.N. of S in H2SO5 is +6
REDOX REACTIONS 8/11

Similarly in S2O82– ion, (g) HNO4 (peroxynitric acid)

The oxidation number of N comes out to be +7. This
O O
is not possible for N. In fact, HNO4 is peroxynitric
–O S O O S O– There is one peroxide acid which contains one peroxide group [– O – O –]2–.
bond The formula may be written as HNO 2 (O 2 ). In
O O this case, the oxidation number comes out to be
S2(O2)O62– 2x + 2(–1) + 6(–2) = –2 or 2x = 12 or x = +6 (+1 + x – 4 – 2 = 0 or x = + 5) + 5.
(b) Oxidation number of Cr in CrO5
By conventional method
CrO5 x + 5(–2) = 0 ∴ x = +10  Example 7.
But this is wrong because maximum O.N. of Cr is
+6 (3d54s1) because it has six electrons in its Calculate the oxidation number of carbon in the
valence shell. The structure of CrO5 is following compounds :
C2H2, CO2, C2H6, CH3OH, HCOOH, CH2O.
O O
Solution: In all these compounds, the O.N. (oxidation
Cr
number) of oxygen is –2 and that of hydrogen is +1.
O O So, oxidation number of carbon assuming x can be
O easily calculated as :
It contains two peroxide bonds and may be written C2H2 : 2x + 2 × 1 = 0 2x = –2 ∴ x = – 1
as Cr(O2)2O CO2 : x – (2 × 2) = 0 ∴ x = +4
O.N. can be calculated as C2H6 : 2x + (1 × 6) = 0 2x = – 6 ∴ x = – 3
x + 1 × (– 2) + 4(– 1) = 0 CH3OH : x + (1 × 4) –2 ∴ x=– 2
(for Cr) (for one O) (for O–O bond) HCOOH : x + (2 × 1) + (–2 × 2) = 0 x –2 = 0 ∴ x = +2
or x–2–4=0 CH2O : x + (1 × 2) + (–2) = 0 ∴ x=0
∴ x=+6
 Example 8.
(c) Oxidation number of Cl in bleaching powder,
CaOCl2
Give examples of substances where carbon can
Average O.N. of Cl in CaOCl2 is
exhibit oxidation states from –4 to + 4 and nitrogen
+ 2 – 2 + 2x = 0
from –3 to +5.
∴ x=0 Solution: Carbon Nitrogen
However, it may be noted that the composition of –4 CH4 –3 NH3
bleaching powder is Ca2+ (OCl–)Cl–. In this O.N. of –3 C2H6 –2 N2H4
Cl in OCl– is + 1 and in Cl– is – 1 and the average –2 C2H4 –1 N2H2
of two oxidation numbers 1 × (+ 1) + 1 × (– 1) = 0 –1 C2H2 0 N2
(d) C3O2 (Carbon suboxide) 0 C6H12O6 +1 N2O
Calculated oxidation number of C +2 CO +2 NO
4 +3 N2O3
= 3x + 2 (– 2) = 0 or x =
3 +4 CO2 +4 NO2
Actual oxidation numbers of different C atoms are :
+2 0 +2 +5 N2O5
O == C == C* == C == O  Example 9.
(the element marked with asterisk (*) shows Calculate the oxidation number of all the atoms
different oxidation number from rest of the atoms in the following compounds and ions :
of the same element). CO2 , SiO2 , PbSO4 , ClO4–
(e) Br3O8 (tribromooctaoxide) Solution: CO2 : Oxidation number of each oxygen
Calculated oxidation number of Br atom = –2
16 Oxidation number of carbon (say x)
= 3x + 8(– 2) = 0 or x =
3 x –2
Actual oxidation number of different Br atoms are :
C O2
x + (–2 × 2) = 0 or x = +4
∴ Oxidation number of C = +4, O = –2
SiO2 : Oxidation number of each oxygen
(f) S4O62– (tetrathionate ion) atom = –2
Calculated oxidation number of S Oxidation number of silicon (say x)
5 x –2
= 4x + 6(– 2) = – 2 or x = + Si O2
2
Actual oxidation number of different S atoms are: x + (–2 × 2) = 0 or x = +4
O O Oxidation number of Si = + 4, O = – 2
0 0
+5 * * +5 PbSO4 : Oxidation number of each oxygen
O S S S S O = –2
O O Oxidation number of lead (Pb) = +2
Oxidation number of sulphur (say x)
 8/12 MODERN'S abc + OF CHEMISTRY–XI

+2 x –2 S2O82–
Pb S O4 2x + (–2 × 6) + (–1 × 2) = –2
+2 + x + (–2 × 4) = 0 or x = + 6 2x = –2 + 14 = +12
Oxidation number of Pb = + 2, S = + 6, ∴ x = +6.
O=–2
Thus, by the application of rules, we can calculate
ClO4– : Oxidation number of each oxygen
= –2
the oxidation number of the desired element in a
Oxidation number of chlorine (say x)
compound or in an ion. Metals have positive oxidation
LM x −2 O − states while non-metals may have positive or negative

O PQ
oxidation states. The atoms of transition elements
NCl 4 (d-block elements) usually exhibit several oxidation
x + (–2 × 4) = –1 or x = +7 states. The highest positive oxidation state of a
∴ Oxidation number of O = 2, Cl = +7 representative element is the group number for the
 Example 10. first two groups (s-block elements) and the group
Calculate the oxidation number of sulphur in number minus 10 for other groups, i.e. p-block elements
S2O82– ion. (except for noble gases). Thus, the highest value of
oxidation state exhibited by an atom of an element
Solution: In S 2O 82– , there is one peroxide bond
(⎯O⎯O⎯) therefore, two oxygen atoms, oxidation generally increases across period in the periodic table.
number is – 1 (i.e.,O22–) and for the other six oxygen For example, in the third period, the highest value of
atoms, the oxidation number is – 2. oxidation state increases from +1 to +7 in the compounds
of the elements, as shown below :

s-block p-block
Group 1 2 13 14 15 16 17
Element Na Mg Al Si P S Cl
Compound NaCl MgSO4 AlF3 SiCl4 PF5, P4O10 SF6, SO3 HClO4
Oxidation state of the +1 +2 +3 +4 +5 +6 +7
group element in the
compound

4. –3, + 3, + 7, + 5, + 2, – 4
5. –1, +1, +7, 0 (+2 –2 –2x = 0 ∴ x = 0) + 4
1. What is the oxidation number of nitrogen in
6. K(+1), Mn(+7), O(–2), K(+1), Cr(+6), O(–2), K(+1),
(a) nitric acid (b) nitrous acid (c) nitric oxide
Cl (+7), O(–2)
(d) nitrous oxide (e) ammonia (f) N2
7. + 2, 0, – 1, – 1
2. What is the oxidation number of the underlined
atoms in the following ? 8. –3, –2.5, + 2, +4 and +4
KMnO4, Na2Cr2O7, Fe3O4, KClO3, PO43–, CCl4 REDOX REACTIONS IN TERMS OF OXIDATION
3. What are the oxidation numbers of the following ? NUMBER
(a) Cr in CrO42– (b) C in C6H12O6
Based upon the concept of oxidation number,
(c) I in IF7 (d) O in O3
oxidation is
4. Determine the oxidation number of the atom in bold
in the following species : a chemical change in which there is an increase
BH3, BF3, BrO4–, HPO42–, S2O32–, SiH4 in oxidation number.
5. Determine the oxidation number of Cl in HCl, On the other hand, reduction is
HClO, ClO4– and Ca(OCl) Cl and ClO2. a chemical change in which there is a decrease
6. Calculate the oxidation number of all the atoms in in the oxidation number.
the following well known oxidants : For example, consider the following reactions:
KMnO4, K2Cr2O7, KClO4
7. Calculate the oxidation number of oxygen in the (i) Reduction
following : OF2, O2, Na2O2 and CH3COOH
8. Calculate the oxidation number of C in the 0 –1 –1 0
following : C2H6, C4H10, CO, CO2 and HCO3– Cl2 (g) + 2Br– (aq) ⎯⎯→ 2Cl– (aq) + Br2 (aq)

Oxidation
1. (a) +5, (b) +3, (c) +2, (d) +1, (e) –3; nitrogen is Here oxidation number of bromine increases from
more electronegative than H, (f) 0. –1 to 0 and that of chlorine decreases from 0 to –1.
2. +7, +6, +2.66, + 5, + 5, + 4 (Cl is more Therefore, bromide ion is oxidised to Br2 and Cl2 is
electronegative than C) reduced to Cl– ions.
3. (a) + 6, (b) 0, (c) + 7, (d) 0
REDOX REACTIONS 8/13
(ii) Reduction In this case, MnO2 is reduced (oxidation number
of Mn decreases from +4 to 0) and Al is oxidised
0 +1 –1 +2 –1 0 (oxidation number increases from 0 to +3). Thus, Al
Zn + 2HCl (aq) ⎯⎯→ ZnCl2 + H2 acts as a reducing agent and MnO 2 acts as an
oxidising agent.
Oxidation Consider an ionic reaction :
In this reaction, oxidation number of zinc Reduction
increases from 0 to +2 and therefore zinc is oxidised.
The oxidation number of hydrogen decreases from +1 +7 –1 +2
0
to 0 and therefore, H2 is reduced. The oxidation 2MnO–4 + 10Cl– + 16 H+ ⎯⎯→ 2Mn2+ + 5Cl2 + 8H2O
number of chlorine remains unchanged.
Oxidation
(iii) Reduction
In this case, MnO–4 is reduced (oxidation number
+4 – 2 +1 –1 +2 –1 0 +1 – 2 of Mn decreases from +7 to +2) and Cl is oxidised
MnO2 + 4HCl ⎯⎯→ MnCl2 + Cl2 + 2H2O (oxidation number increases from –1 to 0). Thus MnO4–
acts as an oxidising agent and Cl– acts as a reducing
Oxidation agent.
In this reaction, the oxidation number of The various terms studied in this chapter can be
manganese decreases from +4 (in MnO2) to +2 (in summed up as :
MnCl2) indicating that manganese dioxide undergoes
reduction. On the other hand, the oxidation number of Oxidation : Loss of electrons or Increase
chlorine increases from –1(in HCl) to 0 (in Cl2) indicating in oxidation number.
that hydrochloric acid undergoes oxidation. Reduction : Gain of electrons or Decrease
Similarly, oxidising and reducing agents can be in oxidation number.
defined as follows : Oxidising agent : Electron acceptor : Substance
Oxidising agent is whose oxidation number
a substance which increases the oxidation decreases.
number of other substance in a chemical
reaction. Reducing agent : Electron donor : Substance
Alternatively, the oxidation number of oxidising whose oxidation number
agent decreases. On the other hand, reducing agent increases.
is a substance which decreases the oxidation
number of other substance in a chemical
reaction.
 Example 11.
Thus, the oxidation number of a reducing agent
increases. Identify the oxidising and reducing agent and the
atoms undergoing oxidation and reduction in the
TO SUM UP:
following reactions :
An increase in oxidation number corresponds to
oxidation of the element in the given compound (a) H2S + HNO3 ⎯⎯→ NO + S + H2O
that acts as a reductant or reducing agent. A (b) Zn + CuSO4 ⎯⎯→ Cu + ZnSO4
decrease in oxidation number corresponds to (c) I2 (g) +H2S (g) ⎯⎯→ 2HI (g) + S(s)
reduction of the element in a compound and it (d) 4Zn (s) + 10H+ (aq) + NO3– (aq) ⎯⎯→
behaves as an oxidant or oxidising agent. 4Zn2+ (aq) + NH4+(aq) + 3H2O(l)
In the above example (iii), manganese dioxide acts Solution: (a)
as an oxidising agent (oxidation number of Mn Reduction
decreases from +4 to +2) while hydrochloric acid acts
as a reducing agent (oxidation number of Cl increases
+ 1 –2 + 1 +5 –2 +2 –2 0 +1 –2
from –1 to 0). Similarly, consider the reaction :
H2S + HNO3 ⎯⎯→ NO + S + H2 O
Reduction
Oxidation
+4 0 0 +3 We observe that oxidation number of S increases from
3MnO2 + 4Al ⎯⎯→ 3Mn + 2Al2O3 –2 (in H2S) to 0 (in S) which means that H2S is being
oxidised or H2S is acting as a reductant. The oxidation
Oxidation number of nitrogen decreases from +5 (in HNO3) to +2 in
(Oxidation numbers of only those atoms are shown (NO) indicating that HNO3 is being reduced or HNO3 is
which undergo change). acting as an oxidant.
 8/14 MODERN'S abc + OF CHEMISTRY–XI

Reduction  Example 13.

Justify that the reaction :
0 +2 +6 –2 0 +2 +6 –2 2Cu2O(s) + Cu2S(s) ⎯⎯→ 6Cu (s) + SO2(g)
(b) Zn + Cu S O4 ⎯⎯→ Cu + Zn S O4 is a redox reaction. Identify the species oxidised,
reduced, acts as an oxidant or a reductant.
Oxidation
Solution:
We observe that oxidation number of zinc increases from
Let us write the oxidation number of each element :
0 (in Zn) to +2 (in ZnSO4) which means that Zn is being
oxidised or zinc is acting as a reducant. On the other hand, Reduction
the oxidation number of copper decreases from +2 (in CuSO4)
to 0 (in Cu), indicating that copper is being reduced or CuSO4 +1 –2 +1 –2 0 +4 –2
is acting as an oxidant. 2Cu2O(s) + Cu2S(s) ⎯⎯→ 6Cu(s) + S O2(g)
Reduction
0 –2 –1 0 Oxidation
(c) I2 (g) + H2S (g) ⎯⎯→ 2HI (g) + S (s) In this reaction copper is reduced from +1 state (in Cu2O
or Cu2S) to 0 ( in Cu) whereas sulphur is oxidised from –2
Oxidation state (in Cu2S) to +4 (in SO2). Therefore, the above reaction
is a redox reaction.
Oxidation number of iodine decreases from 0 to –1. In the reaction, Cu2O helps sulphur in Cu2S to increase its
Therefore, it is reduced and acts as an oxidant. The oxidation oxidation number from –2 to +4 and therefore, Cu2O is oxidant.
number of S in hydrogen sulphide increases from –2 to 0. Alternatively, sulphur in Cu2S helps copper in both
Therefore, it is oxidised and hence acts as a reductant. Cu2O and Cu2S to decrease its oxidation number (i.e., get
Reduction reduced) and therefore, Cu2S is reductant.
0 +1 +5 +2 –3 +1 0
(d) 4Zn(S)+10H+(aq) + NO3– (aq)⎯→4Zn2+(aq) + NH4+ (aq) + 3H2O(l)

Oxidation
9. Identify the oxidants and reductants in the
Oxidation number of zinc increases from 0 to +2. following reactions :
Therefore, it is oxidised and acts as a reductant. The (a) CH4(g) + 4Cl2(g) ––→ CCl4(g) + 2HCl (g)
oxidation number of N decreases from +5 to –3. and, (b) C2H2O4(aq) + 2H+ + MnO2(s) ––→
therefore, it is reduced and acts as an oxidant. Mn2+(aq) + 2CO2 (g) + 2H2O (l)
 Example 12. (c) I2(aq) + S2O3 (aq) ––→ 2I–(aq) + S4O62–(aq)
2–

Determine the change in the oxidation number of S (d) Cl2 (g) + 2Br– (aq) ––→ 2Cl–(aq) + Br2(aq)
in H2S and SO2 in the following industrial reaction:
2H2S (g) + SO2 (g) ⎯⎯→ 3S (s) + 2H2O (g)
9. Oxidants and reductant are respectively
Solution: (a) Cl2, CH4, (b) MnO2, C2H2O4, (c) I2, S2O32–,
(d) Cl2, Br–.
–2 +4 0
2H2 S (g) + SO2 (g) ⎯⎯→ 3 S (s) + 2H2O (g) Oxidation Number and Valency
There have been confusion regarding the usage of
the terms oxidation number and valency. The two
Change in O.N. of S in H2S from – 2 to 0
terms have different meanings as discussed below :
Change in O.N. of S in SO2 from + 4 to 0.
Valency Oxidation number
1. Valency is the combining capacity of an atom. It is 1. Oxidation number is the residual charge which an
expressed as the number of hydrogen atoms or double atom has or appears to have when all the atoms are
the number of oxygen atoms with which an atom of the removed as ions.
element combines. 2. Since it refers to charge, it can be positive, negative or
2. Since it refers to combining capacity, it is a whole zero. For example, in NH3, nitrogen has oxidation
number only. As such it does not carry any plus or minus number of –3 and that of hydrogen is +1.
sign. For example, in NH3 the valency of nitrogen is 3 3. Oxidation number of an element can be zero. For
and that of hydrogen is 1. example, oxidation number of C in CH2Cl2 is zero.
3. Valency of an element cannot be zero (except for noble 4. Oxidation number may have fractional values. For
gases). example, oxidation number of S in Na2S4O6 is +2.5.
4. Since atoms always combine in whole numbers, valency 5. Even the elements C, N and S exhibit variable valency.
of an element is always a whole number. For example, the oxidation number of N (given in
5. In general, elements like C, N and S exhibit constant brackets) in its compounds vary from +5 to –3 as:
valency. Thus, valency of N in all its compounds is three. N2O5(+5), NO2(+4), N2O3(+3), NO(+2), N2O(+1), N2(0),
N2H4(–2) and NH3(–3)
REDOX REACTIONS 8/15

OXIDATION NUMBER AND NOMENCLATURE Solution:

When an element forms two monoatomic cations Knowing oxidation of metallic element, these
(representing different oxidation states), the two ions compounds may be represented as :
are distinguished by using the ending -ous and ic. The +3
suffix -ous is used for the cation with lower oxidation (i) HAuCl4 : HAu(III)Cl4
state and the suffix -ic is used for the cation with higher +1
oxidation state. For example, (ii) Tl2O : Tl2(I)O
Cu + (oxidation number +1) cuprous : Cu 2+
+2
(oxidation number +2) cupric. (iii) FeO : Fe(II)O
However, Albert Stock proposed a new system +3
known as Stock system. In this system, the oxidation (iv) Fe2O3 : Fe2(III)O3
states are indicated by Roman numeral written in
parentheses immediately after the name of the +1
element. For example, (v) CuI : Cu(I)I
Cu2O : Copper (I) oxide +2
(vi) CuO : Cu(II)O
SnO : Tin (II) oxide
+2
FeCl2 : Iron (II) chloride
(vii) MnO : Mn(II)O
FeCl3 : Iron (III) chloride
+4
CuO : Copper (II) oxide (viii) MnO2 : Mn(IV)O2
SnO2 : Tin (IV) oxide TYPES OF REDOX REACTIONS
AuCl : Gold (I) chloride The redox reactions may be classified into the
AuCl3 : Gold (III) chloride following types :
Hg2Cl2 : Mercury (I) chloride 1. Combination reactions
The chemical reactions in which two or more
HgCl2 : Mercury (II) chloride
substances (elements or compounds) combine to form
Many more examples are taken for illustration : a single substance are called combination reactions.
A combination reaction may be expressed as :
Mn2O7 : Manganese (VII) oxide
A + B ⎯⎯→ C
K2Cr2O7 : Potassium dichromate (VI)
For a combination reaction to be a redox reaction
Na2CrO4 : Sodium chromate (VI) one or both A and B must be in the elementary form.
V2O5 : Vanadium (V) oxide All combustion reactions in which elemental oxygen
Stock system is not used for non-metals. is used and all other reactions which involve
elements other than oxygen are redox reactions.
Some common combination redox reactions are :
0 0 +4 –2
 Example 14. C(s) + O2 (g) ⎯⎯→ C O2
Write formulas for the following compounds – 4 +1 0 +4 –2 +1 –2
CH4 (g) + 2O2(g) ⎯⎯→ C O2(g) + 2H2 O(l)
(i) Mercury(II) chloride (ii) Nickel (II) sulphate
0 0 +2 –2
(iii) Tin(IV) oxide (iv) Thallium (I) sulphate 2Mg (s) + O2(g) ⎯⎯→ 2MgO(s)
(v) Iron (III) sulphate (vi) Chromium (III) oxide. 0 0 +2 –3
Solution:
3Mg (s) + N2(g) ⎯⎯→ Mg3N2(s)
0 0 +2–2
(i) HgCl2 (ii) NiSO4 (iii) SnO2 Fe (s) + S(s) ⎯⎯→ FeS(s)
(iv) Tl2SO4 (v) Fe2(SO4)3 (vi) Cr2O3 2. Decomposition reactions
 Example 15. The chemical reactions in which a compound
Using stock notation, represent the following breaks up into two or more simpler substances are
compounds : called decomposition reactions. The decomposition
reactions are the opposite of combination reactions.
(i) HAuCl4 (ii) Tl2O (iii) FeO (iv) Fe2O3 For a decomposition reaction to be a redox reaction,
(v) CuI (vi) CuO (vii) MnO (viii) MnO2 at least one of the component formed after the break
down of the compound must be in the elemental state.
 8/16 MODERN'S abc + OF CHEMISTRY–XI

Some common examples of redox decomposition (b) Non-Metal displacement reactions. The
reactions are : non-metal displacement redox reactions are mainly
+1 –2 0 0
Heat
hydrogen displacement or oxygen displacement
2H2O (l) ⎯⎯⎯ → 2H2(g) + O2(g)
reactions. For example,
+1 –1 0 0 (i) All alkali metals and some alkaline earth metals
Heat
2NaH (s) ⎯⎯⎯ → 2Na(s) + H2(g) (e.g, Ca, Sr, Ba) which are good reducing agents will
+2 –2 0 0 displace hydrogen from cold water.
Heat
2HgO (s) ⎯⎯⎯ → 2Hg(l) + O2(g) 0 +1 –2 +1 –2+1 0
2Na(s)+ 2H2O(l) ⎯⎯→ 2NaOH(aq) + H2(g)
+1 +5 –2 +1 –1 0
2KClO3(s) ⎯⎯⎯ Heat 0 +1 –2 +2 –2 +1 0
→ 2KCl(s) + 3O2(g)
Mg(s)+ 2H2O(l) ⎯⎯→ Mg(OH)2(s) + H2(g)
It may be noted that all decomposition reactions
are not redox reactions. For example, decomposition 0 +1 –2 +2 –2 +1 +0

of calcium carbonate is not a redox reaction because it Ca (s) + 2H2O(l) ⎯⎯→ Ca(OH)2(aq)+ H2(g)
does not involve change in oxidation number of (ii) Less active metals such as magnesium and iron
elements. react with steam to produce dihydrogen gas.
+2 +4–2 +2 –2 +4 –2 0 +1 –2 +2 –2 +1 0
Heat
Heat
CaCO3(s) ⎯⎯⎯→ CaO(s) + C O2(g) Mg(s) + 2H2O(g) ⎯⎯⎯⎯
→ Mg(OH)2 + H2(g)
(Steam)
3. Displacement reactions
The reactions in which one ion (or atom) in a 0 +1 –2 +3 –2 0
Heat
compound is replaced by an ion (or atom) of other 2 Fe(s) + 3H2O(l) ⎯⎯⎯⎯ → Fe2O3 + 3H2(g)
element are called displacement reactions. These (iii) Many metals including those which donot
reactions are very common in chemistry in which a react with cold water displace hydrogen from acids.
more active metal displaces or removes another atom For example,
from a compound. In general, a displacement reaction 0 +1 –1 +2 –1 0
may be expressed as : Zn(s) + HCl (aq) ⎯⎯→ ZnCl2(aq) + H2(g)
XY + Z ⎯⎯→ X + ZY 0 +1 +6 –2 +2 +6 –2 0
In this reaction, the atom X from the compound Zn(s) + H2SO4(aq) ⎯⎯→ ZnSO4(aq) + H2(g)
0 +1 –1 +2 –1 0
XY has been displaced by another atom Z.
Mg(s) + 2HCl(aq) ⎯⎯→ MgCl2(aq) + H2(g)
The displacement reactions are of two types : 0 +1 –1 +3 –1 0
(a) Metal displacement and 2Al(s) + 6HCl(aq) ⎯⎯→ 2AlCl3(aq) + 3H2(g)
(b) Non-metal displacement 0 +1 –1 +2 –1 0
Fe(s) + 2HCl(aq) ⎯⎯→ FeCl2(aq) + H2(g)
(a) Metal displacement reactions. In these
Metals like cadmium and tin which donot react
reactions, a metal in a compound can be displaced by
with steam also react with acids to displace dihydrogen
another metal in the uncombined state. These have
gas :
already been discussed earlier.
0 +1 –1 +2 –1 0
Some common examples of metal displacement Cd(s) + 2HCl(aq) ⎯⎯→ CdCl2(aq) + H2(g)
reactions are :
0 +1 –1 +2 –1 0
+2 +6 –2 0 0 +2+6–2 Sn(s) + 2HCl(aq) ⎯⎯→ SnCl2(aq) + H2(g)
CuSO4(aq) + Zn(s) ⎯⎯→ Cu(s) + ZnSO4(aq) (iv) Very less reactive metals such as silver (Ag),
+2 +6 –2 0 +2 +6 –2 0 gold (Au), etc which occur in the native state donot
NiSO4(aq) + 2Co(s) ⎯⎯→ CoSO4(s) + Ni(s) react even with dilute hydrochloric acid.
+3 –2 0 0 +3 –2 The above reactions may be used to prepare
Fe2O3(s) + Al(s) ⎯⎯→ 2Fe(s) + Al2O3(s) dihydrogen gas in the laboratory. The reactivity of the
+3 –2 0 +3 –2 0 metals can be predicted from the rate of evolution of
Cr2O3(s) + 2Al(s) ⎯⎯⎯⎯ Heat Al2O3(s) + 2Cr(s) H2 from water or aqueous acids . For example, sodium
→
reacts with water very readily (fastest rate),
+4 –1 0 0 +2 –1
Heat
TiCl4(l) + 2Mg(s) ⎯⎯⎯ magnesium reacts slowly while iron reacts at the
⎯→ Ti(s) + 2MgCl2(s) slowest rate while silver and gold donot react at all.
+5 –2 0 0 +2 –2 We have already learnt that metals such as zinc
Heat
V2O5(s) + 5Ca(s) ⎯⎯⎯⎯ → 2V(s) + 5CaO(s) (Zn), copper (Cu) and silver (Ag) though have the
In each of these reactions, the reducing metal is a tendency to lose electrons, but their reducing tendency
better reducing agent than the metal being reduced is in the order Zn > Cu > Ag.
(e.g., Cu, Ni, Fe, Cr, Ti, V, etc.). This is because the Reactivity of non-metals. Like metals, there is
reducing metal has greater tendency to lose electrons also an activity series for non-metals, therefore, their
as compared to the one which is reduced. reactivity depends upon their oxidising power. For
REDOX REACTIONS 8/17

example, oxidising power of halogens decreases as oxidation state is simultaneously oxidised and reduced.
we move down the group 17 from fluorine to iodine. In other words, one reacting substance in a
Thus, fluorine is the strongest oxidising agent. It can disproportionation reaction always contains an
displace in their aqueous solutions Cl2 from Cl– ions, element that can exhibit at least three oxidation states.
Br2 from Br– ions and I2 from I– ions. Thus, fluorine The element in the form of reacting substance is in
can show displacement reactions as : the intermediate oxidation state and both higher and
2X–(aq) + F2(aq) ⎯⎯→X2(g) + 2F–(aq) lower oxidation states exist for that element. The most
where X– = Cl–, Br– and I– common example is the decomposition of hydrogen
peroxide.
In fact, fluorine is so reactive that it even attacks
water and displaces the oxygen of water. 2H2O2(aq) ⎯⎯→ 2H2O(l) + O2(g)
2H2O(l) + 2F2(g) ⎯⎯→ 4HF(aq) + O2(g) In this reaction, oxidation number of O decreases
It is because of this reason, the displacement from – 1 to – 2 (in H2O) and increases from – 1 to 0
reactions of chlorine bromine or iodine using fluorine (in O2).
are usually not carried out in aqueous solutions. This may be simply represented as
On the other hand, chlorine can displace bromide Reduced
and iodide ions in aqueous solution as shown below :
0 +1 –1 +1 –1 0 +1 –1 +1 –2 0
Cl2 + 2K Br (aq) ⎯⎯→ 2K Cl (aq) + Br2(l) H2O2 (aq) ⎯⎯→ H2O(l) + O2(g)
0 +1 –1 +1 –1
Cl2 + 2K I (aq) ⎯⎯→ 2KCl (aq) + I2(s) Oxidised
Since bromine and iodine are coloured and dissolve Some other examples are :
in CCl4 or CS2, these can be easily identified from the
(i) Phosphorus and sulphur undergo dispropor-
colour of their solution. The above reactions may be
written in ionic from as : tionation in alkaline medium as shown below:
− −
– – – – – P4 (s) + 3OH (aq) + 3H2O (l) ⎯⎯
→ PH3 (g) + 3H2PO2 (aq)
2X (aq) + Cl2(g) ⎯⎯→ X2 + 2Cl (aq) (X = Br , I )
–1 0 0 –1 In this reaction, oxidation number of P increases
e.g., 2Br– (aq) + Cl2(g) ⎯⎯→ Br2(l) + 2Cl–(aq) from 0 to + 1 (in H2PO2–) and decreases from 0 to – 3
–1 0 0 –1
– – (in PH3).
2I (aq) + Cl2(g) ⎯⎯→ I2(s) + 2Cl (aq) Reduced
The above two reactions form the basis of identifying
bromide (Br–) and iodide (I–) ions in the laboratory
by carbon tetrachloride (CCl4) or carbon disulphide 0 –3 +1
(CS2). This test is popularly known as ‘layer test’. P4 (s) + 3OH– (aq) ⎯⎯→ PH3(g) + 3H2PO2– (aq)
Similarly, bromine can displace iodine from iodide
ion in the aqueous solution : Oxidised
0 –1 –1 0 (ii) S8(s) + 12OH– (aq) ⎯→ 4S2– (aq) + 2S2O32– (aq)
Br2(l) + 2I–(aq) ⎯⎯→ 2Br– (aq) + I2(s) + 6H2O
The above halogen displacement reactions have In this reaction, oxidation number of S increases
been widely used in the laboratory and industry. The from 0 to + 2 (in S2O32– ion) and decreases from 0 to
halogens can be recovered from the corresponding -- 2 (in S2– ion).
halides by using suitable oxidising agents according Reduced
to the reaction :
Oxidising agent
2X– (aq) ⎯⎯⎯⎯⎯⎯⎯→ X2 + 2e– 0 –2 +2
(where X = halogen element) S8(s) + 12OH–(aq) ⎯→4S2–(aq) + 2S2O2–
3 (aq) + 6H2O
It may be noted that although a number of oxidising
agents such as KMnO4, K2Cr2O7, MnCl2, etc are
available to oxidise Cl–, Br–, and I– ions to liberate Oxidised
Cl2, Br2 and I2 respectively, no oxidising agent is (iii) Chlorine also undergoes disproportionation in
available to oxidise F– ions to F2. This is because, alkaline medium as :
fluorine itself is the strongest oxidising agent. Reduction
Therefore, the only method to prepare fluorine is
to oxidise F– ions electrolytically. 0 +1 –1
4. Disproportionation reactions Cl2(g) + 2OH–(aq) ⎯→ ClO–(aq) + Cl– (aq) + H2O(l)
These are the reactions in which an element in one
Oxidation
 8/18 MODERN'S abc + OF CHEMISTRY–XI

This reaction forms the basis of preparing 0

household bleaching agents. The hypochlorite (ClO–) (vi) 3Tl+ 


 2Tl +Tl
3+

ion acts as a bleaching agent by oxidising the colouring  Example 18.

matter (or stains) to colourless compounds.
Classify the following redox reactions giving reasons:
Like chlorine, bromine and iodine also undergo
similar disproportionation reactions. However, (a) N2(g) + O2(g) ⎯→ 2NO(g)
fluorine does not show this behaviour. This is because 1
(b) 2Pb(NO3) (s) ⎯→ 2PbO(s) + 2NO2(g) + O (g)
fluorine is the most electronegative and strongest 2 2
oxidising agent and therefore, it does not show positive (c) NaH(s) + H2O(l) ⎯→ NaOH (aq) + H2(g)
oxidation states. Therefore, fluorine reacts in different (d) 2NO2(g) + 2OH–(aq)⎯→NO2–(aq) + NO3– (aq)+ H2O(l)
way forming oxygen difluoride as : Solution:
0 −1 +2 −1
2F2 ( g ) + 2OH– (aq) ⎯→ 2 F − ( aq ) + OF2 ( g ) + H2O(l) 0 0 +2 –2
(a) N2(g) + O2(g) ⎯→ 2NO(g)
It may be noted that F2 also reacts with water to
The compound nitric oxide is formed by the combination
produce some oxygen. of elemental substances (N2 and O2). Therefore, it is a
There is another important disproportionation combination redox reaction.
reaction. Copper (I) disproportionates to copper (II)
+2 +5 –2 +2 –2 +4 –2 0
and copper as : 1
Heat
(b)2Pb(NO3)2 (s)⎯⎯⎯
2 Cu+ ⎯⎯→ Cu + Cu2+ → 2PbO(s) + 2NO2(g) + O (g)
2 2
Reduction Lead nitrate decomposes to form three products and
therefore, it is a decomposition redox reaction.
+1 –1 +1 –2 +1 –2 +1 0
+1 0 +2 (c) NaH(s) + H2O(l) ⎯→ NaOH (aq) + 2 H2(g)
2Cu+ ⎯⎯→ Cu + Cu2+ Hydrogen of water has been displaced by hydride ion
to form dihydrogen gas. Therefore, it is displacement redox
reaction.
Oxidation
+4 +3 +5
Therefore, Cu(I) is unstable and only found in the (d) 2NO2(g) + 2OH–(aq) ⎯→ NO2–(aq) + NO3– (aq) + H2O(l)
solid state. In this reaction, the +4 oxidation state of nitrogen
(in NO2) decreases to +3 (in NO2–) and increases to +5 (in
NO 3 – ). Therefore, it is disproportionation redox
 Example 16. reaction.
Which of the two ClO 2 – or ClO 4 – show KEY NOTE
disproportionation reaction and why ?
Pb3O4 reacts with HCl and HNO3 quite differently as:
Write reaction for the species that disproportionates.
Solution: The oxidation state of Cl in ClO2– is + 3 and in Pb3O4 + 8 HCl ⎯→ 3PbCl2 + Cl2 + 4H2O
ClO4–, it is + 7. So, chlorine is present in highest oxidation Pb3O4 + 4 HNO3 ⎯→ 2Pb(NO3)2 + PbO2+ 2H2O
state of + 7 in ClO4– and it cannot increase its oxidation Why does it react differently ? This is an
state. Hence ClO4– does not disproportionates. interesting observation.
The disproportionation reaction of ClO2– is Pb3O4 is not a simple compound. It is a mixture of 2
+3
–
–1
–
+5 mol of PbO and 1 mol of PbO2 as 2 PbO. PbO2.
3ClO2 ⎯⎯→ Cl + 2ClO3– In PbO 2, lead is present in + 4 oxidation state,
 Example 17. whereas the stable oxidation state of lead in PbO is
Write the disproportionation reactions of the + 2. Therefore PbO2 can act as an oxidising agent
following species : and can oxidise Cl– ion in HCl to chlorine.
(i) ClO – (ii) ClO3– (iii) Cl– (iv) ClO2– It may be noted that PbO is a basic oxide. Thus the
(v) ClO4 – (vi) Tl + reaction :
Solution: Pb3O4 + 8 HCl ⎯→ 3PbCl2 + Cl2 + 4H2O
+1 –1 +5 can be splitted into the following two reactions:
(i) 3ClO– ⎯⎯→ 2Cl– + ClO3– 2PbO + 4HCl ⎯→ 2PbCl2 + 2H2O : acid-base reaction
+4 –1 +2 0
+5 –1 +7 PbO2 + 4HCl ⎯→ PbCl2 + Cl2 + H2O : redox reaction
(ii) 4ClO–3 ⎯⎯→ Cl– + 3ClO4–
However, nitric acid is itself an oxidising agent and
(iii) Cl– does not disproportionates. therefore, no reaction occurs betwen PbO2 and HNO3.
+3 –1 +5 But the acid-base reaction between PbO and HNO3
–
(iv) 3ClO2– ⎯⎯→ Cl– + 2ClO3 may occur as :
–
(v) ClO4 does not disproportionate because in this
2PbO + 4HNO3 ⎯⎯→ 2Pb (NO3)2 + 2H2O
oxoanion, chlorine is present in its highest
oxidation state i.e., + 7.
REDOX REACTIONS 8/19

The complete reaction may be written as : Step 7. Finally, balance hydrogen and oxygen. For
Pb3O4 + 4 HNO3 ⎯→ 2Pb (NO3)2 + PbO2 + 2H2O balancing for oxygen atoms add water molecules to
Thus, it is the passive nature of PbO2 against HNO3 the side deficient in it. Balancing of hydrogen atoms
which results in different reactions of Pb3O4 with depend upon the medium (acidic or basic) as explained
HNO3 than those with HCl. below :
(i) For reactions taking place in acidic solutions,
BALANCING OXIDATION–REDUCTION add H+ ions to the side deficient in hydrogen atoms.
REACTIONS
(ii) For reactions taking place in basic solutions,
Though there are a number of methods for add H2O molecules to the side deficient in hydrogen
balancing oxidation-reduction reactions, two methods atoms and simultaneously add equal number of OH–
are very important. These are : ions on the other side of the equation.
1. Oxidation number method
Step 8. Finally balance the equation by cancelling
2. Ion-electron method or half equation method. common species present on both sides of the equation.
1. Oxidation number method. Let us discuss the above method stepwise with
We have learnt that during oxidation, there is the help of reaction between zinc and hydrochloric acid.
always increase in oxidation number and during Step 1. The skeleton equation is :
reduction there is always decrease in oxidation Zn + HCl ⎯⎯→ ZnCl2 + H2
number. Therefore, during a redox reaction, the total
Step 2. Oxidation number of various atoms
increase in oxidation number must be equal to total
involved in the reaction :
decrease in oxidation number. This is the basic
principle for balancing the chemical equations. In 0 +1 –1 +2 –1 0
Zn + HCl ⎯⎯→ ZnCl2 + H2
addition, the law of conservation of mass should not
be violated, i.e., the number of atoms of each kind on Step 3. The oxidation number of zinc has
one side of the equation must be equal to the number increased from 0 to +2 while that of hydrogen has
of atoms of the corresponding elements on the other decreased from +1 to 0. However, the oxidation number
side. The following steps should be followed : of chlorine remains the same on both sides of the
Steps for Balancing Redox Equations by Oxidation equation. Therefore, zinc is reducing agent while HCl
Number Method is oxidising agent in this reaction and the changes are
shown as :
Step 1. Write the skeletal redox equation for all
the known reactants and products of the reaction.
0 +1 –1 +2 –1 0
Step 2. Indicate the oxidation number of all the Zn + HCl ⎯⎯→ Zn Cl2 + H2
atoms in each compound above the symbol of the
element.
Step 4. The increase and decrease in oxidation
Step 3. Identify the element or elements which number per atom can be indicated as :
undergo a change in oxidation number. Usually only
O.N. increases by 2 per atom
two elements will be involved, one whose oxidation
number increases (i.e. reducing agent) and the other
0 +1 +2 0
whose oxidation number decreases (i.e. oxidising
Zn + HCl ⎯⎯→ ZnCl2 + H2
agent).
Step 4. Calculate the increase or decrease in O.N. decrease by 1 per atom
oxidation numbers per atom. If more than one atom
of the same element is involved, find out the total Step 5. The increase in oxidation number of 2 per
increase or decrease in O.N. Then multiply this atom can be balanced with decrease in oxidation
number of increase/decrease of O. N. with the number number of 1 per atom if Zn atoms are multiplied by 1
of atoms which are undergoing the change. and HCl by 2. Consequently the equation will be :
Step 5. Equate the increase in oxidation number Zn + 2HCl ⎯⎯→ ZnCl2 + H2
with decrease in oxidation number on the reactant side Step 6. Balance all other atoms on both sides of
by multiplying the formulae of the oxidising and the equation. By chance, they are equal, otherwise
reducing agents. equate them.
Step 6. Balance the equation with respect to all Hence, balanced chemical equation is :
other atoms except hydrogen and oxygen. Zn + 2HCl ⎯⎯→ ZnCl2 + H2
 8/20 MODERN'S abc + OF CHEMISTRY–XI

3. To balance increase or decrease multiply C by 3

and Fe2O3 by 1 as :
 Example 19. Fe2O3 + 3 C ⎯⎯→ Fe + CO
Copper reacts with nitric acid. A brown gas is
formed and the solution turns blue. The equation 4. Balancing all other atoms, we get
may be written as : Fe2O3 + 3C ⎯⎯→ 2 Fe + 3 CO
Cu + NO3– ⎯⎯→ NO2 + Cu2+ (ii) Fe2+ + Cr2O72– + H+ ⎯⎯→ Cr3+ + Fe3+ + H2O
Balance the equation by oxidation number method.
1. The skeleton equation along with oxidation
Solution: Step 1. Skeleton equation
number of each atom
Cu + NO3– ⎯⎯→ NO2 + Cu2+
Step 2. Writing oxidation numbers of each atom +2 + 6 –2 +1 +3 +3 +1 –2
0 +5 –2 +4 –2 +2 Fe2+ + [Cr2O7]2– + H+ ⎯⎯→ Fe3+ + Cr3+ + H2 O
Cu + NO3– ⎯⎯→ NO2 + Cu2+ 2. The oxidation number of chromium decreases from
Step 3. +6 in Cr2O72– to +3 in Cr3+. The total decrease for
two chromium atoms in Cr2O72– to Cr3+ is 6. On
0 +5 +4 +2
the other hand, the oxidation number of iron
Cu + NO3– ⎯⎯→ NO2 + Cu2+ increases from +2 (in Fe 2+ ) to +3 (in Fe 3+ ).
Therefore, the equation can be written as :
The oxidation number of copper has increased from O.N. increases by 1 per atom
0 to +2 while that of nitrogen has decreased from +5 to +4.
Step 4. Show the increase/decrease of oxidation number +2 +6 +3 +3 +1
O.N. increases by 2 per atom
Fe2+ + [Cr2O7]2– + H+ ⎯⎯→ Fe3+ + Cr3+ + H2O

0 +5 +4 +2 O.N. decreases by 6 for 2 Cr atoms

Cu + NO3– ⎯⎯→ NO2 + Cu2+
3. To balance increase and decrease of oxidation
numbers, multiply Fe2+ by 6 and Cr2O72– by 1. Then
O.N. decreases by 1 per atom
we get
Step 5. Balance the increase/decrease in oxidation
number by multiplying NO3– by 2 and Cu by 1. 6Fe2+ + Cr2O72– + H+ ⎯⎯→ Fe3+ + Cr3+ + H2O
Cu + 2NO3– ⎯⎯→ NO2 + Cu2+ 4. On counting and equating the atoms on both sides,
Step 6. Balance other atoms except H and O as we get the balanced equation as :
Cu + 2NO3– ⎯⎯→ 2NO2 + Cu2+ 6Fe2+ + Cr2O72– + 14H+ ⎯⎯→ 6Fe3+ + 2Cr3+ + 7H2O
Step 7. Reaction takes place in acidic medium, so add (iii) Zn + HNO3 ⎯⎯→ Zn (NO3)2 + NO2 + H2O
H+ ions to the side deficient in H+ and balance H and
O atoms : 1. The skeleton equation along with oxidation
Cu + 2NO3– + 4H+ ⎯⎯→ 2NO2 + Cu2+ + 2H2O number of various atoms is
 Example 20. 0 +1+5–2 +2 +5–2 +4 –2 +1 –2
Balance the following equations : Zn + HNO3 ⎯⎯→ Zn(NO3)2 + NO2 + H2 O
(i) Fe2O3 + C ⎯⎯→ Fe + CO O.N. increases by 2
(ii) Fe2+ + Cr2O72– + H+ ⎯⎯→ Fe3+ + Cr3+ + H2O
(iii) Zn + HNO3 ⎯⎯→ Zn (NO3 )2 + NO2
+ H2O 0 +5 +2 +4
(iv) C6H6 + O2 ⎯⎯→ CO2 + H2O 2. Zn + HNO3 ⎯⎯→ Zn (NO3)2 + N O2 + H2O
Solution:(i) Fe2O3 + C ⎯⎯→ Fe + CO
O.N. decreases by 1
1. The skeleton equation along with oxidation
number of each atom is : 3. Multiply HNO3 by 2
+3 –2 0 0 +2 –2 Zn + 2HNO3 ⎯⎯→ Zn(NO3)2 + NO2 + H2O
Fe2 O3 + C ⎯⎯→ Fe + C O
2. The oxidation number of C increases from 0 to +2 It has been observed that part of nitrogen
while that of Fe decreases from +3 to 0. Therefore, undergoes no change in oxidation number in
the equation may be written as forming Zn(NO3)2. However, in order to balance
O.N. increases by 2 per atom additional two NO3– ions, add 2HNO3 more on
the left hand side as :
+3 0 0 +2
Zn + 4HNO3 ⎯⎯→ Zn(NO3)2 + NO2 + H2O
Fe2 O3 + C ⎯→ Fe + CO
O.N. decreases by 3 per atom 4. Balance all other atoms.
3 × 2 per 2 atoms Zn + 4HNO3 ⎯⎯→ Zn(NO3)2 + 2NO2 + 2H2O
REDOX REACTIONS 8/21
–
(iv) C6 H6 + O2 ⎯⎯→ CO2 + H2O (iii) Cr(OH)3 + IO3– ⎯⎯→ I + CrO42–
1. The skeleton equation along with oxidation (in basic medium)
number of each atom : Solution: (i) FeS2 + O2 ⎯⎯→ Fe2O3 + SO2
–1 +1 0 +4 –2 +1 –2
1. The skeleton equation with oxidation number is :
C6 H6 + O2 ⎯⎯→ CO2 + H2O +2 –1 0 +3 –2 +4 –2

O.N. increases by 5 per atom Fe S2 + O2 ⎯⎯→ Fe2O3 + S O2

(Note : Oxidation number of S in FeS2 is –1 and
or 5 × 6 per 6 atoms not –2).
2. –1 0 +4 –2
2. The oxidation number of iron as well as sulphur
C6H6 + O2 ⎯⎯→ CO2 + H2O increases from +2 to +3 and –1 to +4 respectively.
O.N. decreases by 2 per atom Since Fe and S must maintain their atomic ratio,
or 2 × 2 per molecule the change in oxidation number will be considered
3. Multiply C 6 H6 by 2 and O 2 by 15 to balance together. On the other hand, the oxidation number
increase and decrease in O.N. of oxygen decreases from 0 to –2. Thus,
2 C6H6 + 15O2 ⎯⎯→ CO2 + H2O O.N. increases 1 per Fe and 5 per S atom
i.e. 1 + 2 × 5 = 11 per FeS2
4. Balance all atoms
2 C6 H6 + 15O2 ⎯⎯→ 12CO2 + 6H2O
 Example 21. +2 –1 0 +3 +4–2
Fe S2 + O2 ⎯⎯→ Fe2 O3 + SO2
Permangnate ion reacts with bromide ion in basic
medium to give managanese dioxide and bromate O.N. decreases by 2 per atom
ion. Write the balanced chemical equation for the or 4 per O2
reaction. 3. To balance increase and decrease of oxidation
number, multiply FeS2 by 4 and O2 by 11.
Solution:The chemical equation is :
4FeS2 + 11O2 ⎯⎯→ Fe2O3 + SO2
MnO4– + Br– ⎯⎯→ MnO2 + BrO3– 4. Balancing all atoms
1. The skeleton equation with oxidation number of 4FeS2 + 11O2 ⎯⎯→ 2Fe2O3 + 8SO2
each atom is :
(ii) MnO4– + Fe2+ + H+ ⎯⎯→ Mn2+ + Fe3+ + H2O
+7 –2 –1 +4 –2 +5 –2
1. The skeleton equation along with oxidation
MnO4– + Br– ⎯⎯→ MnO2 + BrO3–
number of each atom is as :
O.N. decreases by 3 per atom +7 –2 +2 +2 +3 +1 –2
Mn O4– + Fe2+ + H+ ⎯⎯→ Mn2+ + Fe3+ + H2 O
+7 –1 +4 +5
O.N. decreases by 5 per atom
MnO4– + Br– ⎯⎯→ MnO2 + BrO3–

O.N. increases by 6 per atom +7 +2 +2 +3

2. To balance increase and decrease in oxidation MnO4– + Fe2+ + H+ ⎯⎯→ Mn2+ + Fe3+ + H2O
numbers, multiply MnO4– by 2.
2MnO4– + Br– ⎯⎯→ MnO2 + BrO3– O.N. increases by 1 per atom
3. Balance all atoms other than H and O. 2. The oxidation number of Mn decreases from +7 to
2MnO4– + Br– ⎯⎯→ 2MnO2 + BrO3– +2 while that of Fe increases from +2 to +3.
4. Since the reaction occurs in basic medium, add OH– 3. Multiply Fe2+ by 5 and MnO4– by 1 to balance
ions to right hand side. increase and decrease in oxidation number.
2MnO4– + Br– ⎯⎯→ 2MnO2 + BrO3– + OH– MnO4– + 5Fe2+ + H+ ⎯⎯→ Mn2+ + Fe3+ + H2O
5. To add H atoms, add H2O molecules on the left 4. Balance all atoms (except H and O)
hand side and equal number of OH– ions on the
MnO4– + 5Fe2+ + H+ ⎯⎯→ Mn2+ + 5Fe3+ + H2O
right hand side
2MnO4– + Br– + H2O⎯⎯→ 2MnO2 + BrO3– + OH– This reaction takes place in acidic medium. The
+ OH– O and H atoms are balanced as given below :
or 2MnO4 + Br + H2O ⎯→ 2MnO2 + BrO3 + 2OH–
– – – 5. Balance O-atoms by adding equal number of H2O
molecules as :
 Example 22.
MnO4– + 5Fe2+ + H+ → Mn2+ + 5Fe3+ + H2O + 3H2O
Balance the following reactions by oxidation
6. Balance H-atoms by adding H+ ions on the side
number method :
deficient in H-atoms.
(i) FeS2 + O2 ⎯⎯→ Fe2O3 + SO2
MnO4– + 5Fe2+ + H+ + 7H+ → Mn2+ + 5Fe3+ + 4H2O
(ii) MnO4– + Fe2+ ⎯⎯→ Mn2+ + Fe3+
(in acidic medium) or MnO4– + 5Fe2+ + 8H+ → Mn2+ + 5Fe3+ + 4H2O
8/22 MODERN'S abc + OF CHEMISTRY–XI

Let us sum up the methods for balancing O and (iii) P + HNO3 ⎯⎯→ H3PO4 +H2O+ NO2
H-atoms in oxidation-reduction reaction taking –
Solution: (i)As2S3 + NO3 ⎯→ AsO43– + NO + S
placing in acidic medium.
1. The skeleton equation with oxidation number of
1. Balance O-atoms by adding H2O molecules each atom is :
on the side deficient in O-atoms. +3 –2 +5 –2 +5 –2 +2–2 0
2. To balance H-atoms, add H+ ions (available –
As2S3 + NO3 ⎯→ AsO43–+ NO + S
in acid solution) on the side deficient in
2. The O.N. of As increases from +3 to +5 and that of
H-atoms.
S increases from –2 to 0. The O.N. of N decreases
(iii) Cr (OH)3 + IO3– ⎯⎯→ I– + CrO42– from +5 to +2. This means that both As and S have
(in alkaline medium) been oxidised while NO3– has been reduced. Since
As and S must maintain their atomic ratio of 2:3
1. The skeleton equation along with oxidation
(as in As2S3), therefore, the change in O.N. of these
number of each atom is :
two atoms must be considered together. Thus,
+3 –2 +1 +5–2 –1 +6 –2
O.N. increases by 2 per
Cr (O H)3 + IO3– ⎯⎯→ I– + CrO42–
As and 2 per S atom ie 2 × 2 + 2 × 3 = 10 per As2S3
O.N. increases by 3 per atom

+3 –2 +5 +5 3– +2 0
+3 +5 –1 +6
As2S3 + N O3– ⎯⎯→ AsO43– + NO + S
Cr(OH)3 + IO3– ⎯⎯→ I– + CrO42–
O.N. decreases by 3 per atom
O.N. decreases by 6 per atom
3. To balance increase and decrease of O.N., multiply
2. To balance increase or decrease in oxidation As2S3 by 3 and NO3– by 10.
numbers, multiply Cr(OH)3 by 2 and IO3– by one.
3As2S3 + 10NO3– ⎯⎯→ AsO43– +NO +S
2Cr(OH)3 + IO3– ⎯⎯→ I– + CrO42– 4. Balance all atoms (except H and O)
3. Balance all atoms (other than H and O). 3As2S3 + 10NO3– ⎯⎯→ 6AsO43– + 10NO + 9S
2Cr(OH)3 + IO3– ⎯⎯→ I– + 2CrO42– This reaction takes place in acidic medium. The O
and H atoms are balanced as :
4. Reaction takes place in basic medium, add OH–
5. Balance O atoms by adding equal number of H2O
to right hand side to balance O-atoms.
molecules as :
2Cr(OH)3 + IO3– ⎯⎯→ I– + 2CrO42– + OH– 3As2S3+10NO3– + 4H2O ⎯→ 6AsO43–+ 10NO + 9S
5. To balance H-atoms, add H2O molecules on right 6. Balance H atoms by adding H+ ions on the side
hand side and equal number of OH– on left hand deficient in H atoms :
side. 3As2S3 + 10NO3– + 4H2O ⎯→ 6AsO43– + 10NO +
2Cr(OH)3 + IO3 + – 5OH– → I– + 2CrO4 2– + OH– 9S + 8H+.
+ 5H2O (ii) MnO4– + C2H4O4 ⎯→ Mn2+ + CO2 + H2O
or 2Cr(OH)3 + IO3– + 4OH– → I– + 2CrO42– + 5H2O 1. The skeleton equation with O.N. of each atom is :
+7 –2 +3 +1 –2 +2 +4 –2 +1 –2
Let us sum up the method for balancing O and H
atoms in oxidation-reduction reactions taking MnO4– + C2H2O4 ⎯→ Mn2++ CO2 + H2O
place in basic medium. 2. The O.N. of C increases from +3 to +4 and the O.N.
1. Balance O atoms by adding ions OH – of Mn decreases from +7 to +2. Thus,
(available from basic solution) on the side O.N. increases by 1 per atom
deficient in O-atoms (step 5) or 2 per molecule

2. To balance H atoms, add one molecule of water

for each H-atom needed on the side deficient +7 +3 +2 +4
in H atom. At the same time add an equal MnO4– + C2H2O4 ⎯⎯→ Mn2+ + CO2 + H2O
number of OH– ions to the opposite side.
O.N. decreases by 5 per atom
 Example 23.
Balance the following equations by oxidation 3. To balance increase and decrease in O.N. multiply
number method : MnO4– by 2 and C2H2O4 by 5.
(i) As2S3(s) + NO3–(aq) ⎯⎯→ 2MnO4– + 5C2H2O4 ⎯⎯→ 2Mn2+ +CO2 +H2O
AsO43–(aq) + NO(g) + S(s) (acidic medium) 4. Balance all atoms (except H and O)
(ii) MnO4–(aq) + C2H2O4(aq) ⎯⎯→ 2MnO4– + 5C2H2O4 ⎯→ 2Mn2+ +10CO2 + H2O
Mn2+ (aq)+ CO2(g) + H2O(l) (acidic medium) This reaction takes place in acidic medium. The
O and H atoms are balanced as :
REDOX REACTIONS 8/23
5. Balance O atoms by adding equal number of H2O Cr2O7 2– + 3SO32– + 8H+ ⎯⎯→ 2Cr3+ + 3SO42– +
molecules as : 4H2O
2MnO4– + 5C2H2O4 ⎯→ 2Mn2+ +10CO2 + 8H2O This is a balanced equation.
6. To balance H atoms add H + ions on the side
deficient in H atoms :
2MnO4– + 5C2H2O4 + 6H+ ⎯→ 2Mn2+ +10CO2 + 10. Balance the following equations by oxidation
8H2O number method :
(iii) P + HNO3 ⎯→ H3PO4 + NO2 + H2O (a) MnO2 + HCl ⎯⎯→ MnCl2 + Cl2 + H2O
1. The skeleton equation with O.N. of each atom is : (b) H2S + KMnO4 + H2SO4 ⎯⎯→ KHSO4 + MnSO4 + S
0 +1 +5 –2 +1 +5 –2 +4 –2 +1 –2 + H2O
P + H N O3 ⎯→ H3PO4 + NO2 + H2O (c) CuO + NH3 ⎯⎯→ Cu + N2 + H2O
2. The O.N. of P increases from 0 to +5 and the O.N. 11. Balance the following ionic equations by oxidation
of N decreases from +5 to +4. Thus, number method :
O.N. increases by 5 per atom (i) Fe2+ + H2O2 ⎯⎯→ Fe3+ + H2O
(acidic medium)
0 +5 +5 +4 (ii) Zn + NO3 ⎯⎯→ Zn2+ + NH4+
P + HNO3 ⎯⎯→ H3PO4 + NO2 + H2O (basic medium)
(iii) H2S + MnO4– ⎯⎯→ S + Mn2+ + H2O
O.N. decreases by 1 per atom
(acidic medium)
3. To balance increase and decrease in O.N. multiply
(iv) Cu + NO3– + H+ ⎯⎯→ NO2 + Cu2+
HNO3 by 5.
(v) MnO4– + H2C2O4 ⎯⎯→ Mn2+ + CO2 + H2O
P + 5HNO3 ⎯⎯→ H3PO4 + NO2 + H2O
(acidic medium)
4. Balance all atoms (except H and O)
P + 5HNO3 ⎯⎯→ H3PO4 + NO2 + H2O 12. Magnesium reacts with nitric acid to give
magnesium nitrate in aqueous solution, nitrous
This is balanced equation. oxide gas and liquid water. Write balanced
 Example 24. equation for this redox reaction.
Write the balanced ionic equation for the reaction 13. Balance the following equations by oxidation
of potassium dichromate (VI), K2 Cr2O7 with number method :
sodium sulphite, Na2SO3 in acid medium to give (i) H2S (aq) + Cl2 (g) ⎯⎯→ S (s) + Cl– (aq)
chromium(III) ion and sulphate ion. (acidic medium)
Solution : The skeleton equation is : (ii) Cl2O7 (g) + H2O2 (g) ⎯⎯→ ClO2– (aq) + O2 (g)
2–
Cr2O72– + SO3 ⎯→ Cr3+ + SO42– (basic medium)
1. The skeleton equation with oxidation number is : (iii) P (s) + OH– (aq) ⎯⎯→ PH3 (g) + H2PO2– (aq)
+6 –2 +4 –2 +3 +6 –2
2– (basic medium)
Cr2O72– + SO3 ⎯→ Cr3+ + SO42–
(iv) N2H4 (g) + ClO3– (aq) ⎯→ NO (g) + 4Cl– (g)
2. O.N. increases by 2 per atom
(v) MnO4–(aq) + C2H2O4––→ Mn2+(aq) + CO2(g) +H2O (l)
(vi) MnO4–(aq) + C2H5OH––→ Mn2+(aq) + CH3COOH
+6 +4 +3 +6 (aq)
2–
Cr2O72– + SO3 ⎯→ Cr3+ + SO42–

O.N. decreases by 3 × 2 per molecule 10. (a) MnO2 + 4HCl ⎯⎯→ MnCl2 + Cl2 + 2H2O
3. To balance increase and decrease multiply SO32– (b) 5H2 S + 2KMnO4 + 4H2SO4 ⎯⎯→ 2KHSO4 + 2MnSO4
by 3 + 5S + 8H2O
Cr2O72– + 3SO32– ⎯⎯→ Cr3+ + SO42– (c) 3CuO + 2NH3 ⎯⎯→ 3Cu +N2 + 3H2O
4. Balance all atoms (except O and H) 11. (i) 2Fe2+ + H2O2 + 2H+ ⎯⎯→ 2Fe3+ + 2H2O
Cr2O72– + 3SO32– ⎯⎯→ 2Cr3+ + 3SO42– (ii) 4Zn + NO3– + 7H2O ⎯⎯→ 4Zn2+ + NH+4 + 10 OH–
This reaction occurs in acidic medium, O and H (iii) 5H2S + 2MnO–4 + 6H+ ⎯⎯→ 5S + 2Mn2+ + 8H2O
atoms are balanced as :
(iv) Cu + 2NO3– + 4H+ ⎯⎯→ 2NO2 + Cu + 2H2O
5. Balance O atoms by adding H2O molecules as :
(v) 2MnO4– + 5H2C2O4 + 6H+ ⎯⎯→ 2Mn2+ + 10 CO2 + 8H2O
Cr2O72– + 3SO32– ⎯⎯→ 2Cr3+ + 3SO42– + 4H2O
12. 4Mg(s) + 10HNO3 (aq) ⎯→ 4Mg(NO3)2 (aq) + N2O (g)
6. Balance H atoms by adding H+ ions on the side + 5H2O(l)
deficient in H atoms :
 8/24 MODERN'S abc + OF CHEMISTRY–XI

Solution:
13.(i) H2S (aq) + Cl2 (g) ⎯⎯→ S (s) + 2Cl– (aq) + 2H+ (aq)
Step 1. Separate the equation into two half
(ii) Cl2O7 (g) + 4H2O2 (aq) + 2OH–(aq) ⎯⎯→
reactions :
2ClO2– (aq) + 4O2 (g) + 5H2O (l)
The oxidation number of various atoms are
(iii) 4P (s) + 3OH– (aq) + 3H2O (l) ⎯⎯→ shown below :
PH3 (g) + 3H2PO2– (aq) +6 –2 +2 +1 +3 +3 +1 –2
(iv) 3N2H4 (s) + 4ClO3– (aq)⎯⎯→ Cr2O72– + Fe2+ + H+ → Cr3+ + Fe3+ + H2 O
6NO (g) + 4Cl– (aq) + 6H2O (l) In this case, chromium undergoes
(v) 2MnO4 –(aq) + 6H+(aq) + 5C2H2O4(aq) ––→ reduction, oxidation number decreases
2Mn2+(aq) + 10CO2(g) +8H2O (l) from +6 (in Cr2O72–) to +3 (in Cr3+)
(vi) 4MnO4–(aq) + 5C2H5OH(aq) + 12H+(aq) ––→ Fe2+ (O.N. = +2) changes to Fe3+ (O.N. = +3).
4Mn2+(aq) + 5CH3COOH (aq) + 11H2O The species undergoing oxidation and
reduction are :
B. Ion-Electron Method (Balancing Equations Oxidation : Fe2+ ⎯⎯→ Fe3+
Using Half Reactions) Reduction : Cr2O72– ⎯⎯→ Cr3+
The balancing of chemical equation by ion-electron Step 2. Balance each half reaction separately as :
method (using half reactions) is done by the following (a) Fe2+ ⎯⎯→ Fe3+
steps : (i) Balance all atoms other than H and O.
Step 1. Find the elements whose oxidation This step is not needed, because, it is
numbers are changed. Choose the substance which already balanced.
acts as an oxidising agent and one that acts as a (ii) The oxidation number on left is +2 and
reducing agent. on right is +3. To account for the difference,
the electron is added to the right as :
Step 2. Separate the complete equation into two
half reactions, one for the change undergone by the Fe2+ ⎯⎯→ Fe3+ + e–
oxidising agent and the other for the change undergone (iii) Charge is already balanced.
by the reducing agent. (iv) No need to add H or O.
Step 3. Balance half equations by the following The balanced half equation is :
steps : Fe2+ ⎯⎯→ Fe3+ + e– ...(i)
(i) balance all atoms other than H and O. Consider the second half equation
(ii) calculate the oxidation number on both sides Cr2O72– ⎯⎯→ Cr3+
of the equation. Add electrons to whichever side is (i) Balance the atoms other than H and O.
necessary, to make up the difference. Cr2O72– ⎯⎯→ 2Cr3+
(iii) balance the half equation so that both sides (ii) The oxidation number of chromium on
get the same charge. the left is +6 and on the right is +3. Each
(iv) add water molecules to complete the balancing chromium atom must gain three electrons.
of the equation. Since there are two Cr atoms, add 6e– on
the left.
Step 4. Add two balanced half equations. Multiply
one or both half equations by suitable numbers so that Cr2O72– + 6e– ⎯⎯→ 2Cr3+
on adding the two equations, the electrons are balanced. (iii) Since the reaction takes place in acidic
It may be noted that redox reaction may take place medium add 14H+ on the left to equate the
net charge on both sides.
in all the three media i.e., acidic or basic or neutral. If H+
ions appear on either side of the equation, the reaction Cr2O72– + 6e– + 14H+ ⎯⎯→ 2Cr3+
takes place in acidic medium. If OH– ions appear on (iv) To balance H atoms, add 7H 2 O
either side of the equation, the solution is basic. If neither molecules on the right.
H+ nor OH– ions are present, the reaction occurs in Cr2O72– + 6e– + 14H+ ⎯⎯→ 2Cr3+ + 7H2O
neutral solution. For balancing redox reactions involving ...(ii)
acidic and basic media, the method has to be modified This is the balanced half equation.
slightly as illustrated in the examples given ahead :
Step 3. Now add up the two half equations.
Multiply eq. (i) by 6 so that electrons are
balanced.
 Example 25. Fe2+ ⎯⎯→ Fe3+ + e–] × 6
Consider the reaction between iron (II) ions and Cr2O72– + 6e– + 14H+ ⎯⎯→ 2Cr3+ + 7H2O
dichromate ions in acidic solution as :
Cr2O72– + Fe2+ + H+ ⎯⎯→Cr3+ + Fe3+ + H2O 6Fe2+ + Cr2O72– + 14H+ ⎯⎯→ 6Fe3+ + 2Cr3+ + 7H2O
REDOX REACTIONS 8/25
The balanced equation is : (iii) & (iv). As the reaction is proceeding in acidic
6Fe2+ + Cr2O72– + 14H+ ⎯⎯→ 6Fe3+ + 2Cr3+ + 7H2O medium add 14H+ on the left to equate the
net charge on both sides. At the same time,
Note. If we carefully see step 2 part (iii) and (iv) we
get a method for balancing redox reaction in acidic add 7H2O to right.
medium. Charge is balanced by adding H+ and then Cr2O72– + 6e– + 14H+ ⎯⎯→ 2Cr3+ + 7H2O
appropriate number of H2O molecules are added on Step 3. Adding the two half reactions.
the other side. Now add up the two half reactions to get
the final equation. But before doing so,
 Example 26.
multiply the oxidation half reaction by 3
Balance the following equations by ion electron
to equate the number of electrons.
method :
C2H4O + H2O ⎯⎯→ C2H4O2 + 2e– + 2H+] × 3
(a) Cr2O72– + C2H4O ⎯⎯→C2H4O2 + Cr3+
Cr2O72– + 14H+ + 6e– ⎯⎯→ 2Cr3+ + 7H2O
(in acidic medium)
(b) Zn + NO3– ⎯⎯→Zn2+ + NH4+ 3C2H4O + Cr2O72– + 8H+ ⎯⎯→ 3C2H4O2 + 2Cr3+ + 4H2O
(in basic medium) (b) Zn + NO3– ⎯⎯→ Zn2+ + NH4+
Solution: Step 1. Write oxidation number of each atom and
Step 1. Separate the equation into the half split the equation into two half equations :
reactions : 0 +5 –2 +2 –3 +1
Cr2O72– + C2H4O ⎯⎯→ C2H4O2 + Cr3+ Zn + N O3– ⎯⎯→ Zn2+ + N H4+
Write the oxidation number of the various In this reaction, zinc undergoes oxidation
atoms. and NO3– undergoes reduction :
+6 –1 0 +3 Oxidation : Zn ⎯⎯→ Zn2+
[Cr2O72–] + C2H4O ⎯⎯→ C2H4O2 + Cr3+ Reduction : NO3– ⎯⎯→ NH4+
The species undergoing change in Step 2. Balance each half reaction separately as :
oxidation number are : (a) Zn ⎯⎯→ Zn2+
–1 0 (i) Balance all atoms other than H and O
Oxidation : C2H4O ⎯⎯→ C2H4O2 (already done)
(ii) Add electrons to make up the difference in
+6 +3
oxidation number,
Reduction : Cr2O72– ⎯⎯→ Cr3+ Zn ⎯⎯→ Zn2+ + 2e–
Step 2. Balance each half reaction separately as : ...(i)
(a) C2H4O ⎯⎯→ C2H4O2 (iii) Balance the charges (already done)
(i) The equation is already balanced in terms (iv) No need to add water.
of carbon atoms. The balanced oxidation half reaction is :
(ii) The O.N. of carbon on the left is –1 while Zn ⎯⎯→ Zn2+ + 2e–
on the right, it is 0. To account for the (b) NO3– ⎯⎯→ NH4+
difference in oxidation number, add two (i) Balance all atoms other than H and O
electrons on the right. (already done).
C2H4O ⎯⎯→ C2H4O2 + 2e– (ii) Nitrogen changes its oxidation number
(iii) & (iv) Since the reaction is taking place in from +5 to –3 and there is difference of 8
acidic medium, and 2H+ on the right and a electrons. To balance the electrons :
H2O molecule on the left NO3– + 8e– ⎯⎯→ NH4+
C2H4O + H2O ⎯⎯→ C2H4O2 + 2e– + 2H+ (iii) Balance the charges. Since the reaction
(b) Balancing of reduction half reaction : takes place in basic medium, add 10 OH–
ions on the right side.
Cr2O72– ⎯⎯→ Cr3+
NO3– + 8e– ⎯⎯→ NH4+ + 10 OH–
(i) Balance the Cr atoms on both sides of the
(iv) Add water molecules to complete
equation
balancing,
Cr2O72– ⎯⎯→ 2Cr3+
NO3– + 8e– + 7H2O ⎯⎯→ NH4+ + 10 OH–
(ii) The O.N. of Cr atom on the left is +6 and
...(ii)
on the right is +3. Thus, each Cr atom has
Step 3. To add up the two half reactions, multiply
gained three electrons i.e. total number of
eq. (i) by 4 as :
electrons gained is six. Add six electrons
Zn ⎯⎯→ Zn2+ + 2e–] × 4
on the reactant side to account for
difference in O.N. NO3 + 7H2O + 8e– ⎯⎯→ NH4+ + 10 OH–
–

Cr2O72– + 6e– ⎯⎯→ 2Cr3+ 4Zn + NO3– + 7H2O ⎯⎯→ 4Zn2+ + NH4+ + 10 OH–
 8/26 MODERN'S abc + OF CHEMISTRY–XI

 Example 27. +7 +2

Balance the following redox equations by half Reduction : Mn O4– ⎯⎯→ Mn2–
reaction method : +4 +6

(a) Cr (OH)3 + IO3– ⎯⎯→ I – + CrO42– Oxidation : S O32– ⎯⎯→ SO42–

(in basic medium) These can be balanced by following the
steps as given above.
(b) MnO4– + SO3– ⎯⎯→ Mn2+ + SO42–
(i) MnO4– ⎯⎯→ Mn2+
(in acidic medium)
MnO–4 + 5e– ⎯⎯→ Mn2+
(c) Br2 + H2O2 ⎯⎯→ BrO3– + H2O
MnO–4 + 5e– ⎯⎯→ Mn2+ + 4H2O
(in acidic medium)
MnO4– + 8H+ + 5e– ⎯⎯→ Mn2+ + 4H2O
Solution: (a) Cr(OH)3 + IO3– ⎯⎯→ I– + CrO42–
(ii) SO32– ⎯⎯→ SO42–
Step 1. Separate the equation into two half
SO32– ⎯⎯→ SO42– + 2e–
reactions :
SO32– + H2O ⎯⎯→ SO42– + 2e–
Cr(OH)3 + IO3– ⎯⎯→ I– + CrO42–
Write the oxidation number of various + H2O ⎯⎯→ SO42– + 2e– + 2H+
SO32–
atoms. (iii) Adding the two half reactions by equating
the number of electrons
+3 +5 –1 +6
Cr(OH)3 + IO3– ⎯⎯→ I– + CrO42– MnO4– + 8H+ + 5e– ⎯⎯→ Mn2+ + 4H2O ] × 2
The species undergoing change in SO32– + H2O ⎯⎯→ SO42– + 2H+ + 2e– ] × 5
oxidation number are :
+3 +6
2MnO4– + 5SO32– + 6H+ ⎯⎯→ 2Mn2+ + 5SO42– + 3H2O
Oxidation : Cr (OH)3 ⎯⎯→ CrO42– (c) Br2 + H2O2 ⎯⎯→ BrO3– + H2O
+5 –1 0 +1 –1 +5 –2
Reduction : I O3– ⎯⎯→ I– Br2 + H2O2 (Br O3)– + H2O
Step 2. Balance each half reaction separately as : Separating the equation into two half
(i) Cr(OH)3 ⎯⎯→ CrO42– reactions :
The O.N. of Cr on the left is +3 and on the 0 +5
right it is +6. To account for the difference Oxidation : Br2 ⎯⎯→ BrO3–
add 3 electrons on the right. –1 –2
Cr(OH)3 ⎯⎯→ CrO42– + 3e– Reduction : H2O2 ⎯⎯→ H2O
Since, it is occurring in basic medium Balancing the two half reactions separately
Cr(OH)3 + OH– ⎯⎯→ CrO42– + 3e– 0 +5
Cr(OH)3 + OH– + 4OH– ⎯⎯→ CrO42– + 4H2O + 3e– (i) Br2 ⎯⎯→ BrO3–
or Cr(OH)3 + 5OH– ⎯⎯→ CrO42– + 4H2O + 3e– Since each Br loses 5 electrons
(ii) IO3– ⎯⎯→ I– Br2 ⎯⎯→ 2BrO3– + 10e–
The oxidation number of iodine on the left Br2 + 6H2O ⎯⎯→ 2BrO3– + 10e–
is +5 and on the right is –1. To account for
Br2 + 6H2O ⎯⎯→ 2BrO3– + 10e– + 12H+
the difference, add 6 electrons on the left.
IO3– + 6e– ⎯⎯→ I– –1 –2

Other steps are : (ii) H2O2 ⎯⎯→ H2O

IO3– + 6e– ⎯⎯→ I– + 3OH– Each O atom gains one electron
IO3 + 3H2O + 6e– ⎯⎯→ I– + 3OH– + 3OH–
– –1 –2
H2O2 + 2e– ⎯⎯→ H2O
or IO3– + 3H2O + 6e– ⎯⎯→ I– + 6OH–
Step 3. Add the two half reactions. To equate the H2O2 + 2e– ⎯⎯→ 2H2O
number of electrons, multiply the oxidation H2O2 + 2e– + 2H+ ⎯⎯→ 2H2O
half reaction by 2. (iii) Adding the two half reactions by equating
Cr(OH)3 + 5OH– ⎯⎯→ CrO42– + 4H2O + 3e– ] × 2 the number of electrons.
IO3– + 3H2O + 6e– ⎯⎯→ I– + 6OH– Br2 + 6H2O ⎯⎯→ 2BrO3– + 12H+ + 10e–
H2O2 + 2H+ + 2e– ⎯⎯→ 2H2O ] × 5
2Cr(OH)3 + IO3– + 4OH– ⎯⎯→ 2CrO42– + 5H2O + I–
(b) The equation is : Br2 + 5H2O2 ⎯⎯→ 2BrO3– + 4H2O + 2H+
MnO4– + SO32– ⎯⎯→ Mn2+ + SO42–  Example 28.
(in acidic medium) In passing chlorine gas through a concentrated
The equation can be separated as : solution of alkali we get chloride and chlorate ions.
REDOX REACTIONS 8/27

Obtain balanced chemical equation for this or 4P + 3OH– + 3H2O ⎯→ PH3 + 3H2PO2 –

reaction (ii) Ion electron method

Solution: The chemical equation for the reaction is 1. Oxidation number of each atom :
Cl2 + ⎯⎯→
OH– Cl–
+ ClO3 + H2O – 0 –3 +1

Separating the equation into two half P + OH– ⎯⎯→ PH3 + H2PO2–
reactions : In this P undergoes oxidation to H 2 PO 2 – and
0 –2 +1 –1 +5 –2 +1 –2 reduction to PH3
Cl2 + OH– ⎯⎯→ Cl– + ClO3– + H2O Oxidation : P ⎯⎯→ H2PO2–
0 +5 Reduction : P ⎯⎯→ PH3
Oxidation : Cl2 ⎯⎯→ ClO3– 2. Balance each reaction separately
0 –1 +1
Reduction : Cl2 ⎯⎯→ Cl– (a) P ⎯⎯→ H2PO2–
Balancing the two half reactions separately, (i) Add electron to make up the difference in
0 +5 oxidation number
(i) Cl2 ⎯⎯→ ClO3 P ⎯⎯→ H2PO2– + e–
Each Cl atom loses 5 electrons (ii) Balance OH– ions to balance charge
Cl2 ⎯⎯→ 2ClO3– + 10 e– P + 2OH– ⎯⎯→ H2PO2– + e– .....(i)
Cl2 + 6H2O ⎯⎯→ 2ClO3– + 10 e– 0 –3
Cl2 + 6H2O + 12OH– ⎯⎯→ 2ClO3– + 10 e– + 12 H2O (b) P ⎯⎯→ PH3
(ii) Cl2 ⎯⎯→ Cl– (i) Add electrons to balance oxidation state
Each Cl atom gains one electron. P + 3e– ⎯⎯→ PH3
Cl2 + 2e– ⎯⎯→ 2Cl– (ii) Add OH– ions to balance charge
(iii) Adding the two half reactions by equating the number P + 3e– ⎯⎯→ PH3 + 3OH–
of electrons :
(iii) Add 3H2O molecules on L.H.S. to balance O
Cl2 + 6H2O + 12OH– ⎯⎯→ 2ClO3– + 12H2O + 10e– and H atoms
Cl2 + 2e– ⎯⎯→ 2Cl– ] × 5 P + 3H2O + 3e– ⎯⎯→ PH3 + 3OH– ....(ii)
3. Multiply eqn (i) by 3 and add to eqn (ii)
6Cl2 + 12OH– ⎯⎯→ 2ClO3– + 10 Cl– + 6H2O
4P + 3H2O + 6OH– ⎯⎯→ PH3 + 3OH– + 3H2PO2–
or 3Cl2 + 6OH– ⎯⎯→ ClO3– + 5Cl– + 3H2O
or 4P + 3H2O + 3OH– ⎯⎯→ PH3 + 3H2PO2–
 Example 29.  Example 30.
Balance the following equation by oxidation Permanganate (VII) ion, MnO4– in basic solution
number as well as ion–electron method : oxidises iodide ion, I– to produce molecular iodine
P(s) + OH–(aq) ⎯⎯→ PH3(g) + H2PO2–(aq) (I2) and manganese (IV) oxide (MnO2). Write a
balanced ionic equation to represent this redox
Solution: (i) Oxidation number method :
reaction.
1. The skeleton equation with oxidation number is
0 –2 +1 –3 +1 +1 +1 –2 Solution: The skeleton equation for the reaction is :
P + OH– ⎯→ PH3 + H2PO2– MnO4–(aq) + I–(aq) ⎯→ MnO2(s) + I2 (s)
O.N. increases by 1 per atom 1. Separating the equation into two half
reactions :
0 –3 +1 –1 0
Oxidation : I– ⎯⎯→ I2
P + OH– ⎯⎯→ PH3 + H2P O2 –
+7 +4
O.N. decreases by 3 per atom Reduction: MnO4– ⎯⎯→ MnO2

2. To balance increase and decrease, multiply H2PO2–

Balancing the two half reactions separately
by 3.
–1 0
P + OH– ⎯⎯→ PH3 + 3H2PO2–
(i) I– ⎯⎯→ I2
3. To balance all atoms (other than H and O) multiply –
Each I ion loses one electron each
P by 4
2I– ⎯⎯→ I2 + 2e–
4P + OH– ⎯⎯→ PH3 + 3H2PO2–
+7 +4
4. To balance O atoms add OH– ions to L.H.S.
(ii) MnO4– ⎯⎯→ MnO2
4P + OH– + 5OH– ⎯⎯→ PH3 + 3H2PO2– MnO4– + 3e– ⎯⎯→ MnO2
5. To balance H atoms add H2O molecules on L.H.S. Since the reaction occurs in basic medium, add OH–
and equal number of OH– ions on other side ions on R.H.S. to balance O atoms
4P + 6OH– + 3H2O ⎯→ PH3 + 3H2PO2– + 3OH– MnO4– + 3e– ⎯⎯→ MnO2 + 2OH–
8/28 MODERN'S abc + OF CHEMISTRY–XI

To balance H atoms add H2O molecules on L.H.S. APPLICATIONS OF REDOX REACTIONS

and equal number of OH– ions on the other side
Redox reactions are the basis of many applications
MnO4– + 3e– + 2H2O ⎯⎯→ MnO2 + 2OH– + 2OH– in chemistry. Some of the important applications of
Adding the two half reactions by equating the redox reactions are :
number of electrons :
1. Photosynthesis. Photosynthesis is used to
2I– ⎯⎯→ I2 + 2e– ] × 3 convert carbon dioxide and water by chlorophyll of
MnO4– + 2H2O + 3e– ⎯⎯→ MnO2 + 4OH– ] × 2 green plants in the presence of sunlight to
2MnO4– + 6I– + 4H2O ⎯⎯→ 2MnO2 + 3I2 + 8OH– carbohydrates.
Chlorophyll
A verification of this equation shows that it is 6CO2(g) + 6H2O (l) ⎯⎯⎯⎯⎯
Sunlight
→ C H O (aq) + 6O (g)
6 12 6 2
balanced in respect to the number of atoms and
charges on both sides. In this case, CO2 is reduced to carbohydrates and
water is oxidised to oxygen. The light provides the
energy required for the reaction. This reaction is a
source of food for plants and animals.
14. Balance the following equations by ion electron 2. In metallurgy. Many metal oxides are
method : reduced to metals by using suitable reducing agents.
(a) NO3– + Bi(s) ⎯⎯→ Bi3+ + NO2 For example, Al 2O 3 is reduced to aluminium by
(in acidic medium) cathodic reduction in electrolytic cell. Fe2O3 is reduced
to iron in a blast furnace using coke. Other metals
(b) MnO4– + H2C2O4 ⎯⎯→ Mn2+ + CO2
such as magnesium, calcium, strontium, barium,
(in acidic medium) sodium, potassium, etc., are produced commercially
(c) Cr2O72– + Fe2+ ⎯⎯→ Cr3+ + Fe3+ by electrolysis methods.
(in acidic medium) 3. Production of chemicals. Many chemical
compounds of our common need are commercially
(d) –
MnO4 + Br– ⎯⎯→ Mn2+ + Br2
prepared by redox reactions. For example, sodium
(in acidic medium) hydroxide, Cl 2 , F 2 , KOH, etc. are produced by
(e) MnO4– + SO32– ⎯⎯→ Mn2+ + SO42– electrolysis which is based on redox reactions.
(acidic medium) 4. Oxidation of fuels. Oxidation of fuels is an
important source of energy which satisfies our daily
(f) Cl2O7(g) + H2O2(g) ⎯⎯→ ClO2– (aq)+ O2(g) need of life. These are used for obtaining energy for
15. Starting with correctly balanced half reactions, domestic, transport or industrial purposes. They are
write the overall net reactions for the following also used for digestion of food in animals.
changes: Fuels + O2 ⎯⎯→ CO2 + H2O + Energy
(a) Nitrous acid (HNO2) oxidises, I– to I2 in acidic In living cells, glucose (C6H12O6) is oxidised to CO2
medium. and H2O in the presence of oxygen and energy is released.
(b) Chloride ion is oxidised to Cl2 by MnO4– in acidic C6H12O6 (aq) + 6O2(g) ⎯⎯→ 6CO2(g) + 6H2O(l)
medium. + Energy
5. Electrochemical cells or batteries. The
electrochemical cells or batteries are most important
14. (a) 3NO3– + Bi + 6H+ ⎯⎯→ 3NO2 + 3H2O + Bi3+ and are contributing significantly in different fields.
They provide a source of electricity in many motors in
(b) 2MnO4– + 5H2C2O4 + 6H+ ⎯⎯→ 2Mn2+ + 8H2O small and large equipments. Our vehicles cars, trucks,
+ 10CO2 buses, etc. are moving on the storage cells based on
(c) Cr2O72– + 6Fe2+ + 14H+ ⎯⎯→ 2Cr3+ + 7H2O redox reactions. The electrochemical cells involving
+ 6Fe3+ reaction between hydrogen and oxygen using hydrogen
and oxygen electrodes in fuel cells meet our demand
(d) 2MnO4– + 10 Br– + 16H+ ⎯⎯→ 2Mn2+ + 5Br2 of electrical energy in space capsule.
+ 8H2O 6. Quantitative relationships and
–
(e) 2MnO4 + 5SO3 2–+ 6H+ ⎯⎯→ stoichiometry. Redox reactions also play significant
2Mn2+ + 5 SO42– + 3H2O role in quantitative analysis of different species by
redox titrations. These titrations involve the reactions
(f) Cl2O7 + 4H2O2 + 2OH– ⎯⎯→
between oxidising and reducing agents and help to
2Cl2– + 4O2+5H2O
calculate the amount of unknown species in solutions.
15. (a) 2I– + 2NO2– + 4H+ ⎯⎯→ I2 + 2NO + 2H2O REDOX TITRATIONS : REDOX REACTIONS AS
THE BASIS FOR TITRATIONS
(b) 2MnO4– + 16H+ + 10Cl – ⎯⎯→ 5Cl2 + 2Mn2+
The titration of an acid with a base or of a base
+ 8H2O
with an acid is very convenient method for the
REDOX REACTIONS 8/29

measurement of quantities of the substances in MnO4– + 8H+ + 5e– ⎯⎯→ Mn2+ + 4H2O] × 2
solution. The titration is carried out by adding a COO–
solution of the reagent of known concentration
(standard solution) taken in a burette to unknown
solution taken in a flask known as titration flask. The
COO–
⎯⎯→ 2CO2 + 2e– × 5
]
COO–
solution taken in a burette is called titrant and the
2MnO4– +5 + 16H+ ⎯→ 2Mn2+ + 10CO2 + 8H2O
other solution taken in the titration flask is called COO–
analyte. The titration is continued until the
2. Potassium dichromate titrations
stoichiometric amounts of the two reagents (titrant
and analyte) have been mixed. For example in a Acidified potassium dichromate K2Cr2O7 is also
titration of a strong acid such as HCl and a strong used as an oxidising agent in redox titrations. It is a
base such as NaOH, the following reaction occurs. relatively weak oxidising agent as compared to KMnO4.
HCl (aq) + NaOH (aq) ⎯⎯→ NaCl (aq) + H2O (l) However, unlike KMnO4, it does not act as a self indicator
The stoichometric point corresponds to the because no dramatic auto-colour change (as with MnO4–
neutralisation of HCl and NaOH. It is also called titrations) occurs in these titrations. In these titrations,
equivalence point or end point. indicators such as diphenylamine, N–phenylanthranilic
There are several methods for determining the acid (and external indicator potassium ferricyanide,
equivalence point. The simplest method is to add K4[Fe(CN)6] are commonly used. For example, K2Cr2O7
to the solution a dye that shows change in colour at oxidises the indicator diphenylamine just after the
the equivalence point. Such dyes are called indicators. equivalence point to give intense blue colour indicating
The indicator helps to determine the end point by the end point. The chemical equation showing Cr2O72–
showing change in colour. For example, when as an oxidising agent is :
phenolphthalein is added to a basic solution, it gives Cr2O72– + 14 H+ + 6e– ⎯⎯→ 2Cr3+ + 7H2O
pink colour. When this solution is titrated against an
acid solution, the end point is indicated by Oxidation of ferrous salts with K2Cr2O7 may be
disappearance of pink colour. written as:
The same principles apply to redox titrations. 6Fe2+ + Cr2O72– + 14H+ ⎯→ 2Cr3+ + 6Fe3+ + 7H2O
However, the indicators used in acid-base titrations Iodimetric and Iodometric titrations
are not used for redox titrations. There are a number Iodine, I2 also acts as a mild oxidising agent in
of oxidising agents such as acidified KMnO4, acidified solution according to the reaction :
K2Cr2O7, iodine solution, potassium iodate etc. which
can be titrated against reducing agents such as ferrous I2 + 2e– ⎯⎯→ 2I–
suphate (or Fe2+ ions), oxalic acid, sodium thiosulphate, It may be noted that iodine being nonpolar is
potassium iodide etc. For example : very slightly soluble in water. However, it
1. Potassium permanganate titrations dissolves in water in the presence of potassium
Potassium permanganate, KMnO4 is a versatile iodide due to the formation of KI3 as :
and strong oxidising agent used in estimation of many 
KI + I2  
 KI3
reducing agents such as Fe2+ ions, oxalates ions etc. Iodine can be used for titrating strong reducing
In these titrations, no indicator is used because KMnO4 agents like sodium thiosulphate according to the
is itself intensely coloured (dark purple). So, KMnO4 reaction :
acts as a self indicator and when it is titrated against
I2 (aq) + S2O32– (aq) ⎯⎯→ 2I– (aq) + S4O62–(aq)
a reducing agent (e.g. Fe 2+ , C 2 O 4 2– ) its colour
disappears. As soon as the reducing agent has been These titration in which iodine is directly titrated
used up, the additional a single drop of potassium against a reducing agent are called iodimetric
permanganate gives a tinge of pink colour to the titrations.
solution. For example, pink colour appears at MnO4– There is another method in which iodine is
concentration as low as 10–6 mol L–1. This ensures a liberated from potassium iodide by some oxidising
minimal ‘overshoot’ in the colour beyond the agent and liberated iodine is titrated against standard
equivalence point i.e., the point where the reductant sodium thiosulphate solution. These titrations in
and oxidant are equal in terms of their stoichiometry. which liberated iodine from an oxidising agent is
The reaction for titration of MnO4– against Fe2+ titrated against a standard solution of sodium
ions is : thiosulphate are called iodometric titration. For
MnO4– + 8H+ + 5e– ⎯⎯→ Mn2+ + 4H2O example, Cu 2+ ions (e.g. CuSO 4) is estimated by
Fe2+ ⎯⎯→ Fe3+ + e–] ×5 oxidising I– ions (from KI) to liberate I2, which is
titrated against Na2S2O3.
MnO4– + 5Fe2+ + 8H+ ⎯⎯→Mn2+ + 5Fe3+ + 4H2O
2Cu2+ (aq) + 4I–(aq) ⎯⎯→ Cu2I2(s) + I2 (aq)
Similarly, the reaction for the titration of MnO4–
against oxalate ions is 2Na2S2O3 + I2 ⎯⎯→ 2NaI + Na2S4O6
 8/30 MODERN'S abc + OF CHEMISTRY–XI

In these iodine titrations, end point can be detected

by adding freshly prepared starch solution. It reacts
with iodine in the presence of iodide to form intensely  Example 31.
blue coloured complex. Iodine appearance or How many grams of potassium dichromate are
disappearance can be identified very sharply by this required to oxidise 20.0 g of Fe2+ in FeSO4 to Fe3+
method. if the reaction is carried out in an acidic solution ?
STOICHIOMETRY OF REDOX REACTIONS Solution: When dissolved in water, K 2 Cr 2 O 7
The quantitative relationships between different dissociates into K + and Cr 2 O7 2– ions and FeS O 4
chemical species in redox reactions are derived exactly dissociates into Fe2+and SO42– ions. The skeleton
equation is :
in the same way as discussed in Unit 1 for general
Fe2+ + Cr2O72– ⎯⎯⎯→ Fe3+ + 2Cr3+
chemical reactions. To perform stoichiometric
The balanced equation is
calculations, we need a balanced redox equation for
Cr2O72– + 6Fe2+ + 14H+ ⎯⎯⎯→ 6Fe3+ + 2Cr3+ + 7H2O
the reaction because the coefficients in the equation
From the balanced equation, it is clear that
tell us the ratio by moles in which the reactants
combine and in which the products are formed. If we 1 mol K2Cr2O7 ≡ 6 mol FeSO4
know the molarities of the reductant and oxidant and Formula weight of
their volumes used in titration and n1 and n2 are their K2Cr2O7 = 2 × 39 + 2 × 52 + 7 × 16 = 294
stoichiometric coefficients, then molarity equation may Formula weight of FeSO4
be written as : = 56 + 32 + 4 × 16 = 152
∴ 1 mol K2Cr2O7 ≡ 6 mol FeSO4
M 1 V1 M 2 V2
= for volumetric estimation. 294 6 × 152
n1 n2 6 × 152 g of FeSO4 require K2Cr2O7 = 294 g
For example, in the titration of FeSO 4 with
20 g of FeSO4 require K2Cr2O7
KMnO4, the balanced equation is :
10FeSO4 + 2KMnO4 + 8H2SO4 ⎯→ 5Fe2 (SO4)3 = 294 × 20 = 6.45 g
6 × 152
+ K2SO4 + 2MnSO4 + 8H2O K2Cr2O7 required to oxidise 20 g of FeSO4
If FeSO4 is considered as reagent 1 and KMnO4 = 6.45 g
is reagent 2, then molarity equation becomes :
M 1 V1 M 2 V2  Example 32.
= How many millilitres of 0.125 M KMnO4 are
10 2
M 1 V1 M 2 V2 required to react completely with 25.0 mL of
or = 0.250 M FeSO4 solution in the acidic medium ?
5 1
This relation can be used to calculate unknown Solution: The balanced chemical equation is :
quantity if other three quantities are known. MnO4– + 5Fe2+ + 8H+ ⎯⎯⎯→ Mn2+ + 5Fe3+ + 4H2O
It may be noted that normality equation can also From the balanced equation, it is clear
be used to determine the stoichiometry of redox 1 mol KMnO4 = 5 mol FeSO4
reactions. The normality equation is 158 5 × 152
Moles of FeSO4 present in 25 mL of 0.250 M solution :
N1V1 ≡ N2V2
0.250
If we know the normality (N1) of any solution of = × 25 = 0.00625 mol
1000
an oxidising agent and volume (V1) of this solution
Let us determine the number of moles of KMnO4
which completely oxidises the known volume (V2) of that must react
the solution of a reducing agent then normality of 5 mol of FeSO4 react with KMnO4
reducing agent can be calculated or vice-versa. = 1 mol
Once the normality of the reducing (or the 0.00625 mol of FeSO4 will react with KMnO4
oxidising) agent is known, its strength can be 1
calculated as : = × 0.00625 = 0.00125 mol
5
Strength = Normality of the solution × Now, we are to calculate the volume of 0.125 M
Equivalent weight of the oxidising KMnO4 solution which contain 0.00125 mol.
(or the reducing) agent. According to definition of molarity, 0.125 M solution
However, it may be noted that molarity equation means that
is preferred over normality equation. The basic rules 0.125 mol of KMnO4 is present in
for calculations are same as discussed in Unit 1. = 1000 mL
0.00125 mol of KMnO4 is present in
The main important step is to write the balanced 1000
redox equation. =
0.125
× 0.00125 =10 mL
REDOX REACTIONS 8/31
This can also be calculated as : Solution: The balanced chemical equation is :
Moles × 1000 2MnO4– + 5C2O42– + 16H+ ⎯⎯→ 2Mn2+ + 10CO2 + 8H2O
Molarity = Applying molarity equation,
Volume
0.00125 × 1000
0.125 = ⎛ M1 V1 ⎞ ⎛ M2 V2 ⎞
Volume ⎜⎝ n ⎟⎠ ≡ ⎜
0.00125 × 1000 1 KMnO4
⎝ n2 ⎟⎠ C O2−
2 4
∴ Volume = = 10 mL
0.125 1 30 M 2 × 20
× ≡
50 2 5
 Example 33.
30 × 5
How many millilitres of 0.025 M K 2 Cr 2 O 7 M2 = = 0.075 M
50 × 2 × 20
are required to react completely with 25.0 mL of
Molecular wt. of C2O42– = 88
0.20 M solution of FeSO4 ?
Wt. of C2O42– = 0.075 × 88 = 6.6 g
Solution: The balanced chemical equation is 6.6
Amount of C2O42– in 250 mL = × 250 = 1.65g
6Fe2+ + 6Cr2O72 + 14H+ ⎯⎯⎯→ 6Fe3+ + 2Cr3+ + 7H2O 1000
1.65
1 mol of K2Cr2O7 ≡ 6 mol of FeSO4 % Purity = × 100 = 91.7%
1.80
Moles of FeSO4 present in 25.0 mL of 0.20 M solution
0.20  Example 36.
× 25.0 = 0.005 mol 2.48 g of hydrated sodium thiosulphate
1000
Now 6 mol of FeSO4 require K2Cr2O7 (Na2S2O3·xH2O) was dissolved per litre of the
= 1 mol solution. 25 mL of this solution required 12.5 mL
1 of M/100 iodine solution. Determine the value
× 0.005 = 0.000833 mol
= of x.
6
Let us calculate the volume of K2Cr2O7 solution Solution: The balanced chemical equation is :
containing 0.000833 mol 2Na2S2O3 + I2 ⎯⎯⎯→ Na2S4O6 + 2NaI
0.025 mol of K2Cr2O7 are present in
Let the molarity of Na2S2O3·xH2O be M1
= 1000 mL
Applying molarity equation,
0.000833 mol of K2Cr2O7 are present in
1000 × 0.000833 ⎛ M1 V1 ⎞ ⎛ M2 V2 ⎞
⎜⎝ n ⎟⎠ ≡ ⎜
=
0.025
= 33.3 mL
1 Na2S2O3
⎝ n2 ⎟⎠ I
2

 Example 34. M1 × 25 1 12.5

M ≡ ×
Determine the volume of KMnO4 solution 2 100 1
10
required to react completely with 25.0 mL of M/5 12.5 × 2
M1 = = 0.01 M
oxalic acid solution. 100 × 25
Solution: The balanced chemical equation is Molecular wt. of Na2S2O3·xH2O
= 2 × 23 + 2 × 32 + 3 × 16 + x × 18
2KMnO4 + 5(COOH)2 + 3H2SO4 ⎯⎯⎯→
= 158 + 18x
K2SO4 + 2MnSO4 + 10CO2 + 8H2O Amount of Na2S2O3·xH2O = 0.01 × (158 + 18x) g
From the balanced equation, it is clear that But actual amount = 2.48 g
2 mol of KMnO4 ≡ 5 mol of (COOH)2 ∴ 0.01(158 + 18x) = 2.48
Applying molarity equation 2.48
(158 + 18x) = = 248
0.01
⎡ M1 V1 ⎤ ⎡ M2 V2 ⎤
⎢ ⎥ ≡ ⎢ ⎥ 18x = 248 – 158 = 90
n
⎣ 1 ⎦KMnO4 ⎣ n2 ⎦(COOH)2
90
∴ x = = 5.
18
1 V 1 25.0
× 1 = ×
10 2 5 5

25.0 × 10 × 2
or V1 = = 20.0 mL.
5×5
16. How many millilitres of 0.125 M K2Cr2O7 are required
 Example 35. to react completely with 25.0 mL of 0.250 M
1.80 g of impure sample of oxalate was dissolved FeSO4 solution in acidic medium?
in water and the solution made to 250 mL. On 17. A 16.4 ml volume of 0.14 M KMnO 4 solution is
titration 20 mL of this solution required 30 mL required to oxidise 20.0 ml of FeSO4 solution in acidic
of M/50 KMnO 4 solution. Calculate the medium. What is the concentration of FeSO 4
percentage purity of the sample. solution ?
8/32 MODERN'S abc + OF CHEMISTRY–XI

18. How many millilitres of 0.150 M KMnO4 solution are ∴ 0.014 mol of KMnO4 is present in solution
required to react completely with 35.0 ml of 1000
0.150 M SnCl2 solution, given the chemical equation = × 0.014 = 280 mL.
0.05
for the reaction :
5 Sn2+ + 2 MnO–4 + 16H+ → 5 Sn4+ + 2Mn2 + + 8H2O INDIRECT REDOX REACTIONS:
19. Calculate the concentration of hypo (Na2S2O3·5H2O) ELECTROCHEMICAL CELLS
solution in gL –1 if 10.0 mL of this solution In the direct redox reaction, the transference of
decolourised 25 mL of M/50 iodine solution.
electrons is limited to very small distances and,
20. Calculate the volume of 0.05 M KMnO4 solution therefore, no useful electrical work could be obtained.
required to completely oxidise 3.20 g of oxalic acid In these reactions, chemical energy appears as heat.
(H2C2O4) in acidic medium.
However, if the transference of electrons from zinc
to copper ions is allowed to occur through some
metallic wires, useful electrical work could be
16. The balance equation is performed. Such redox reactions are called indirect
6Fe2+ + Cr2O72– + 14 H+ ––→ 6Fe3+ + 2Cr3+ + 7H2O redox reactions and electrical energy is produced
From the equation, it is clear during such spontaneous reactions instead of heat
energy. Let us consider the above redox reaction
⎛ M1 V1 ⎞ ⎛ M2 V2 ⎞
⎜⎝ n ⎟⎠ K Cr O ≡ ⎜⎝ n ⎟⎠ FeSO between Zn metal and Cu2+ ions performed indirectly
1 2 2 7 2 4
in separate vessels.
0.125 × V1 0.250 × 25.0
= The arrangement consists of two beakers, one
1 6
of which contains 1.0 M solution of zinc sulphate
0.250 × 25.0 and the other 1.0 M solution of copper sulphate. A
∴ V1 = 0.125 × 6
= 8.33 mL
zinc rod is dipped into ZnSO4 solution while a copper
rod is dipped into CuSO4 solution. These rods are
17. MnO4– + 5Fe2+ + 8 H+ ––→ Mn2+ + 5Fe3+ + 4H2O known as electrodes. The metallic rods in the beaker
are connected to the ammeter by means of an
M1 V1 M2 V2
= insulated wire through a key having an on or off
1 5
switch. The solutions in the two beakers are
0.14 × 16.4 20.0 × M2
or = connected by an inverted U-tube containing
1 5
concentrated aqueous solution of some electrolyte
0.14 × 16.4 × 5
∴ M2 = 20.0
= 0.574 mL such as KCl, KNO 3, or NH 4NO 3 which does not
undergo a chemical change during the process. The
18. 5Sn2+ + 2MnO4– + 16 H+ ––→ 5Sn4+ + 2Mn2+ + 8 H2O
two openings of the U-tube are plugged with some
M1 V1 M2 V2 porous material such as glass wool or cotton (Fig. 3).
=
5 2
The U-tube which connects the two glass beakers is
35.0 × 0.150 0.150 × V2 called a salt bridge. Its function will be discussed
or =
5 2
separately.
35.0 × 0.150 × 2
∴ V2 = = 14.0 mL.
0.150 × 5
Electrons flow
19. 2S2O3 2– + I2 ⎯→ S4O6 2– + 2I– e e
Key
M 1 × 10 1 25 Ammeter Current
= × or M1 = 0.1 M
2 50 1 Salt bridge Cathode (Cu)
Anode (Zn)
Conc. of Na2S2O3·5H2O = 0.1 × 248 = 24.8 gL–1.
20. 2KMnO4 + 5(COOH)2 + 3H2SO4 ⎯→
K2SO4 + 2MnSO4 + 8H2O + 10CO2 Cotton Plugs
3.25 2+
Moles of oxalic acid = = 0.035 Zn
90 Cu
2+

5 moles of (COOH)2 ≡ 2 moles of KMnO4

1M ZnSO4 (aq) 1M CuSO4 (aq)
2
0.035 moles of (COOH)2 = × 0.035 = 0.014 mol.
5 Fig. 3. Indirect redox reaction between zinc and copper
Now, 0.05 mol of KMnO4 is present in solution sulphate.
= 1000 mL.
REDOX REACTIONS 8/33

When the switch is in the off position, no reaction

takes place in either of the beakers and no current
flows through the metallic wire. When the switch is
in the on position, the following observations can be
made :
(i) There is a flow of electric current through the
external circuit.
(ii) The zinc rod loses its weight and the copper
plate gains weight.
(iii) The concentration of ZnSO4 solution increases
and that of CuSO4 solution decreases.
(iv) The solutions in the two beakers remain
electrically neutral.
From these observations, it is clear that the overall
reaction is : Fig. 4. Working of an electrochemical cell.
Zn(s) + Cu2+ (aq) ⎯⎯→ Zn2+ (aq) + Cu(s)
During the reaction, zinc is oxidised to Zn2+ ions neither involved in any electrochemical change nor
which go into the solution. The electrons released do they react chemically with the electrolytes
Zn(s) ⎯⎯→ Zn2+ (aq) + 2e– electrically connected by them. Generally salts like
at the electrode move towards the other electrode KCl, KNO3, NH4NO3, etc. are used. For preparing a
through outer circuit. These electrons are accepted by salt bridge, gelatin or agar agar is dissolved in a hot
Cu2+ ions of CuSO4 solution which are reduced to aqueous solution of KCl, KNO3 or NH4NO3 and filled
copper. The metal gets deposited on the copper in a U-tube. On cooling, the agar agar solution becomes
electrode. solid and is used as salt bridge.
Cu2+ (aq) + 2e– ⎯⎯→ Cu(s) The important functions of the salt bridge are :
Thus, zinc plate gradually loses its weight while (i) Salt bridge connects the solutions in the two
copper plate gains in weight. half cells and completes the cell circuit. For the flow
The redox reaction occurring in this indirect of electric current through the circuit, we know that
arrangement is the same as that taking place in a single there should not be broken contacts throughout the
beaker. The basic difference between the two is that in circuit. As already explained, the solutions of the half
the direct redox reaction, energy is liberated in the form cells are connected by a salt bridge and their electrodes
of heat energy whereas in indirect redox reaction, by means of a wire. Therefore, the salt bridge
energy is liberated in the form of electrical energy. Thus, completes the circuit.
indirect redox reactions lead to the production of (ii) Salt bridge keeps the solutions in the two
electrical energy. The arrangement for carrying out half cells electrically neutral. In order to understand
indirect redox reactions is called electrochemical cell. this, let us consider Zn–CuSO4 cell. In the oxidation
Thus, an electrochemical cell is half cell, zinc atoms lose electrons and change into
Zn 2+ ions. The positively charged Zn 2+ ions pass
a device used to convert chemical energy
into the solution. After some time, this results
produced in a redox reaction into electrical into accumulation of extra positive charge in the
energy. solution around the anode. Similarly, in the reduction
The electrochemical cells are also called galvanic half cell, Cu2+ ions accept electrons and get reduced
cells or voltaic cells after the names of the scientists to Cu. After some time, the solution around cathode
Luigi Galvani (1780) and Alessandro Volta (1800) who will acquire extra negative charge due to excess of
were the first to device such experiments for SO 42— ions. The accumulation of positive charge
converting chemical energy into electrical energy. around zinc rod will prevent the further flow of
electrons from the zinc rod. Similarly, the
Salt Bridge and its Functions accumulation of negative charge around copper
A salt bridge has an important role to play in an electrode will prevent the flow of electrons to the
electrochemical cell. It is usually an inverted U- tube copper ions. Thus, in the absence of salt bridge the
filled with concentrated solution of inert electrolytes flow of electrons will occur only momentarily and the
(Fig 4). An inert electrolyte is the one whose ions are cell will stop working.
 8/34 MODERN'S abc + OF CHEMISTRY–XI

However, the accumulation of charges in the two Oxidation half Cu(s) ⎯⎯→ Cu2+ (aq) + 2e–
half cells is prevented by using a salt bridge. When reaction
the concentration of Zn2+ ions around anode increases, Reduction 2Ag+ (aq) + 2e– ⎯⎯→ 2Ag(s)
sufficient number of Cl– ions migrate from the salt reaction
bridge to the anode half cell. Similarly, to neutralise
Net reaction Cu(s) + 2Ag+ (aq)⎯⎯→Cu2+ (aq) + 2Ag(s)
the excess negative charge due to the additional SO42–
ions in cathode half cell, sufficient number of K+ ions The electrons lost in the oxidation half reaction
migrate from the salt bridge to this half cell. Thus, must be equal to the electrons gained in the reduction
the salt bridge provides cations and anions to replace half reaction. In order to equate them, the ionic
the ions lost or produced in the two half cells to equations may be multiplied suitably if necessary.
maintain electrical neutrality.
It may be noted that the salt bridge in a cell can be
replaced by a porous partition which allows the migration  Example 37.
of ions without allowing the solutions to intermix. Write the half reactions for the following redox
The working of the electrochemical cell is reactions :
represented in Fig. 4. (a) 2Fe3+(aq) + 2I– (aq) ⎯⎯→2Fe2+(aq) + I2(aq)
+
Half Cells and Half Cell Reactions (b) Zn(s) + 2H (aq) ⎯⎯→ Zn2+(aq) + H2(g)
In the indirect redox reactions, the oxidation and (c) Al(s) + 3Ag+ (aq) ⎯⎯→Al3+(aq) + 3Ag(s)
reduction occur separately and these are called half cells.
The reactions occurring in half cells are called half cell Solution:
reactions. The half cell in which oxidation (loss of (a) 2Fe3+(aq) + 2I– (aq) ⎯⎯→2Fe2+(aq) + I2(aq)
electrons) occurs is called oxidation half cell and the
Oxidation half reaction :
reaction taking place in it is called oxidation half cell
reaction. Similarly, half cell in which reduction (gain of 2I– (aq) ⎯⎯→ I2(aq) + 2e–
electrons) occurs is called reduction half cell and the Reduction half reaction :
reaction taking place in it is called reduction half cell 2Fe3+(aq) + 2e– (aq) ⎯⎯→2Fe2+(aq)
reaction.The two half cells constitute a redox couple. A +
redox couple is defined as having together the oxidized (b) Zn(s) + 2H (aq) ⎯⎯→ Zn2+(aq) + H2(g)
and reduced forms of a substance taking part in an Oxidation half reaction :
oxidation or reduction half reaction. Zn(s) ⎯⎯→ Zn2+(aq) + 2e–
The net reaction is the sum of two half cell reactions. Reduction half reaction :
This can be illustrated by the following examples :
Reaction between Zn metal and Cu2+ ions (CuSO4 2H+ (aq) ⎯⎯→ H2(g)
solution) may be written as : (c) Al(s) + 3Ag+ (aq) ⎯⎯→ Al3+(aq) + 3Ag(s)
Oxidation half Zn(s) ⎯⎯→ Zn2+ (aq) + 2e– Oxidation half reaction :
reaction
Reduction half Cu2+ (aq) + 2e– ⎯⎯→ Cu(s) Al(s) ⎯⎯→ Al3+(aq) + 3e–
reaction Reduction half reaction :
Net reaction Zn(s) + Cu2+ (aq)⎯⎯→ Zn2+ (aq) + Cu(s) 3Ag+ (aq) ⎯⎯→ 3Ag (s)
Similarly, in case of aluminium metal displacing
silver ions from a solution of silver nitrate we get the REPRESENTATION OF AN
half reactions as : ELECTROCHEMICAL CELL
Oxidation half Al(s) ⎯⎯→ Al3+ (aq) + 3e– We have seen that an electrochemical cell or
reaction galvanic cell consists of two electrodes i.e., anode and
Reduction half Ag+(aq) + e– ⎯⎯→ Ag(s) cathode. The electrolyte solutions containing these
reaction electrodes are called half cells. When these two half
To balance the number of electrons, we multiply cells are combined, a cell is formed. The following
reduction half reaction by 3 and then add so that net universally accepted conventions are used for
reaction becomes representing an electrochemical cell.
Al(s) + 3Ag+(aq) ⎯⎯→ Al3+(aq) + 3Ag(s) 1. A galvanic cell is represented by writing the anode
Similarly, reaction between Cu metal and Ag+ ions (where oxidation occurs) on the left hand side and
(AgNO3 solution) may be written as : cathode (where reduction occurs) on the right hand side.
REDOX REACTIONS 8/35

2. The anode of the cell is represented by writing Sometimes negative and positive signs are also
metal first and then the electrolyte. The two are put on the electrodes. Anode is a negative pole while
separated either by a semicolon (;) or by a vertical line. cathode acts as positive pole. The electrons flow from
The electrolyte may be written as ionic species or by the negative pole (anode) to the positive pole (cathode)
the formula of the whole compound. For example, in the external circuit. On the other hand,
Zn ; Zn2+ or Zn | Zn2+ conventionally, the current is said to flow in the
For further information, the concentration of the opposite direction.
electrolyte is also mentioned within bracket after the The important generalisations in an electro-
cation, i.e., chemical cell may be summed up as :
Zn ; Zn2+ (1 M) or Zn | Zn2+ (1 M)
Oxidation occurs at anode.
In case of gas electrodes such as hydrogen
Reduction occurs at cathode.
electrode, inert metal which serves as the electric
contact for the electrode is also written as : Cathode is positive and anode is negative in a
galvanic cell.
Pt, H2 (1 atm); H+ (1 M)
In this case, Pt, H2 (1 atm) stands for hydrogen Electrons flow from anode to cathode in the
and platinum together as solid phase, in which H2 is external circuit.
absorbed under 1 atm pressure. Comma is used to Chemical energy is converted into electrical
indicate that they form one phase. energy.
3. The cathode of the cell is represented by writing
the electrolyte first (or cation of the electrolyte) and ELECTRODE POTENTIAL
then metal. For example, When an electrode say copper, is immersed in
Cu2+ ; Cu or Cu2+ | Cu or Cu2+ (1 M) | Cu contact with a solution of its ions, then either of the
Cl– (0.1 M); Cl2 (1 atm), Pt following three possibilities can take place :
4. The salt bridge which separates the two half (a) The metal ions (Cu2+) may collide with the
cells is indicated by two vertical lines. For example, electrode and do not undergo any change.
Zn | Zn2+ (1M) || Cu2+ (1M) | Cu (b) Cu2+ ions may collide with the electrode, gain
The complete formula of a cell may be represented electrons and get converted into metal atoms (i.e., the
as follows : ions are reduced).
Electrons Cu2+ + 2e− ⎯⎯→ Cu (Reduction)
(c) Cu atoms on the electrode may lose electrons
to the electrode and become Cu2+ ions and go into the
⊕ solution.
Zn Zn2+ (1M) Cu2+ (1M) Cu
Cu ⎯⎯→ Cu2+ + 2e− (Oxidation)
These possibilities are shown in Fig. 5.
Anode Cathode
Now, if the metal has relatively high tendency to
Oxidation occurs Salt bridge Reduction occurs get oxidised, its atoms will lose electrons readily and
form Cu 2+ ions, which go into the solution. The

Cu2+

Fig. 5. Concept of electrode potential.

 8/36 MODERN'S abc + OF CHEMISTRY–XI

electrons lost on the electrode would be accumulated Since the potential depends upon the concen-
on the metal electrode and the electrode acquires a tration of the ions in solution we adopt a standard as
slight negative charge with respect to the solution. 1 mole of ions per litre of solution. This is called
Some of the Cu2+ ions from the solution will take up standard electrode potential.
electrons and become Cu atoms. After some time, an The absolute value of the electrode potential
equilibrium will be established as : cannot be determined experimentally because
Cu (s) Cu2+ + 2e− neither the oxidation nor the reduction reaction can
Electrode Solution (on electrode) occur by itself. This difficulty can be solved by
When such an equilibrium is attained, it results selecting one of the electrodes as a reference
in separation of charges (negative on the electrode with electrode and arbitrarily fixing the potential of this
respect to the solution). electrode as zero. For this purpose, reversible
hydrogen electrode has been universally accepted
Similarly, if the metal ions have relatively greater
as reference electrode. It is called standard hydrogen
tendency to get reduced, they will take electrons from
electrode (S.H.E.) or normal hydrogen electrode
the electrode. As a result, a net positive charge will be
(N.H.E.).
developed on the electrode with respect to the solution.
This will also result into separation of charges (positive Standard Hydrogen Electrode
on the electrode with respect to the solution). It consists of platinum wire sealed in a glass
Due to separation of charges between the electrode tube and has a platinum foil attached to it.
and the solution, an electrical potential is set up
The foil is coated with finely divided platinum
between metal electrode and its solution. The electrical
and acts as platinum electrode. It is dipped into an
potential difference set up between the metal and its
acid solution containing H+ ions in 1 M concentration
solution is known as electrode potential. Thus, the
(1 M HCl). Pure hydrogen gas at 1 atmospheric
electrode potential is a measure of tendency of an
pressure is constantly bubbled into the solution at
electrode in a half cell to gain or lose electrons. The
constant temperature of 298 K. The surface of the
electrode potential may be of two types :
foil acts as a site for the reaction.
(i) Oxidation potential. The tendency of an
electrode to lose electrons or to get oxidised is called its
oxidation potential. Thus, oxidation potentials give
the tendency of an electrode to lose electrons, i.e.,
M(s) Mn+ (aq) + ne–
e.g., Zn(s) Zn2+ (aq) + 2e–
H2 2H+ (aq) + 2e–
(ii) Reduction potential. The tendency of an
electrode to gain electrons or to get reduced is called its
reduction potential. Therefore, it measures the
tendency of an electrode to gain electrons i.e.,
Mn+ (aq) + ne– M(s)
e.g., Cu2+ (aq) + 2e– Cu(s)
2H+ (aq) + 2e– H2(g)
It is evident that the oxidation potential is the
reverse of reduction potential. For example, if Fig. 6. Standard hydrogen electrode.
reduction potential of Zn is – 0.76 volts, its oxidation
potential is + 0.76 volts. The following reactions occur in this half cell
According to the present convention, the half cell depending upon whether it acts as an anode or as a
reactions are always written as reduction half cathode.
reactions and their potentials are represented as If S.H.E. acts as anode
reduction potentials. H2(g) ⎯⎯→ 2H+ + 2e–
The electrode potential depends upon If S.H.E. acts as cathode
(i) the nature of the metal and its ions 2H+ + 2e– ⎯⎯→ H2(g)
(ii) concentration of the ions in the solution and The standard hydrogen electrode is also
(iii) temperature. regarded as a reversible electrode.
REDOX REACTIONS 8/37

H2(g) 2H+ + 2e– Now, if the cell potential and the electrode potential for
one of the half cell reactions were known, the electrode
The electrode potential of an electrode can be
potential of the other electrode can be calculated. To
determined by connecting its half cell with a
solve the problem, therefore, a standard hydrogen
standard hydrogen electrode. The electrode
potential of the standard hydrogen electrode is electrode has been chosen and it has been assigned a
assigned zero electrode potential. The electrode standard reduction potential of zero volts. All other
potential of a metal electrode as determined with half cell reactions can be compared with this standard
respect to a standard or normal hydrogen electrode and a set of E° values is obtained.
is called electrode potential (E). If the ● In case, the electron accepting tendency of the metal
concentration of the ions is 1 mol L–1 solution, the electrode is more than that of a S.H.E., its standard
electrode potential is also called standard reduction potential gets a positive sign
electrode potential (E°). ● In case the electron accepting tendency of the metal
Standard hydrogen electrode is represented electrode is lesser than that of S.H.E. its standard
as : Pt, H2(g) |H+ (aq) and has zero potential at all reduction potential gets a negative sign. It must be
temperatures. remembered that according to latest convention, all
standard potentials are taken as reduction potentials.
E.M.F. OR CELL POTENTIAL OF A CELL The electrode at which reduction occurs with respect
As discussed earlier, an electrochemical cell to S.H.E. (i.e., weaker reducing agent than H+/H2 couple)
has +ve reduction potential.
consists of two half cells. One of the electrodes in a
half cell has a higher value of reduction potential as The electrode at which oxidation occurs with respect
to S.H.E. (i.e., stronger reducing agent than H+/H2 couple)
compared to the other. As a result of this potential
has – ve reduction potential.
difference, there is a flow of electrons from the
electrode with a lower reduction potential (or higher The standard electrode potentials are very
oxidation potential) to the electrode with higher important and give a lot of useful information. The
reduction potential (or lower oxidation potential). The basic point regarding the series is the stability of
difference between the electrode potentials of the two oxidized form or reduced form. If the standard
electrodes constituting an elecrochemical cell is known electrode potential is more than zero, then its reduced
as electromotive force or cell potential of a cell. form will be more stable compared to hydrogen gas.
In other words, it will be readily reduced in comparison
The electromotive force is commonly abbreviated
to hydrogen and therefore, acts as strong oxidizing
as E.M.F. and is expressed in volts. The E.M.F. of a
agent. On the other hand; if the standard electrode
cell may be expressed in terms of the difference in the
potential is negative than hydrogen, then hydrogen
reduction electrode potential as : gas is more stable than the reduced form of the species.
E.M.F. = Esubstance reduced − Esubstance oxidised In other words, it will be readily oxidized in comparison
= ER − EL to hydrogen and therefore, acts as strong reducing
agent. Similarly, we can compare two species. The
or E.M.F. = Ecathode − Eanode species having higher electrode potential will be
where ER and EL represent electrode potential of readily reduced (acts as oxidising agent) in comparison
electrode on right hand side and electrode on left hand to the other.
side respectively. It depends upon the nature of the ELECTROCHEMICAL SERIES
electrodes and the concentrations of the solutions in
In the previous section, we have discussed the
the two half cells. For example, the E.M.F. of a Daniell measurement of the standard reduction potentials (E°)
cell in which the concentrations of aqueous solutions of of a few electrodes. In a similar manner, the E° values
CuSO4 and ZnSO4 in the two half cells is 1 M at 298 K of other electrodes can also be measured. When the
is 1.10 volts. standard reduction potentials of the electrodes are
It may be noted that it is not possible to measure arranged in an increasing order, a series called
experimentally the absolute value of a single electrode electrochemical series is obtained.
because a half cell reaction cannot take place The arrangement of elements in order of
independently. We can measure only the difference decreasing reduction potential values is called
between the electrode potentials of any two half cell electrochemical series.
reactions. Then, a question arises as to how we can The electrochemical series, also called activity
obtain the reduction potential of any single electrode. series, of some typical electrodes is given in Table 1.
 8/38 MODERN'S abc + OF CHEMISTRY–XI

Table 1. Standard reduction electrode potentials at 298 K.

Electrode Electrode reaction E° (V)

(Oxidized form + ne– ⎯→ Reduced form)

F2 | F– Strongest oxidizing F2 (g) + 2e– ⎯→ 2F– (aq) Weakest reducing 2.87

Co3+ | Co2+ agent Co3+ + e– ⎯→ Co2+ agent 1.81
H2O2 | H2O H2O2 + 2H+ + 2e– ⎯→ 2H2O 1.78
MnO2, H | Mn + 2+ MnO2 (s) + 4H+ + 2e– ⎯→ Mn2+ + 2H2O 1.61
3+
Au | Au Au3+ + 3e– ⎯→ Au (s) 1.50
MnO4 | Mn– 2+ –
MnO4 + 8H+ + 5e– ⎯→ Mn2+ + 4H2O 1.49
Cl2 | Cl– Cl2 (g) + 2e– ⎯→ 2Cl– 1.36
2–
Cr2O7 , H | Cr + 3+ 2–
Cr2O7 + 4H+ + 6e– ⎯→ 2Cr3+ + 7H2O 1.33
+
O2, H | H2O O2 + 4H+ + 4e– ⎯→ 2H2O 1.23
Br2 | Br – Br2 (l) + 2e– ⎯→ 2Br– 1.09

STRENGTH OF REDUCING AGENT

STRENGTH OF OXIDIZING AGENT

–
NO3 , H | NO+ –
NO3 + 4H+ + 3e– ⎯→ NO (g) + 2H2O 0.97
Hg2+ | Hg22+ 2Hg2+ + 2e– ⎯→ Hg22+ 0.92
–
ClO | Cl – ClO + H2O + 2e–
– ⎯→ Cl– + 2OH– 0.89
2+
Hg | Hg Hg2+ + 2e– ⎯→ Hg 0.85
+
Ag | Ag Ag+ + e– ⎯→ Ag 0.80
2+
Hg2 | Hg Hg22+ + e– ⎯→ 2Hg 0.79
Fe3+ | Fe2+ Fe3+ + e– ⎯→ Fe2+ 0.78
–
MnO4 | MnO4 2– MnO4– + e– ⎯→ MnO42– 0.56
I2 | I – I2 + 2e– ⎯→ 2I– 0.54
+
Cu | Cu Cu+ + e– ⎯→ Cu 0.52
2+
Cu | Cu Cu2+ + 2e– ⎯→ Cu 0.36
AgCl |Ag AgCl + e– ⎯→ Ag + Cl– 0.22
2+
Cu | Cu + Cu2+ + e– ⎯→ Cu+ 0.15
AgBr | Ag AgBr + e– ⎯→ Ag + Br– 0.10

H+ | H2 2H+ + 2e– ⎯→ H2 0.00

Fe3+ | Fe Fe3+ + 3e– ⎯→ Fe INCREASING –0.04

INCREASING

Pb2+ | Pb Pb2+ + 2e– ⎯→ Pb –0.13

Sn2+ | Sn Sn2+ + 2e– ⎯→ Sn –0.16
Ni2+ | Ni Ni2+ + 2e– ⎯→ Ni –0.25
Fe2+ | Fe Fe2+ + 2e– ⎯→ Fe –0.44
Cr3+ | Cr Cr3+ + 3e– ⎯→ Cr –0.74
Zn2+ | Zn Zn2+ + 2e– ⎯→ Zn –0.76
Al3+ | Al Al3+ + 3e– ⎯→ Al –1.66
Mg2+ | Mg Mg2+ + 2e– ⎯→ Mg –2.36
Ce3+ | Ce Ce3+ + 3e– ⎯→ Ce –2.48
Na+ | Na Na+ + e– ⎯→ Na –2.71
Ca2+ | Ca Ca2+ + 2e– ⎯→ Ca –2.87
Ba2+ | Ba Ba2+ + 2e– ⎯→ Ba –2.91
Cs+ | Cs Cs+ + e– ⎯→ Cs –2.92
K+ | K Weakest oxidizing K+ + e– ⎯→ K Strongest –2.93
Li+ | Li agent Li+ + e– ⎯→ Li reducing agent –3.05
It may be noted that the standard oxidation are given below :
potential will have the same magnitude but opposite 1. Relative strengths of oxidising and
sign. For example, the standard oxidation potential of
reducing agents.
first electrode, Li, Li+ is + 3.05 V and standard oxidation
potential of the last electrode F–, F2 is – 2.87 V. The electrochemical series helps us to pick out
Applications of Electrochemical Series substances that are good oxidising agents and those
The main applications of the electrochemical series which are good reducing agents. In the electrochemical
REDOX REACTIONS 8/39

series, the substances are arranged in the decreasing 3. Calculation of the E.M.F. of the cell
order of reduction potential i.e. decreasing tendency The E.M.F. of the cell which is the difference
for reduction to occur or power as oxidising agent. between the reduction potential of the cathode and
Therefore, the elements at the top of the table have anode is determined by the following steps :
maximum tendency to get reduced and consequently,
they will act as good oxidising agents. On the other Step I. Write the two half cell reactions in such a
hand, the substances at the bottom of the table have way that the reaction taking place at the left hand
lower reduction potential, therefore, they have least electrode is written as an oxidation reaction and that
taking place at the right hand electrode is written as
tendency to get reduced. Consequently, they may be
reduction.
oxidised and act as good reducing agents. Thus, the
substances which have lower reduction potentials are Step II. Multiply one of the equations if necessary
stronger reducing agents while those which have by suitable number to equate the number of electrons
higher reduction potentials are stronger oxidising in the two equations. However, it may be noted that
agents. For example, a very high negative reduction electrode potential values, E° are not multiplied.
potential of lithium electrode indicates that Li+ cannot Step III. The E.M.F. of the cell is equal to the
accept electrons easily from other species. In other difference between the standard electrode potential
words, lithium can readily lose electrons and, of the right hand side electrode (E°R) and the standard
therefore, behaves as strong reducing agent. Thus, all electrode potential of the left hand side electrode (E°L).
the substances appearing at the bottom of the series Thus,
behave as good reducing agents. For example, E°cell = E°R – E°L
Li, K are the best reducing agents.
The electrode potentials of both the electrodes
Similarly, the substances at the top of the table are taken to be reduction potentials.
have high reduction potentials and they can be easily Step IV. If the E.M.F. of the cell is +ve, the reaction
reduced and act as oxidising agents. For example, is feasible in the given direction. But if E.M.F. of the
fluorine has the highest electrode potential indicating cell is –ve, the cell reaction is not feasible in the given
that fluorine is very powerful oxidizing agent. From direction. The reaction must be occurring in the
the position of the electrodes in the table we can reverse direction. Thus, to get positive value for the
conclude that H+ is a better oxidising agent than Zn2+ E.M.F. of the cell, the electrodes are to be reversed.
but Cu2+ is a better oxidising agent than H+. Thus,
good oxidising agents are the substances appearing
at the top of the table.
 Example 38.
2. Comparison of reactivities of metals
Write the half cell reaction and the overall cell
The reduction potential values indicate the
reaction for the electrochemical cell :
relative ease with which the various species of metals
and ions may be oxidised or reduced. The metals Zn | Zn2+ (1.0 M) || Pb2+ (1.0 M) | Pb
having lower reduction potential, will not be reduced Calculate the standard e.m.f. for the cell if
easily. On the contrary, such metals would be easily standard electrode potentials (reduction) for
oxidized to their ions losing electrons. These electrons Pb2+ | Pb and Zn2+ | Zn electrodes are – 0.126 V
and – 0.763 V respectively.
would reduce the other metals having higher
reduction potentials. In other words, a metal having Solution: Zn electrode acts as anode while Pb electrode
acts as cathode and, therefore, oxidation occurs at zinc
smaller reduction potential can displace metals
electrode and reduction occurs at lead electrode. The
having larger reduction potentials from the solutions half cell reactions are :
of their salts. For example, copper has lower Oxidation half reaction :
reduction potential than silver in the electrochemical Zn(s) ⎯→ Zn2+ (aq) + 2e–
series, therefore, if copper foils are added to AgNO3 Reduction half reaction :
solution, silver is displaced from the solution. In
Pb2+ (aq) + 2e– ⎯→ Pb(s)
general a metal occupying lower position in the series
can displace the metals lying above it from the Overall cell reaction :
solutions of their salts. In other words, we can say Zn(s) + Pb2+ (aq) ⎯→ Zn2+ (aq) + Pb(s)
that the metals occupying lower positions in the
E.M.F. = E°R – E°L
electrochemical series are more reactive in displacing
= – 0.126 – (–0.763)
the other metals from the solutions of their salts.
= 0.637 V.
 8/40 MODERN'S abc + OF CHEMISTRY–XI

Note. The EMF of the cell can also simply be

calculated as :
E°cell = E°R – E°L  Example 39.
If the value of E°cell is positive, then the cell is Iodine (I 2 ) and bromine (Br2 ) are added to a
correctly represented, i.e., oxidation occurs at left solution containing iodide (I–) and bromide (Br–)
electrode (anode) and reduction occurs at the right ions. What reaction would occur if the
electrode (cathode). On the other hand, if the value concentration of each species is 1M ? The
of E°cell comes out to be negative, then the cell is electrode potentials for the reactions are :
wrongly represented. Its order is reversed to get I2 + 2e– ⎯⎯→ 2I– E° = + 0.54 V
positive value for E°cell. Br2 + 2e ⎯⎯→ 2Br
– – E° = + 1.02 V
4. Predicting feasibility of a redox reaction. Solution: Since the reduction potential of Br2 is more
than that of I2, it means that bromine can readily be
The electrochemical series helps in finding out
reduced. Therefore, I– will be oxidised to I2 and this
whether a given redox reaction is feasible or not from reaction should be written as oxidation. Therefore,
the E° values of the two electrodes. the following reactions will occur :
In general, a redox reaction is feasible only if the Br2 + 2e– ⎯⎯→ 2Br–
species which has higher reduction potential is reduced 2I– ⎯⎯→ I2 + 2e–
i.e., accepts the electrons and the species which has
Br2 + 2I– ⎯⎯→ 2Br– + I2
lower reduction potential is oxidised i.e., loses the
electrons. Otherwise, a redox reaction is not feasible. Alternatively, the problem can also be solved by
considering the half cell reactions.
In other words, the species to release electrons must
have lower reduction potential as compared to the (i) I2 + 2e– ⎯⎯→ 2I– E° = + 0.54 V
species which is to accept electrons. (ii) Br2 + 2e– ⎯⎯→ 2Br– E° = + 1.02 V
The electrochemical series (Table 1) gives the Since for the feasibility of the reaction, the e.m.f. should
decreasing order of electrode potentials (reduction) of be +ve, therefore to get + ve value for the overall cell
different electrodes on moving down the table. This reaction, subtract the equation representing lower
value of E° from the equation representing the higher
means that the species to accept the electrons (getting
value of E°. Thus, subtract Eq. (i) from (ii).
reduced) must be higher in the electrochemical series
as compared to the other which is to lose electrons Br2 + 2I– ⎯⎯→ 2Br– + I2
(getting oxidised). E° = 1.02 – 0.54 = 0.48 V
Let us illustrate this by predicting the feasibility  Example 40.
of the reaction : What will be the spontaneous reaction between
Cu2+ (aq) + 2Ag(s) ⎯⎯→ Cu(s) + 2Ag+ (aq) the following half cell reactions?
From the electrochemical series (Table 1), E° (i) Cr3+ (aq) + 3e– ⎯→ Cr(s) E° = – 0.74 V
value of Cu = +0.34 V and the E° value of Ag = + 0.80 V. (ii) MnO2 (s) + 4H + 2e ⎯→ Mn (aq) + 2H2O (l)
+ – 2+
Since the reduction potential of Ag is more than that E° = 1.28 V
of Cu, this means that silver has greater tendency to Calculate E°cell.
get reduced in comparison to copper. Thus, the reaction
Solution: Since the reduction potential of reaction
Ag+ (aq) + e– ⎯⎯→ Ag(s) (ii) is more than that of reaction (i) ; reaction (ii) will
occurs more readily than the reaction occur as reduction. Therefore, reaction (i) should be
written as oxidation. To obtain the net reaction, we
Cu2+ (aq) + 2e– ⎯⎯→ Cu(s)
multiply by appropriate coefficients so that electrons
Similarly, since reduction potential of copper is get cancelled.
less than that of Ag, this means that copper will be MnO2 (s) + 4H+ (aq) + 2e– ⎯⎯→ Mn2+ (aq) + 2H2O
oxidised in comparison to Ag. Thus, the reaction, (l)] × 3
Cu(s) ⎯⎯→ Cu2+ (aq) + 2e– Cr(s) ⎯⎯→ Cr3+ (aq) + 3e–] × 2
occurs more readily than 2Cr(s) + 3 MnO2 (s) + 12H+ (aq) ⎯⎯→ 2 Cr3+ (aq) + 3 Mn2+
Ag (s) ⎯⎯→ Ag+ (aq) + e– (aq) + 6H2O
E°cell = ESubstance reduced – ESubstance oxidised
Therefore, silver will be reduced and copper will
be oxidised and the above reaction is not feasible. = 1.28 – (–0.74) = 2.02 V
Rather the reverse reaction,  Example 41.
Cu(s) + 2Ag+ (aq) ⎯⎯→ Cu2+ (aq) + 2Ag(s) can The standard electrode potential corresponding
occur. to the reaction : Au3+ (aq) + 3e– ⎯→ Au (s) is
1.42 V. Predict (i) if gold can be dissolved in 1M
REDOX REACTIONS 8/41

HCl solution and (ii) on passing hydrogen gas

through gold salt solution, metallic gold will be
precipitated or not.
Solution: The standard reduction potential is greater
than zero, therefore, reduced form of gold is more stable 21.Calculate E° For the cell :
than hydrogen. In other words, gold cannot be oxidized by Al | Al3+ (1M) || Cu2+ (1 M)|Cu
hydrogen to give hydrogen. Hence gold does not dissolve in Given E° (Al3+ | Al) = –1.66 V and
1 M HCl solution. On the other hand, if hydrogen gas is
E° (Cu2+ | Cu) = 0.34 V
passed through the salt solution of the gold, it will reduce
Au3+ ion and metallic gold will be precipitated. 22. The standard electrode potentials of some electrodes
are :
 Example 42. Electrode Zn2+|Zn Cd2+|Cd Ag+|Ag Fe2+|Fe
Is it possible to store E° (V) –0.76 –0.40 0.80 V –0.44 V
(i) Copper sulphate in a zinc vessel ? Which of the following cells are feasible and give their
(ii) Copper sulphate in a silver vessel ? E°cell?
(iii) Copper sulphate in a nickel vessel ? (i) Zn|Zn2+ || Cd2+|Cd (ii) Fe|Fe2+ || Zn2+|Zn
(iv) Copper sulphate in a gold vessel ? (iii) Cd|Cd2+|| Ag+|Ag (iv) Fe|Fe2+ || Ag+|Ag
Solution: (i) From Table 18.1, it is clear that electrode 23. An iron wire is immersed in a solution containing
potential of copper (Cu 2+ | Cu = 0.34) is more than ZnSO4 and NiSO4. When the concentration of each
zinc (Zn2+ | Zn = –0.76 V), therefore, it will be readily salt is 1 M, predict giving reasons which of the
reduced to copper and zinc will be oxidized. As a result, following reactions is likely to proceed ?
zinc vessel will dissolve.
(i) Iron reduces Zn2+ ions
(ii) It is possible to store copper sulphate in a silver
vessel because silver vessel will not dissolve (ii) Iron reduces Ni2+ ions. Given
(Ag+|Ag = 0.80V). E° (Zn2+|Zn) = –0.76V, E° (Fe2+|Fe) = –0.44V,
(iii) It is not possible to store copper sulphate in nickel and E° (Ni2+|Ni) = –0.25V
vessel because Ni will dissolve (Ni 2+ |Ni 24. Can a solution of 1 M CuSO4 be stored in a vessel
= –0.13 V).
made of nickel metal ? Given E° (Ni2+|Ni) = –0.25V
(iv) It is possible to store copper sulphate in gold and E° (Cu2+|Cu) = 0.34V
vessel (Au3+ | Au = 1.61 V).
25. Can chlorine gas be stored in a copper cylinder?
 Example 43. Given E° (Cu2+|Cu) = 0.34V and E° (Cl–|Cl) = 1.36V.
Give two examples each of oxidants which can 26. Why does blue colour of copper sulphate get
oxidize discharged when zinc rod is dipped in it ?
(i) Cl– (aq) to Cl2 (g)
Given E° (Cu 2+|Cu) = 0.34V and E° (Zn 2+|Zn)
(ii) Fe (s) to Fe2+ (aq)
= –0.76V.
(iii) I– (aq) to I2 (aq)
Solution: 27. A copper wire is dipped in silver nitrate solution in
beaker A and a silver wire is dipped in a solution of
(i) Au, F2 (ii) Ni, Sn
copper sulphate kept in beaker B. If the standard
(iii) Fe, Ag
electrode potential for
5. Predicting whether a metal can liberate
hydrogen from the acid or not. The metals like zinc, Cu+ + 2e– ⎯⎯→ Cu is +0.34 and for
magnesium and nickel can liberate hydrogen from the Ag+ + e– ⎯⎯→ Ag is + 0.80 V.
acids like HCl, H2SO4 etc., but metals like copper and Given E° (Ni2+|Ni) = –0.25V and E° (Cu2+|Cu)
silver cannot do so. In general, only those metals can = 0.34V
liberate hydrogen from the acids which have negative Predict in which beaker the ions present will get
values of reduction potentials i.e., –E° values. Obviously, reduced ?
hydrogen will have greater tendency to get reduced
(accept electrons) and the metal can lose electrons (get
oxidised) and hydrogen gas is liberated.
M ⎯⎯→ M+ (aq) + e– 21. 2.0 V
(Monovalent) 22. (i) Feasible, + 0.36 V (ii) not feasible, –0.32 V
1
H+ (aq) + e– ⎯⎯→ H or 2 H2 (iii) feasible, +1.20 V (iv) feasible, +1.24 V.
23. Iron reduces Ni2+ ions.
Metals like copper and silver have + E° values
24. No.
i.e., electron accepting tendencies. Their atoms are not
in a position to lose electrons to H+ ions of the acid. 25. No.
Therefore, hydrogen gas is not liberated. 27. In beaker A, Ag+ will be reduced.
8/42 MODERN'S abc + OF CHEMISTRY–XI

Q. 1. Arrange the following molecules in the decreasing order of oxidation state (+ve to
–ve) of nitrogen : NO2, NH3, HN3, NO2–, N2H4.
Ans. Oxidation states of N are :
1
NO2 = + 4, NH3 = –3, HN3 = –
3
NO2– = + 3, N2H4 = –2
Decreasing order of oxidation state :
NO2 > NO2– > HN3 > N2H4 > NH3
Q. 2. Can the reaction :
Cr2O72– + H2O ⎯→ 2CrO42– + 2H+
be regarded as a redox reaction ?
Ans. In this reaction,
Oxidation number of Cr in Cr2O72– = +6
Oxidation number of Cr in CrO42– = +6
Since during this reaction, the oxidation number of Cr has neither increased nor decreased, therefore,
the above reaction cannot be regarded as a redox reaction.
Q. 3. Calculate the oxidation number of Fe in
(i) Fe3O4 (ii) Fe4[Fe(CN)6]3
Ans. (i) Fe3O4 3x – 8 = 0 or x = 8/3 (fractional)
Actually the composition of Fe3O4 is FeO.Fe2O3
The O.N. of Fe in FeO is +2 and in Fe2O3, it is +3.
On the average O.N. comes out to be 8/3.
(ii) Fe4[Fe(CN)6]3. In this case the O.N. of Fe in the bracket is +2 and that of Fe outside the brackets is +3.
Fe4+3[Fe+2(CN)6]3
Q. 4. Split the following redox reactions in the oxidation and reduction half reactions :
(i) 2K (s) + Cl2 (g) ⎯⎯→ 2KCl (s)
(ii) 2Al (s) + 3Cu2+ (aq) ⎯⎯→ 2Al3+(aq) + 3Cu (s)
Ans. (i) Oxidation half reaction : 2K (s) ⎯⎯→ 2K+(aq) + 2e–
Reduction half reaction : Cl2 (g) + 2e– ⎯⎯→ 2Cl–
(ii) Oxidation half raction : 2Al (s) ⎯⎯→ 2Al3+ (aq) + 6e–
Reduction half reaction : 3Cu2++ 6e– ⎯⎯→ 3Cu (s)
Q. 5. Nitric acid acts only as an oxidising agent while nitrous acid acts both as an oxidising as well as
reducing agent. Explain.
Ans. (i) HNO3. Oxidation number of N in HNO3 is +5.
Maximum oxidation number of N is +5 because it has five electrons in the valence shell (2s22p3).
Minimum oxidation number of N is –3 because it can accept 3 more electrons to get noble gas
configuration.
Since O.N. of N in HNO3 is maximum, therefore, it can only decrease. Thus, HNO3 can act as an
oxidising agent.
(ii) HNO2. Oxidation number of N = + 3
Maximum O.N. of N = + 5
Minimum O.N. of N = – 3
Therefore, the O.N. of N can increase by losing electrons or can decrease by accepting electrons. Thus,
HNO2 can act both as an oxidising as well as a reducing agent.
Q. 6. Calculate the oxidation number of the underlined element in
(a) VO2+ (b) UO22+ (c) Ba2XeO6 (d) K4P2O7 (e) K2S
Ans. The O.N. of underlined atom is represented by x
(a) VO2+ x + 2 (-2) = +1 or x = +5
(b) UO2 2+ x + 2 (-2) = +2 or x = +6
REDOX REACTIONS 8/43

(c) Ba2XeO6 +2(2) + x + 6 (–2) = 0 or x = +8

(d) K4P2O7 1× 4 + 2x + 7 (–2) = 0 or x = +5
(e) K2S 1× 2 + x = 0 or x = –2
Q. 7. Which of the following equations represent oxidation reduction reaction ? Identify each oxidising
agent and each reducing agent.
(a) KOH + H2O2 ⎯⎯→ KHO2 + H2O
(b) Cr2O72– + 2 OH– ⎯⎯→ 2CrO42– + H2O
(c) K + O2 ⎯⎯→ KO 2
(d) Ca(HCO3)2 ⎯⎯→ CaCO3 + CO2 + H2O
Ans.(i) a, b, and d are not redox reactions.
c is a redox reaction. The oxidising agent is O2 and reducing agent is K.
Q. 8. Identify the oxidising and reducing agent in the following reaction :
Fe2+ + 2H+ + NO3– ⎯⎯→ Fe3+ + NO2 + H2O
Ans. +2 +5 3+ +4
Fe2+ + 2H+ + NO3– ⎯⎯→ Fe3+ + NO2 + H2O
Fe2+ is oxidised to Fe3+ by NO3– ion and therefore, NO3– is an oxidising agent. NO3– is reduced from N(+5)
to N(+4) in NO2 by Fe2+ and therefore, Fe2+ is a reducing agent.
Q. 9. Nitric acid is an oxidising agent and reacts with PbO but it does not react with PbO2. Explain
Why ?
Ans. PbO is a basic oxide and reacts with. HNO3 and simple acid base reaction takes place.
2PbO + 4HNO3 ⎯⎯
→ 2Pb(NO3)2 + 2H2O
But in PbO2, lead is in +4 oxidation state and cannot be further oxidised. Therefore, it does not react with
HNO3.
Q. 10. Predict the maximum and minimum oxidation states for (i) Cl (ii) Ti
Ans. Maximum oxidation state for Cl = +7
Minimum oxidation state for Cl = –1
Maximum oxidation state for Ti = +4
Minimum oxidation state for Ti = 0
For metals minimum O.N. is zero but for non–metals, it is group number minus 8.
Q. 11. The electrode reduction potentials of four metallic elements A, B, C and D are respectively +0.79,
– 0.74, 1.08 and – 0.31 V. Arrange these in order of decreasing electropositive character.
Ans. Higher the electrode reduction potential, lower is its tendency to lose electrons and therefore, lower is
the electropositive character of the metal. So, the metals can be arranged as : B, D, A, C
Q. 12. An iron rod is immersed in a solution containing NiSO4 and ZnSO4. When the concentration
of each salt is 1M, predict giving reasons which of the following reactions is likely to
proceed ?
(i) Iron reduces Zn2+ ions (ii) Iron reduces Ni2+ ions
Given : E°(Zn 2+|Zn) = – 0.76 V, E°(Fe2+|Fe) = – 0.44 V and E°(Ni 2+|Ni) = – 0.25 V
Ans. (i) The reduction potential of iron is more than that of zinc. Therefore, iron will be reduced. In other
words, Zn2+ will not be reduced by iron.
(ii) The reduction potential of Ni2+ is more than that of iron. Therefore, Ni2+ will be reduced by iron.
Q. 13. Which of the following reactions are not feasible ?
(a) Zn(s) + 2Ag+(aq) ⎯⎯→ Zn2+(aq) + 2Ag(s)
(b) I2(s) + 2Br–(aq) ⎯⎯→ 2I–(aq) + Br2
(c) 2Fe3+(aq) + 2I–(aq) ⎯⎯→ I2(aq) + 2Fe2+(aq)
(d) 2Ag + 2H+(aq) ⎯⎯→ H2 + 2Ag+(aq)
Ans. (a) and (c) are feasible.
Q. 14. At what concentration of Cu2+ (aq) will its electrode potential become equal to its standard
electrode potential ?
Ans. At 1 M concentration.
8/44 MODERN'S abc + OF CHEMISTRY–XI

Q.15. How does Cu2O act as both oxidant and reductant ? Explain with proper reactions showing the
change of oxidation number in each case.
Ans. In Cu2O, copper is in +1 (Cu+) oxidation state and it undergoes disproportionation to form Cu and Cu2+
as :
2Cu+(aq) ⎯→ Cu(s) + Cu2+(aq)
+
Thus, Cu or Cu2O acts both as an oxidant as well as a reductant.
For example,
(i) When heated in air, Cu2O is oxidised to CuO

+1 +2
1
Cu2O + O ⎯→ 2CuO
2 2
Thus, Cu2O acts as a reductant and reduces O2 to O2–.
(ii) When heated with Cu2S, it oxidises S2– to SO2 and hence Cu2O acts as an oxidant.
+1 +1 0
2Cu2O + Cu2S ⎯→ 6Cu + SO2
Q. 16. A solution of silver nitrate was stirrred with an iron rod. Will it cause any change in the concentration
of silver and nitrate ions ?
Ans. The Eo of Fe2+ | Fe (– 0.44 V) is lower than that of Ag+ | Ag (+0.80 V), therefore, Ag+ gets reduced and Fe
gets oxidised. As a result, the concentration of Ag+ ions decreases and that of NO3– ions remains unchanged.
2 Ag+ (aq) + 2 NO3– (aq) + Fe(s) ⎯→ 2 Ag (s) + Fe2+ (aq) + 2 NO3– (aq)
Q. 17. What is the oxidation number of N in HNO4?
Ans. By conventional method, O.N. of N is : +1 + x + 4(– 2) = 0 or x = +7.
However, N cannot have O.N. more than +5. Therefore, O.N. of N in HNO4 (peroxynitric acid) must be
calculated from its structure. The structure of HNO4 is H—O—O—N ⎯→ O. It contains one peroxide

O
linkage and therefore, each of the two oxygen atoms of peroxide bonds has an O.N. of –1.
Thus, +1 – 1 – 1 + x – 2 – 2 = 0 or x = +5.
Q. 18. Calculate the oxidation number of nickel in Ni(CO)4, iron in Fe(CO)5 and carbon in CH2O.
Ans. Ni(CO)4 : x + 4(0) = 0 or x = 0
Fe(CO)5 : x + 5(0) = 0 or x = 5
CH2O : x + 2(+1) – 2 = 0 or x = 0.
Q. 19. At what concentration of Zn2+ (aq) will its electrode potential become equal to its standard electrode
potential ?
Ans. At 1 M concentration.
Q. 20. The Eo (Al3+|Al) and Eo (Cu2+|Cu) are – 1.66 V and + 0.34 V respectively. Is the cell :
Cu|Cu2+ (1M)|| Al3+ (1M)|Al feasible or not feasible?
Ans. Not feasible.

Key Terms
• Oxidation is a process which involves loss of electrons or increase in oxidation number.
• Reduction is a process which involves gain of electrons or decrease in oxidation number.
• Oxidation number is the charge which an atom appears to have when all other atoms are removed from it as ions.
• Oxidising agent is a substance which accepts one or more electrons or its oxidation number decreases.
• Reducing agent is a substance which loses one or more electrons or its oxidation number increases.
REDOX REACTIONS 8/45
 8/46 MODERN'S abc + OF CHEMISTRY–XI

NCERT
Q. 1. Assign oxidation number to the underlined But oxidation number cannot be fractional. In fact
elements in each of the following species : KI3 exists as : K+ [I–I ←⎯ I]– in which a coordinate
(a) NaH2PO4 (b) NaHSO4 bond is formed between I2 molecule and I–. In this
(c) H4P2O7 (d) K2MnO4 the oxidation number of two iodine atoms forming
I2 molecule is zero and that of iodine forming the
(e) CaO2 (f) NaBH4
coordinate bond is –1. Thus, the actual oxidation
(g) H2S2O7 (h) KAl(SO4)2.12H2O number of atoms are :
Ans. Let the oxidation number of underlined atom be x. + 0 −1
+1 +1 x −2 K I2 I
(a) Na H P O
2 4
(b) H2S4O6. The oxidation number may be calculated
1(+1) + 2(+1) + x + 4 (–2) = 0 ∴ x = +5
as :
Oxidation number of P in NaH2PO4 is + 5 +1 x −2
+1 +1 x −2 H 2 S 4 O6
(b) Na H S O
4 5
1(+1) + 1(+1) + x + 4 (–2) = 0 2 (+1) + 4x + 6 (–2) = 0 ∴ x=+
2
x–6=0 ∴ x=+6
Since oxidation number cannot be fractional,
+1 x −2
(c) H4 P2 O7 the actual oxidation number of different S atoms
are:
4(+1) + 2(x) + 7 (–2) = 0
2x – 10 = 0 ∴ x=+5 Ο Ο
+1 x −2 +5 || 0 0 +5 ||
(d) K Mn O H⎯O⎯S⎯S⎯S⎯ S ⎯O⎯H
2 4 || ||
2(+1) + x + 4(–2) = 0 O O
x–6=0 ∴ x=+6
(c) Fe3O4. The oxidation number may be calculated
+2 x as :
(e) Ca O
2
x −2
+2 + 2 (x) = 0 ∴ x=–1 Fe3 O4
+1 x −1 8
(f) Na B H 4 3x +4 (–2) = 0 or ∴ x=+
3
1(+1) + x + 4(–1) = 0 In fact, Fe3O4 exists as a mixture of FeO and
x–3=0 ∴ x=+3 Fe2O3 as :
+1 x −2 +2 −2 + 3 −2
(g) H S O FeO. Fe2 O3
2 2 7
2(+1) + 2 (x) + 7(–2) = 0 Fe has oxidation number of +2 and +3.
2x – 12 = 0 ∴ x=+6 (d) CH3CH2OH – By conventional method, the
+1 +3 x −2 +1 −2
oxidation number may be calculated as :
(h) K Al (S O ) . 12 H O x +1 x +1 − 2 +1
4 2 2
C H 3 C H2 O H
1(+1) + 1 (+3) + 2x + 8 (–2) + 12 (2 × 1– 2) = 0
x + 3 (+1) + x + 2(+1) + 1(–2) + 1(+1) = 0
2x – 12 = 0 ∴ x=+6
2x + 4 = 0 ∴ x=–2
Q. 2. What are the oxidation number of the underlined
In fact, ethanol may be written as :
elements in each of the following and how do you
rationalise your results ? H H
| 2 |1
(a) KI3 (b) H2S4O6 H ⎯ C ⎯ C ⎯ OH
(c) Fe3O4 (d) CH3CH2OH | |
H H
(e) CH3COOH
Ans. (a) In KI3, since the oxidation number of K is +1, C2 is attached to three H atoms (less electronegative
therefore, the average oxidation number of iodine than carbon) and one CH 2 OH group (more
electronegative than carbon). Therefore,
1
is – . O.N. of C2 : 3 (+1) + x +1(–1) = 0 or x = –2
3
C1 is attached to one OH (O.N. = –1) and one
+1 x 1
K I3 + 1 + 3(x) = 0 ∴ x=– CH3(O.N. = +1) and two H-atoms
3
O.N. of C1 = + 1 + 2 (+1) + x + 1(–1) = 0 ∴ x = –2
REDOX REACTIONS 8/47

(e) CH3COOH. By conventional method Q. 4. Fluorine reacts with ice and results in the
x +1 x −2 −2 +1 change :
C H3 C O O H H2O(s) + F2(g) ⎯→ HF(g) + HOF(g)
x + 3 (+1) + x + (–2) + (–2) + 1(+1) = 0 Justify that this reaction is a redox reaction.
2x + 0 = 0 ∴ x=0 +1 −2 0 +1 −1 +1 −2 +1
Ans. H2 O (s) + F2 ( g) ⎯⎯→ H F + H O F
But according to structure,
H O In this case, F2 is reduced to HF and oxidised to
| 2 || 1 HOF. Therefore, it is redox reaction. HOF is unstable
H ⎯ C ⎯ C ⎯ OH and decomposes to form O2 and HF.
|
+1 −2 +1 +1 −1 0
H
C2 is attached to three H atoms (less electronegative 2 H O F ⎯⎯→ 2H F + O
than C) and one –COOH group (more electronegative In this reaction, F of HOF is reduced while O of HOF
than C). is oxidised. Therefore, it is a redox reaction but not
a disproportionation reaction. If oxygen of HOF
O.N. of C2 = 3 (+1) + x + 1(–1) = 0 ∴ x = –2
disproportionates, then oxygen must show three
C1 is attached to one oxygen atom by a double bond, oxidation states. If we assume that oxidation state
one OH-group (O.N. = –1) and one CH3 (O.N. = +1). of O is zero in HOF, then its oxidation state decreases
O.N. of C1 = + 1 + x + 1(–2) + 1 (–1) = 0 to –2. HOF is reduced to H2O and increases to +2
x – 2 = 0 or x = +2 if if HOF gets oxidised to OF2.
Q.3. Justify that the following reactions are redox Therefore, the possible reaction is
reactions : +1 0 −1 +1 −2 +2 −1
(a) CuO(s) + H2(g) ⎯→ Cu(s) + H2O(g) 2H O F ⎯⎯→ H2 O + O F2
(b) Fe2O3(s) + 3CO(g) ⎯→ 2Fe(s) + 3CO2(g) Q.5. Calculate the oxidation number of sulphur,
(c) 4BCl3(g) + 3LiAH4 (s) ⎯→ 2B2H6(g) + chromium and nitrogen in H2SO5, Cr2O72– and
3LiCl(s) + 3AlCl3(s) NO3–. Suggest structure of these compounds.
Count for the fallacy.
(d) 2K(s) + F2(g) ⎯→ 2K F–(s)
+
Ans. (i) H2SO5. By conventional method
(e) 4NH3(g) + 5O2(g) ⎯→ 4NO(g) + 6H2O(g)
+1 x −2
+2 −2 0 0 +1 −2
Ans. (a) Cu O(s) + H2 ( g) ⎯⎯→ Cu(s) + H O( g) H 2 S O5
2
In this case, O.N. of Cu decreases from +2 (in 2(+1) + x + 5 (–2) = 0 or x=+8
CuO) to 0 (in Cu) and that of H increase from This is not possible because S cannot have O.N.
0 (in H2) to +1 (in H2O). Therefore, CuO is more than 6. The fallacy is overcomed if we
reduced to Cu while H2 is oxidised to H2O. calculate its O.N. from its structure as :
Thus, this is a redox reaction. Ο
||
+ 3 −2 +2 −2 0 +4 −2
(b) Fe O + 3CO ⎯⎯→ 2Fe( s) + 3CO H⎯O⎯S⎯O⎯O⎯H
2 3 2 ||
O.N. of Fe decreases from +3 (in Fe2O3) to 0 (in O
Fe) and that of C increases from +2 (in CO) to 2 × (+1) + x + 2(–1) + 3 × (–2) = 0
+4 (in CO2). Therefore, Fe2O3 is reduced while (for H) (for S) (for O—O) (for other
CO is oxidised. Thus, this is a redox reaction. O atom)

+3 −1 +1 +3 −1 −3 +1 +1 −1 or x = + 6
(c) 4 B Cl3 ( s) + 3Li Al H4 ( s) ⎯
→ 2B 2 H 6 ( g) + 3Li Cl( s) (ii) Cr2O72–
+3 −1 2x + 7(–2) = –2
+ 3Al Cl3 (s)
2x = 12 ∴ x=+6
O.N. of B. decreases from +3 (in BCl3) to –3 in This is correct and there is no fallacy.
B2H6 and that of H increases from –1 (in LiAlH4)
(iii) NO3–. By conventional method,
to + 1 (in B2H6). Therefore, BCl3 is reduced and
x + 3(–2) = –1 or x = +5
LiAlH4 is oxidised. Hence, it is a redox reaction.
+1 −1
From the structure,
0 0
(d) 2 K( s) + F2 ( g) ⎯⎯→ 2K + + F − ( s) O
O.N. of K increases from 0 (in K) to +1 (in K+) and O– — N
that of F decreases from 0 in (F2) to – 1 (in F–). O
Hence, K has been oxidised while F2 has been x + 1 (– 1) + 1(– 2) + 1(– 2) = 0 or x = + 5
reduced. Therefore, it is a redox reaction. (for O–) (for = O) (for →O)
−3 +1 0 +2 −2 +1 −2 Hence, there is no fallacy about O.N. of N in
(e) 4 N H ( g) + 5 O ( g) ⎯⎯→ 4N O ( g) + 6H O( g) NO3– as + 5 whether we calculate by
3 2 2
In this case O.N. of N increases from – 3 (in NH3) conventional method or by chemical bonding.
to +2 (in NO) and that of O decreases from 0 Q.6. Write formulas for the following compounds :
(in O2) to – 2 (in H2O). Therefore, NH3 has been (a) Mercury (II) chloride
oxidised while O2 has been reduced. Hence, it (b) Nickel (II) sulphate
is a redox reaction. (c) Tin (IV) oxide
 8/48 MODERN'S abc + OF CHEMISTRY–XI

(d) Thallium (I) sulphate Q. 11. Whenever a reaction between an oxidising agent
(e) Iron (III) sulphate and a reducing agent is carried out, a compound
(f) Chromium (III) oxide of lower oxidation state is formed if the reducing
Ans. (a) HgCl2 (b) NiSO4 (c) SnO2 agent is in excess and a compound of higher
oxidation state is formed if the oxidising agent
(d) Tl2SO4 (e) Fe2(SO4)3 (f) Cr2O3
is in excess. Justify this statement giving three
Q. 7. Suggest a list of the substances where carbon illustrations.
can exhibit oxidation states from – 4 to + 4 and
Ans. (i) C is a reducing agent while O2 is an oxidising
nitrogen from – 3 to + 5.
agent. If excess of C is burnt in a limited supply of
Ans. Refer Solved Example 8. (Page 11). O2, CO is formed in which the oxidation state of C
Q. 8. While sulphur dioxide and hydrogen peroxide is +2. However, if O2 is excess, the initially formed
can act as oxidising as well as reducing agents CO gets oxidised to CO in which the oxidation state
in their reactions, ozone and nitric acid act only of C is +4.
as oxidants. Why ? +2
Ans. Refer HOTS Questions, Q.1 (Page 58). 2C(s) + O2 ( g) ⎯⎯→ 2CO
(excess)
Q. 9. Consider the reactions :
+4
(a) 6CO2(g) + 6H2O(l) ⎯→ C6H12O6(aq) + 6O2(g) C(s) + O2 ( g) ⎯⎯→ CO2
(b) O3(g) + H2O2(l) ⎯→ H2O(l) + 2O2(g) (excess)

Why it is more appropriate to write these (ii) Sodium is a reducing agent while O2 is an
reactions as : oxidising agent. When excess of Na is used, sodium
(a) 6CO2 + 12H2O(l) ⎯→ oxide is formed in which the oxidation state of O is
–2. If however, excess of O2 is used, Na2O2 is formed
C6H12O6(aq) + 6H2O(l) + 6O2(g)
in which the oxidation state of O is –1, which is
(b) O3(g) + H2O2(l) ⎯→ H2O(l) + O2(g) + O2(g) higher than –2.
Also suggest a technique to investigate the
−2
path of the above (a) and (b) redox reactions.
4Na(s) + O2 ( g) ⎯⎯→ 2 Na 2O(s)
Ans. It is believed that the photosynthesis reaction occurs (excess)
in two steps. In the first step, H2O decomposes to −1
give H2 and O2 in the presence of chlorophyll and 2Na(s) + O2 ( g) ⎯⎯→ Na 2O2 ( s)
the H2 produced reduces CO2 to C6H12O6 in the (excess)
second step. During the second step, some H2O (iii) P4 is a reducing agent while Cl2 is an oxidising
molecules are also produced and therefore, the agent. When excess of P4 is used, PCl3 is formed in
reaction occurs as : which the oxidation state of P is +3. However, if
(i) 12H2O (l) ⎯→ 12H2(g) + 6O2 (g) excess of Cl2 is used, then initially formed PCl3
(ii) 6CO2(g) + 12H2(g) ⎯→ C6H12O6 (s) + 6H2O(l) reacts further to form PCl5, in which the oxidation
state of P is +5.
(iii) 6CO2(g) + 12H2O(l) ⎯→
+3
C6H12O6(s) + 6H2O(l) + 6O2(g) P4 (s) + 6Cl2 ⎯⎯→ 4PCl3
Therefore, it is more appropriate to write the reaction (excess)
for photosynthesis as (iii) because it means that 12 +5
molecules of H 2 O are used per molecule of P4 (s) + 10Cl 2 ⎯⎯→ 4PCl5
(excess)
carbohydrate and 6H2O molecules are produced per
molecule of carbohydrate during the process. Q. 12. How do you account for the following obser-
vations ?
(ii) O2 is written two times in the product which
(a) Though alkaline potassium permanganate
suggests that O2 is being obtained from the two
and acidic potassium permanganate both are
reactants as:
used as oxidants, yet in the manufacture of
O3 (g) ⎯→ O2 (g) + O (g)
benzoic acid from toluene we use alcoholic
H2O2 (l) + O (g) ⎯→ H2O (l) + O2(g) potassium permanganate as an oxidant.
O3(g) + H2O2 (l) ⎯→ H2O(l) + O2(g) + O2(g) Why ? Write a balanced redox equation for the
The path of the reaction can be studied by using reaction.
H2O18 in reaction (a) or by using H2O218 or O318 in (b) When concentrated sulphuric acid is added to
reaction (b). an inorganic mixture containing chloride, we get
Q. 10. The compound AgF2 is unstable compound. colourless pungent smelling gas HCl, but if the
However, if formed, the compound acts as a very mixture contains bromide then we get red vapour
strong oxidising agent. Why ? of bromine. Why ?
Ans. In AgF2, oxidation state of Ag is +2 which is very Ans. When conc. H2SO4 is added to an inorganic mixture
containing chloride, a pungent smelling gas HCl is
unstable. Therefore, it readily accepts an electron to
produced because a stronger acid displaces a weaker
form a more stable oxidation state of +1 as
acid from its salt.
Ag2+ + e– ⎯⎯→ Ag+
2NaCl + 2H2SO4 ⎯→ 2NaHSO4 + 2HCl
Therefore, AgF2 if formed will act as a strong
2 HCl + H2SO4 ⎯×→ Cl2 + SO2 + 2H2O
oxidising agent.
REDOX REACTIONS 8/49
Since HCl is a weak reducing agent, it cannot reduce Q. 14. Consider the reactions :
H2SO4 to SO2 and therefore, HCl is not oxidised to 2S2O32–(aq) + I2(s) ⎯→ S4O62–(aq) + 2I–(aq)
chlorine. S2O32–(aq) + 2Br2(l) + 5H2O(l) ⎯→ 2SO42– (aq)
However, if the mixture contains bromide ion, the + 4Br–(aq) + 10H+(aq)
initially produced HBr is a stronger reducing agent. Why does the same reductant, thiosulphate
Therefore, it reduces H2SO4 to SO2 and itself gets react differently with iodine and bromine ?
oxidised to produce red vapour of Br2. Ans. The O.N. of S in S2O32– is +2, in S4O62– it is +2.5
2 NaBr + 2H2SO4 ⎯→ 2NaHSO4 + 2HBr (average) and in SO42– it is +6. Since Br2 is a stronger
2HBr + H2SO4 ⎯→ Br2+ SO2 + 2H2O oxidising agent than I2, it oxidises S of S2O3 2–to
Q. 13. Identify the substance oxidised, reduced, oxidising SO42– (with higher O.N. of +6). However, I2 being a
agent and reducing agent for each of the following weaker oxidising agent oxidises S of S2O32– into a
reactions : lower O.S. of +2.5 in S4O62–. Therefore, S2O32– reacts
(a) 2AgBr(s) + C6H6O2(aq) ⎯→ 2Ag(s) + differently with Br2 and I2.
2HBr(aq) + C6H4O2(aq) Q. 15. Justify giving reactions that among halogens,
(b) HCHO(l) + 2[Ag(NH3)2]+(aq) + 3OH–(aq) ⎯→ fluorine is the best oxidant and among hydrohalic
2Ag(s) + HCOO–(aq) + 4NH3(aq) + 2H2O(l) compounds, hydroiodic acid is the best reductant.
(c) HCHO(l) + 2Cu2+(aq) + 5OH–(aq) ⎯→ Ans. The oxidising power of halogens decreases in the
Cu2O(s) + HCOO–(aq) + 3H2O(l) order : F2 > Cl2 > Br2 > I2. Therefore, F2 can oxidise
(d) N2H4(l) + 2H2O2(l) ⎯→ N2(g) + 4H2O(l) Cl–, Br– and I– to respective Cl2, Br2, I2.
(e) Pb(s) + PbO2(s) + 2H2SO4(aq) ⎯→ F2(g) + 2Cl–(aq) ⎯⎯→ 2F–(aq) + Cl2(g)
2PbSO4(s) + 2H2O(l) F2(g) + 2Br–(aq) ⎯⎯→ 2F–(aq) + Br2(l)
Ans. Reduction F2(g) + 2I–(aq) ⎯⎯→ 2Cl–(aq) + I2(s)
Cl2 can oxidise Br– to Br2 and I– to I2
+1 0 Cl2(g) + 2Br–(aq) ⎯⎯→ 2Cl–(aq) + Br2(l)
2AgBr(s) + C6H6O2(aq) ⎯→ 2Ag(s) + 2HBr(aq) + C6H4O2(aq) 2Cl2(g) + 2I–(aq) ⎯⎯→ 2Cl–(aq) + I2(s)
However, Cl2 cannot oxidise F– to F2.
Oxidation Br2 can oxidise only I– (aq) to I2 and not F– or Cl–
AgBr : reduced, C6H6O2 (aq) : oxidised to F2 or Cl2.
AgBr : Oxidising agent, C6H6O2 (aq) : reducing agent Br2(l) + 2I–(aq) ⎯⎯→ 2Br–(aq) + I2(s)
Reduction Thus, F2 is the best oxidant.
Among hydrohalic acids, the reducing power
decreases as : HI > HBr > HCl > HF. For example,
(b) HCHO(l) + 2[Ag(NH3)2]+(aq) + 3OH– ⎯→ 2Ag(s)
HI and HBr reduce H2SO4 to SO2 while HCl and HF
+ HCOO– (aq) + 4NH3(aq) + 2H2O(l)
donot.
Oxidation 2HBr + H2SO4 ⎯⎯→ Br2 + SO2 + 2H2O
[Ag(NH3)2]+ (aq) : reduced, HCHO(l) : oxidised 2HI + H2SO4 ⎯⎯→ I2 + SO2 + 2H2O
[Ag(NH3)2]+ (aq) : oxidising agent, HCHO(l) : reducing Similarly, I– reduces Cu2+ to Cu+ but Br– does not.
agent 2Cu2+ (aq) + 4I– (aq) ⎯⎯→ Cu2I2 (s) + I2(aq)
Reduction Further among HCl and HF, HCl is a stronger
reducing agent than HF because HCl can reduce
(c) HCHO(l) + 2Cu2+(aq) + 5OH–(aq) → Cu2O(s) + HCOO–(aq) MnO2 to Mn2+.
+ 3H2O MnO2(s) + 4HCl (aq) ⎯→ MnCl2(aq) + Cl2(g) + 2H2O
But HF does not reduce MnO2. Therefore, among
Oxidation
hydrohalic acid HI is the strongest reducing agent.
Cu2+ (aq) : reduced, HCHO(l) : oxidised
Cu2+ (aq) : oxidising agent, HCHO(l) : reducing agent Q. 16. Why does the following reaction occur ?
Reduction XeO64– (aq) + 2F–(aq) + 6H+(aq) ⎯→ XeO3(g) +
F2(g) + 3H2O(l)
(d) N2H4(l) + 2H2O2(l) ⎯→ N2(g) + 4H2O(l) What conclusion about the compound Na4XeO6
(of which XeO64– is a part) can be drawn from
the reaction?
Oxidation
+8 −1
H2O2 : reduced, N2H4(l) : oxidised
Ans. Xe O6 4 − ( aq) + 2F − (aq) + 6H + (aq) ⎯⎯→
H2O2 : oxidising agent, N2H4(l) : reducing agent
Reduction +6 0
Xe O3 ( s) + F2 ( g) + 3H 2O(l)
0 +4 +2 O.N. of Xe decreases from +8 (in XeO64–) to +6 (in
(e) Pb(s) + PbO2(s) + 2H2SO4(aq) ⎯→ 2PbSO4(s) + 2H2O(l) XeO3) and that of F increases from –1 (in F–) to 0
(in F2). Therefore, XeO64– is reduced while F– is
Oxidation oxidised. The reaction occurs because Na4XeO6 (or
PbO2 : reduced Pb(s) : oxidised XeO64–) is a stronger oxidising agent than F2.
PbO2 (s) : oxidising agent, Pb(s) : reducing agent
 8/50 MODERN'S abc + OF CHEMISTRY–XI

Q. 17. Consider the reactions : SO2(g) + 2H2O(l) ⎯⎯→ HSO4– (aq) + 3H+ + 2e–
(a) H3PO2(aq) + 4AgNO3(aq) + H2O(l) ⎯→ To balance reduction half reaction.
H3PO4(aq) + 4Ag(s) + 4HNO3(aq) MnO4– (aq) ⎯⎯→ Mn2+ (aq)
(b) H3PO2(aq) + 2CuSO4(aq) + H2O(l) ⎯→ (i) Balance all atoms other than H and O (already
H3PO4(aq) + 2Cu(s) + H2SO4(aq) done).
(c) C6H5CHO(l) + 2[Ag(NH3)2](aq) + 3OH–(aq) (ii) Manganese changes its oxidation number from
⎯→ C6H5COO–(aq) + 2Ag(s) + 7 to + 2 and there is difference of 5 electrons. To
+ 4NH3(aq) + 2H2O(l) balance the electrons,
(d) C6H5CHO(l) + 2Cu2+(aq) + 5OH–(aq) ⎯→ MnO4– (aq) + 5e– ⎯⎯→ Mn2+ (aq)
No change observed. (iii) Since the reaction takes place in acidic medium
What inference do you draw about the add 8H+ on the left to equate the net charges on both
behaviour of Ag+ and Cu2+ from these ? sides and 4 H2O to the right to balance oxygen atoms.
Ans. Reaction (a) and (b) infer that H 3 PO 2 MnO4– + 8 H+ + 5e– ⎯⎯→ Mn2+
(hypophosphorus acid) is a reducing agent and MnO–4 + 8H+ + 5e– ⎯⎯→ Mn2+ + 4H2O
reduces both AgNO3 and CuSO4 to Ag and Cu Adding two half reactions by equating the number
respectively. This also means that both AgNO3 and of electrons.
CuSO4 act as oxidising agent and oxidise H3PO2 to MnO4– (aq) + 8H+ + 5e– ⎯⎯→ Mn2+(aq) + 4H2O(l)] × 2
H3PO4 (phosphoric acid). SO2(g) + 2H2O ⎯⎯→ HSO4– (aq) + 3H+(aq) + 2e–] × 5
Reaction (c) indicate that [Ag(NH3)2]+ oxidises
C6H5CHO (benzaldehyde) to C6H5COO– (benzoate 2MnO–4 (aq) + 5SO2(g) + 2H2O(l) + H+(aq) ⎯→ 2Mn2+(aq)
ion) but reaction (d) indicates that Cu2+ ions cannot + 5 HSO4– (aq)
oxidise C6H5CHO to C6H5COO–. Thus, we can infer +2
--- 1 +3 −2
2+
from the above reactions that Ag+ ion is a stronger (c) H2 O 2 (aq ) + Fe (aq ) ⎯⎯→ Fe3 + ( aq) + H2 O(l)
oxidising agent than Cu2+ ion.
in acidic medium.
Q. 18. Balance the following redox reactions by ion
– electron method : In this reaction, the oxidation number of Fe increases
from + 2 (in Fe2+) to +3 (in Fe3+) and therefore, Fe2+
(a) MnO4–(aq) + I–(aq) ⎯→ MnO2(s) + I2(s)
has been oxidised. The oxidation number of oxygen
(in basic medium)
has decreased from –1 (in H2O2) to – 2 in H2O and
(b) MnO4–(aq) + SO2(g) ⎯→
therefore, H2O2 has been reduced.
Mn2+(aq) + HSO4–(aq)
Oxidation half reaction : Fe2+(aq) ⎯⎯→ Fe3+(aq)
(in acidic solution)
Reduction half reaction : H2O2(aq) ⎯⎯→ H2O(aq)
(c) H2O2(aq) + Fe2+(aq) ⎯→ Fe3+(aq) + H2O(l)
These can be balanced by following the steps of
(in acidic solution)
balancing as :
(d) Cr2O72– + SO2(g) ⎯→ Cr3+(aq) + SO42–(aq)
Oxidation half reaction :
(in acidic solution)
Fe2+(aq) ⎯⎯→ Fe3+(aq)
Ans. (a) Refer Solved Example 30. (Page 27).
Fe2+(aq) ⎯⎯→ Fe3+(aq) + e– ...(i)
+7 +4 +2 +6
(b) M nO4 − (aq) + SO2 ( g) ⎯→ Mn 2+ ( aq) + HSO4− (aq)
Reduction half reaction
H2O2(aq) ⎯⎯→ H2O(l)
In this reaction, manganese undergoes reduction
H2O2(aq) + e– ⎯⎯→ H2O(l)
because oxidation number of Mn decreases from
H2O2(aq) + 2H+ (aq) + 2e– ⎯⎯→ 2H2O(l) ...(ii)
+7(in MnO–4) to +2 (in Mn2+). SO2 gets oxidised
because oxidation number of sulphur increases from Multiply eq (i) by 2 and add it to eq. (ii) to balance
+ 4 (in SO2) to + 6 in (HSO4–). electrons.
Oxidation half reaction : SO2(g) ⎯⎯→ HSO4– (aq) H2O2(aq) + 2Fe2+ (aq) + 2H+ ⎯⎯→ 2Fe3+ (aq) + 2H2O(l)
Reduction half reaction : MnO4–(aq) ⎯⎯→ Mn2+(aq) +6 +4 +3 +6
(d)Cr 2 O72− (aq) + S O2 ( g) ⎯→ Cr3+ (aq) + S O42− (aq)
Balancing each half reaction separately as :
SO2(g) ⎯⎯→ HSO4– (aq) (in acidic medium)
(i) Balance all atoms other than H and O (already Oxidation half reaction : SO2(g) ⎯⎯→ SO42– (aq)
done). Reduction half reaction : Cr2O72– (aq) ⎯⎯→ Cr3+(aq)
(ii) Sulphur changes its oxidation number from + 4 Balancing the oxidation and reduction half reactions
to + 6 and there is a difference of 2 electrons. To separately following the steps of balancing.
balance the electrons,
Oxidation half reaction :
SO2(g) ⎯⎯→ HSO4– (aq) + 2e–
SO2(g) ⎯⎯→ SO42– (aq)
(iii) Since the reaction takes place in acidic medium
SO2(g) ⎯⎯→ SO42– (aq) + 2e–
add 3H+ on the right hand side and two H2O
molecules on the left hand side. SO2(g) + 2H2O(l) ⎯⎯→ SO42– + 2e– + 4H+(aq) ...(i)
REDOX REACTIONS 8/51

Reduction half reaction : Reduction half reaction

Cr2O72– (aq) ⎯⎯→ Cr3+(aq) 0 −3
P4 ⎯⎯→ P H ( g)
Cr2O72– ⎯⎯→ 2Cr3+ (aq) 3

Cr2O72– (aq) + 6e– ⎯⎯→ 2Cr3+ (aq) P4(s) ⎯⎯→ 4PH3(g)

Cr2O7 (aq) + 6e– + 14 H+(aq) ⎯⎯→ 2Cr3+(aq)
2– P4(s) + 12e– ⎯⎯→ 4PH3(g)
Cr2O72–(aq) + 6e– + 14H+(aq) ⎯⎯→ 2Cr3+(aq) P4(s) + 12e– ⎯⎯→ 4PH3(g) + 12 OH– (aq)
+ 7H2O...(ii) P4(s) + 12H2O (l) + 12e– ⎯⎯→ 4PH3(g) + 12 OH– (aq)
Multiply eq. (i) by 3 and add it to eq (ii) to balance ...(ii)
electrons : To balance electrons, multiply eq. (i) by 3 and add
Cr2O72– (aq) + 3SO2(g) + 2H+(aq) ⎯⎯→ 2Cr3+ (aq) to eq. (ii).
+ 3SO42– (aq) + H2O 4P4(s) + 12OH– (aq) + 12H2O(l) ⎯⎯→ 4PH3(g)
Q. 19. Balance the following equations in basic medium + 12 H2PO2– (aq)
by ion-electron method and oxidation number or P4(s) + 3OH (aq) + 3H2O(l) ⎯⎯→ PH3(g)
–

methods and identify the oxidising agent and the + 3H2PO2– (aq)
reducing agent.
Oxidation
(a) P4(s) + OH–(aq) ⎯→ PH3(g) + H2PO2–(aq)
(b) N2H4(l) + ClO3–(aq) ⎯→ NO(g) + Cl–(g) –2 +5
–
+2 –1
–
(b) N2 H4(l) + ClO3 (aq) ⎯⎯ → NO(g) + Cl (g)
(c) Cl2O7(g) + H2O2(aq) ⎯→ ClO2–(aq) + O2(g)
+ H+
Reduction Reduction

0 –3+1 +1 In this reaction, N2H4 gets oxidised and acts as a

Ans. (a) P4 (s) + OH–(aq) ⎯⎯ → PH (g) + H2PO– reducing agent and ClO3– gets reduced and acts as
3 2
an oxidising agent.
Oxidation
Oxidation number method
P4 gets oxidised to H2PO2– and reduced to PH3 and
therefore, P4 acts as reducing agent as well as O.N. increases by 4 per N atom
oxidising agent. or 4 × 2 per N2 H 4 molecule
–2 +5 –2 –1
Oxidation number method –
N2 H4(l) + ClO 3– (aq) ⎯⎯ → NO(g) + Cl (aq)
O.N. decreases by 3 per atom
or 3 × 4 per P4 molecule O.N. decreases by 6 per Cl atom
0 –3+1 +1
–
P4 (s) + OH (aq) ⎯⎯ → PH3 (g) + H2PO2– (aq) To balance the increase or decrease in oxidation
O.N. increases by 1 per atom number, multiply N2H4 by 3 and ClO–3 by 4 and add
or 1 × 4 per P4 molecule 3N2H4(l) + 4ClO3– (aq) ⎯⎯→ NO(g) + Cl– (aq)
Balance the increase or decrease in oxidation number Balance N and Cl atoms on R.H.S.
by multiplying H2PO–2 by 3 and PH3 by 1. 3N2H4(l) + 4ClO3– (aq) ⎯⎯→ 6NO(g) + 4Cl–(aq)
P4(s) + OH– (aq) ⎯⎯→ PH3(g) + 3H2PO2– (aq) To balance O atoms add 6H2O molecules on R.H.S.
To balance O atoms, multiply OH– by 6, 3N2H4(l) + 4ClO3– (aq) ⎯⎯→ 6NO(g)+ 4Cl– (aq) + 6H2O
P4(s) + 6OH–(aq) ⎯⎯→ PH3(g) + 3H2PO2– (aq) Since H atoms are balanced automatically, the above
To balance H atoms, add 3 H2O to L.H.S. and 3OH– equation represents balanced chemical equation.
on R.H.S, we have Ion electron method
P4(s) + 6OH– (aq) + 3H2O(l) ⎯⎯→ PH3(g) + Oxidation half reaction : N2H4(l) ⎯⎯→ NO(g)
3H2PO2– (aq) + 3OH–(aq) Reduction half reaction : ClO3– (aq) ⎯⎯→ Cl–(aq)
–
or P4(s) + 3OH (aq) + 3H2O(l) ⎯⎯→ PH3(g) + These can be balanced separately as :
3H2PO2–(aq) Oxidation half reaction :
Ion electron method N2H4(l) ⎯⎯→ NO(g)
The equation can be split up as N2H4(l) ⎯⎯→ 2NO(g)
Oxidation half reaction : P4(s) ⎯⎯→ H2PO2–(aq) −2 +2
Reduction half reaction : P4(s) ⎯⎯→ PH3(g) N2 H4 (l) ⎯⎯→ 2 NO( g) + 8e−
These can be balanced separately as : N2H4(l) + 8OH– (aq) ⎯⎯→ 2NO(g) + 8e–
Oxidation half reaction (balancing OH– ions)
0 +1
P4 (s) ⎯⎯→ H2 P O2 − (aq) N2H4(l) + 8OH–(aq) ⎯⎯→ 2NO(g) + 6H2O(l) + 8e–
...(i)
P4(s) ⎯⎯→ 4H2PO2– (aq)
Reduction half reaction
P4(s) ⎯⎯→ 4H2PO2– (aq) + 4e–
ClO–3 (aq) ⎯⎯→ Cl– (aq)
P4(s) + 8OH–(aq) ⎯⎯→ 4H2PO2– (aq) + 4e– ...(i)
 8/52 MODERN'S abc + OF CHEMISTRY–XI

+5 −1 Q. 20. What sorts of informations can you draw from

C lO3− + 6 e− ⎯⎯→ Cl − (aq)
the following reaction ?
ClO–3 (aq) + 6e– ⎯⎯→ Cl– (aq) + 6OH–(aq) (CN)2(g) + 2OH–(aq) ⎯→ CN–(aq) + CNO–(aq) +
ClO–3 (aq) + 3H2O(l) + 6e– ⎯⎯→ Cl– (aq) + 6 OH–(aq) H2O(l)
...(ii) Ans. (i) It is a disproportionation reaction.
To balance electrons, multiply eq (i) by 3 and eq (ii) (ii) The reaction occurs in basic medium.
by 4 (iii) O.N. of N in (CN)2 is –3 and that in CN– is
3N2H4(l) + 4ClO–3(aq) ⎯⎯→ 6NO(g) + 4 Cl–(aq) + 6H2O(l) –2 and in CNO– it is –5.
Reduction
(iv) Cyanogen, (CN)2 gets simultaneously reduced
+7 –1 +3 0
to CN– ion as well as oxidised to cyanate,
+ CNO– ion.
(c) Cl2 O7 (g) + H 2O2 (aq) ⎯⎯ → ClO–2 (aq) + O2 (g) + H
Q. 21. The Mn3+ ion is unstable in solution and
Oxidation undergoes disproportionation to give Mn2+, MnO2,
In this reaction, Cl2O7 gets reduced and acts as an and H+ ion. Write a balanced ionic equation for
oxidising agent while H2O2 gets oxidised and acts the reaction.
as a reducing agent.
Ans. The reaction may be written as :
Oxidation number method
Mn3+(aq) ⎯→ Mn2+(aq) + MnO2(s) + H+(aq)
O.N. decreases by 4 per atom
This may be balanced as :
or 4 × 2 per molecule
+7 –1 +3 0 Oxidation half equation :
Cl2 O7 (g) + H 2O2 (aq) ⎯⎯ → ClO–2 (aq) + O2 (g) 3+ +4
O.N. increases by 1 per atom Mn3+ (aq) ⎯⎯→ Mn O2 (s)
or 1 × 2 per molecule Balance O.N. by adding electrons
To balance the increase or decrease in oxidation +4
number, multiply H2O2 by 4 and add Mn 3+ (aq) ⎯⎯→ Mn O2 ( s) + e−
Cl2O7(g) + 4 H2O2 (aq) ⎯⎯→ ClO2– (aq) + O2(g) Balance charge by adding H+ ions
Balance Cl atoms and O2 Mn3+ (aq) ⎯⎯→ MnO2(s) + 4H+ + e–
Cl2O7 (g) + 4H2O2(aq) ⎯⎯→ ClO2– (aq) + 4O2(g) Balance O atoms by adding H2O
To balance Cl multiply ClO–2 by 2. Mn3+(aq) + 2H2O(l) ⎯→ MnO2(s) + 4H+ (aq) + e–
Cl2O7 (g) + 4H2O2(aq) ⎯⎯→ 2ClO2– (aq) + 4O2(g) .....(i)
To balance O atoms, add 3H2O molecules on R.H.S. Reduction half equation
Cl2O7(g) + 4H2O2 (aq) ⎯⎯→ 2ClO2– (aq) + 4O2(g) Mn3+(aq) ⎯⎯→ Mn2+(aq)
+ 3H2O(l) Balancing O.N. by adding electrons.
To balance H atoms, add 2H+ on R.H.S. since the Mn3+(aq) + e– ⎯⎯→ Μn2+(aq) .....(ii)
medium is acidic Adding eq. (i) and eq. (ii)
Cl2O7(g) + 4 H2O2 (aq) ⎯⎯→ 2ClO2– (aq) + 4O2(g) 2Mn3+ (aq) + 2H2O(l) ⎯⎯→
+ 3H2O(l) + 2H+(aq) MnO2(s) + Mn2+(aq) + 4H+(aq)
Ion electron method Q. 22. Consider the elements :
−1 0 Cs, Ne, I and F
Oxidation half reaction : H2 O2 (aq) ⎯⎯⎯ O 2 (g) (a) Identify the element that exhibits only
Reduction half reaction : Cl2O7(g) ⎯⎯→ ClO3– (aq) negative oxidation state.
These can be balanced separately as : (b) Identify the element that exhibits only positive
Oxidation half reaction oxidation state.
−1 (c) Identify the element that exhibits neither the
H 2 O2 (aq) ⎯⎯→ O2(g) negative nor does the positive oxidation
−1 state.
H2 O2 (aq) ⎯⎯→ O2(g) + 2e– Ans. (a) F : being most electronegative; shows only a –ve
Since the reaction occurs in acidic medium add 2H+ oxidation state of –1.
on R.H.S. to equate charge, (b) Cs : Alkali metals have only one electron in their
H2O2(aq) ⎯⎯→ O2(g) + 2e– + 2H+ (aq) ...(i) valence shell and hence exhibits only +1 oxidation
Reduction half reaction state.
Cl2O7(g) ⎯⎯→ ClO2– (aq) (c) I : because of the presence of 7 electrons in its
Cl2O7(g) ⎯⎯→ 2ClO2– (aq) valence shell, I shows O.S of –1 (to have stable
Cl2O7(g) + 8e– ⎯⎯→ 2ClO2– (aq) noble gas configuration) and +ve oxidation states
Cl2O7(g) + 8e– + 6H+(aq) ⎯⎯→ 2ClO2– (aq) of +1, +3, +5 and +7 because of the presence of
d-orbitals.
(medium is acidic)
Cl2O7(g) + 6H+(aq) + 8e– ⎯⎯→ 2ClO2– (aq) + 3H2O ...(iii) (d) Ne : It is an inert gas and therefore, does not
exhibit –ve or +ve O.S.
To balance electrons, multiply eq. (i) by 4 and add
to eq (ii) Q. 23. Chlorine is used to purify drinking water.
Cl2O7(g) + 4 H2O2 (aq) ⎯⎯→ 2ClO–2 (aq) + 4O2(g) Excess of chlorine is harmful. The excess of
+ 3H2O(l) + 2H+ (aq) chlorine is removed by treating with sulphur
REDOX REACTIONS 8/53

dioxide. Present a balanced equation for this ∴ O2 is a limiting reagent.

redox change taking place in water. 160 g of O2 produces NO = 120 g
Ans. The skeletal equation is : 120
Cl2(g) + SO2(aq) + H2O(l) ⎯→ Cl–(aq) + SO42–(aq) 20 g of O2 will produces NO = × 20
160
Reduction half equation : = 15 g
Cl2(aq) ⎯→ Cl–(aq) Q. 26. Using the standard electrode potentials given in
Balancing Cl atoms the Table 8.1, predict if the reaction between the
Cl2(aq) ⎯→ 2Cl–(aq) following is feasible :
Balancing O.N. by adding electrons : (a) Fe3+(aq) and I–(aq)
0 (b) Ag+(aq) and Cu(s)
Cl2(aq) + 2e– ⎯→ 2Cl–(aq) ....(i) (c) Fe3+ (aq) and Cu(s)
Oxidation half equation : (d) Ag(s) and Fe3+(aq)
SO2(aq) ⎯→ SO42– (aq) (e) Br2(aq) and Fe2+(aq).
Balancing O.N. by adding electrons Ans. (a) It is clear from the table that electrode potential
+4 +6 Fe3+ | Fe (0.77V) is more than that of I2 | I– (0.54V),
SO2(aq) ⎯→ SO42– (aq) + 2e– therefore, Fe3+ will be readily reduced and the
Balancing charge by adding H+ ions following reaction is feasible.
1
SO2(aq) ⎯→ SO42– (aq) + 2e– + 4H+(aq) Fe3+(aq) + I– (aq) ⎯→ Fe2+(aq) + I2(s)
Balancing O atoms by adding H2O 2
(b) The electrode potential of Ag+ | Ag (0.80V) is
SO2(aq) + 2H2O(l) ⎯→ SO42– (aq) + 2e– + 4H+(aq) more than that of Cu2+ | Cu (0.34V) and therefore,
....(ii) Ag+ will be reduced by copper. The following reaction
Adding equations (i) and (ii) we get is feasible.
Cl2(aq) + SO2(aq) + 2H2O(l) ⎯→ 2Ag+(aq) + Cu (s) ⎯→ 2Ag(s) + Cu2+(aq)
2Cl–(aq) + SO42–(aq) + 4H+(aq) (c) The electrode potential of Fe3+ | Fe (0.77V) is
Q. 24. Refer to the periodic table given in your book and more than that of Cu2+ | Cu (0.34V), therefore, Fe3+
now answer the following questions : can be reduced . The following reaction is feasible.
(a) Select the possible non-metals that can show Fe3+(aq) + Cu (s) ⎯→ Fe2+(aq) + Cu2+(aq)
disproportionation reaction. (d) The electrode potential of Ag | Ag+ (0.80V) is
(b) Select three metals that can show more than that of Fe3+ | Fe (0.77V) and therefore,
disproportionation reaction. Ag+ will not be reduced by Fe3+. Therefore, the
Ans. (a) Non-metals showing disproportionation reactions reaction will not be feasible.
are : P4, Cl2 and S8 Ag(s) + Fe3+ (aq) ⎯→ 2Ag(aq) + Fe2+(aq)
0 –3 +3 (e) The electrode potential of Br | Br– (1.09V) is more
P4(s) + 3OH–(aq) + 3H2O(l) ⎯→ PH3(g) + 3H2PO2– (aq) than that of Fe3+ | Fe2+ (0.77V) and therefore, Br will
0 –1 +1 be able to reduce by Fe3+. Therefore, the following
Cl2(aq) + 2OH–(aq) ⎯→ Cl–(aq) + ClO– (aq) + H2O(l) reaction is feasible.
0 –2 +2 1
S8(s) + 12OH–(aq) ⎯→ S(aq) + 2S2O32– + 6H2O(l) Br (aq) + Fe2+ (aq) ⎯→ Br–(aq) + Fe3+(aq)
2 2
(b) Metals exhibiting disproportionation reactions Q. 27. Predict the products of electrolysis in each of the
are : following :
Cu+, Ga+ In+ (i) An aqueous solution of AgNO3 with silver
+1 +2 0 electrodes
2Cu+(aq) ⎯→ Cu2+(aq) + Cu(s) (ii) An aqueous solution of AgNO3 with platinum
+1 +3 0 electrodes
3Ga+(aq) ⎯→ Ga3+(aq) + 2Ga(s) (iii) An aqueous solution of H2SO4 with platinum
+1 +3 0
electrodes
3In+(aq) ⎯→ In3+(aq) + 2In(s)
(iv) An aqueous solution of CuCl2 with platinum
Q. 25. In Ostwald’s process for the manufacture of nitric
electrodes
acid, the first step involves the oxidation of
Ans. (i) Electrolysis of aqueous solution of AgNO3 using
ammonia gas by oxygen gas to give nitric oxide
silver electrodes :
gas and steam. What is the maximum weight of
nitric oxide that can be obtained starting only AgNO3(s) +nH2O ⎯→ Ag+ (aq) + NO3– (aq)
with 10.00 g. of ammonia and 20.00 g of oxygen 
H2O  

 H+ + OH–
? At cathode : Ag+ ions have lower discharge potential
Ans. 4NH3(g) + 5O2(g) ⎯→ 4NO(g) + 6H2O(g) than H+ ions.
4 × 17 5 × 32 4 × 30 Hence Ag+ ions will be deposited as silver (in
= 68 g = 160 g = 120 g preference to H+ ions).
160 g of O2 will react with 68 g of NH3 At anode : Since silver electrode is attacked by
68 NO3– ions, Ag anode will dissolve to form Ag+ ions
20 g of O2 will react with NH3 = × 20 in the solution.
160
= 8.5 g Ag ⎯→ Ag+ + e–
 8/54 MODERN'S abc + OF CHEMISTRY–XI

(ii) Electrolysis of aqueous solution of AgNO3 using Thus copper will be deposited on the cathode and Cl2
platinum electrodes : will be liberated at anode.
At cathode : same as above. Q. 28. Arrange the following metals in the order in
At anode : Since silver is not attackable, out of OH– which they displace each other from the
and NO3– ions, OH– ions have lower discharge potential solution of their salts.
and hence OH– ions will be discharged in preference Al, Cu, Fe, Mg and Zn.
to NO3–. The OH– will decompose to give O2. Ans. Mg, Al, Zn, Fe, Cu
OH–(aq) ⎯→ OH + e– Q. 29. Given the standard electrode potentials,
4OH–(aq) ⎯→ 2H2O(l) + O2(g) K+ | K = –2.93V, Ag+ | Ag = 0.80V,
(iii) Electrolysis of H2SO4 with Pt electrodes : Hg2+ | Hg = 0.79 V
Mg2+ | Mg = –2.37V, Cr3+ | Cr = –0.74V
H2SO4 (aq) ⎯→ 2H+(aq) + SO42–(aq)
arrange these metals in their increasing order
H2O 
 H+ + OH– of reducing power.
At cathode : H + e ⎯→H
+ –
Ans. Ag+ | Ag, Hg2+ | Hg, Cr3+ | Cr, Mg2+ | Mg, K+ | K
H + H ⎯→ H2(g) Q. 30. Depict the galvanic cell in which the reaction
At anode : OH– ⎯→ OH + e– Zn(s) + 2Ag+(aq) ⎯→ Zn2+ (aq) + 2Ag(s) takes
4OH ⎯→ 2H2O + O2(g) place. Further show :
(iv) Electrolysis of aqueous solution of CuCl2 with (i) which of the electrode is negatively charged,
platinum electrodes : (ii) the carriers of the current in the cell, and
CuCl2 (s) + (aq) ⎯→ Cu2+(aq) + 2Cl–(aq) (iii) individual reaction at each electrode.
H2O  Ans. The cell may be depicted similar to Fig. 8.3. The cell
 H+ + OH– may be represented as
2+
At cathode : Cu will be reduced in preference to
Zn(s) | Zn2+ (aq) || Ag+(aq) | Ag(s)
H+ ions.
(i) Zinc electrode (anode)
Cu2+ + 2e– ⎯→ Cu
(ii) Current will flow from silver to zinc in the
At anode : Cl– ions will be oxidised in preference external circuit.
to OH– ions (iii) At anode : Zn (s) ⎯→ Zn2+(aq) + 2e–
Cl– ⎯→ Cl + e–
At cathode : Ag+ (aq) + e– ⎯→ Ag(s)
Cl + Cl ⎯→ Cl2

NCERT Exemplar Problems

Note:
Objective Questions from Exemplar Problems are Subjective Questions
given in Competition File, page 72

Short Answer Questions Carrying 2 or 3 marks

3MnO42– + 4H+ ⎯⎯ → 2MnO4– + MnO2 + 2H2O
Q. 1. The reaction Cl2(g) + 2OH–(aq) → ClO–(aq) +
Cl–(aq) + H2O(l) represents the process of Here O.N. of Mn increases from +6 (in MnO42–) to +7 (in
bleaching. Identify and name the species that MnO4–) and decreases to +4(in MnO2).
bleaches the substances due to its oxidising Q. 3. PbO and PbO2 react with HCl according to
action. following chemical equations :
Ans. 0 –2 +1 +1 –2 –1 +1 –2 2PbO + 4HCl ⎯ → 2PbCl2 + 2H2O
Cl2(g) + 2OH (aq) ⎯→ Cl O (aq) + Cl (aq) + H2O(l)
– – –
PbO2 + 4HCl ⎯ → PbCl2 + Cl2 + 2H2O
In this reaction, O.N. of Cl increases from 0 (in Cl2) Why do these compounds differ in their
to +1(in ClO–) and decreases to –1(in Cl–). Therefore, reactivity ?
Cl2 is both oxidised to ClO– and reduced to Cl–. +2 +2
Since Cl– ion cannot act as an oxidising agent
Ans. (i) 2PbO + 4HCl ⎯→ 2PbCl2 + 2H2O
(because it cannot decrease its O.N. lower than
–1), therefore, Cl 2 bleaches substances due to +4 +2 0
oxidising action of hypochlorite, ClO–, ion. PbO2 + 4HCl ⎯→ PbCl2 + Cl2 + 2H2O
Q. 2. MnO42– undergoes disproportionation reaction In reaction (i), O.N. of none of the atoms undergo a
in acidic medium but MnO4– does not. Give change. Therefore, it is not a redox reaction. It is an
reason. acid-base reaction, because PbO2 is a basic oxide
Ans. In MnO4–, Mn is in the highest oxidation state (+7). which reacts with HCl acid.
Therefore, it cannot be oxidised further and hence does The reaction (ii) is a redox reaction in which PbO2
not undergo disproportionation. However, in MnO42–, gets reduced and acts as an oxidising agent.
Mn is in +6 oxidation state. Therefore, it can increase Q. 4. Nitric acid is an oxidising agent and reacts with
its O.N to + 7 and decrease its O.N. to some lower value. PbO but it does not react with PbO2. Explain
Thus, it undergoes disproportionation as : why ?
REDOX REACTIONS 8/55

Ans. PbO is a basic oxide and therefore, it reacts with nitric (ii) I2 + NO3− ⎯→ NO2 + IO3−
acid. It is a simple acid-base reaction between PbO
and HNO3. (iii) I2 + S 2O3 2 − ⎯→ I– + S 4O6 2 −
2PbO + 4HNO3 ⎯→ 2Pb(NO3)2 + 2H2O (iv) MnO2 + C2O42 − ⎯→ Mn2+ + CO2
(Acid-base reaction) Ans. Try yourself. Balanced equations are
On the other hand in PbO2, lead is in +4 oxidation state
(i) 6Fe2+ + Cr2O72− + 14H+ ⎯→
and cannot be oxidised further. Therefore
PbO2 is passive towards HNO3 and no reaction takes 2Cr3+ + 6Fe3+ + 7H2O
place. (ii) I2 + 10NO3− + 8H+ ⎯→ 10NO2 + 2IO3− + 4H2O
Q. 5. Write balanced chemical equations for the
(iii) I2 + 2S2O32− ⎯→ 2I– + S4O62−
following reactions :
(i) Permanganate ion (MnO4− ) reacts with (iv) MnO2 + C2O24− + 4H+ ⎯→ Mn2+ + 2CO2 + 2H2O
sulphur dioxide gas in acidic medium to Q. 9. Identify the redox reactions out of the
produce Mn2+ and hydrogen sulphate ion. following reactions and identify the oxidising
(Balance by ion electron method) and reducing agents in them.
(ii) Reaction of liquid hydrazine (N2H4) with (i) 3HCl(aq) + HNO3(aq) ⎯→
chlorate ion (ClO3− ) in basic medium Cl2(g) + NOCl(g) + 2H2O(l)
(ii) HgCl2(aq) + 2KI(aq) ⎯→ HgI2(s) + 2KCl(aq)
produces nitric oxide gas and chloride ion
in gaseous state. (Balance by oxidation (iii) Fe2O3(s) + 3CO(g) ⎯⎯ Δ
→ 2Fe(s) + 3CO2(g)
number method) (iv) PCl3(l) + 3H2O(l) ⎯→ 3HCl(aq) + H3PO3(aq)
(iii) Dichlorine heptaoxide (Cl2O7) in gaseous (v) 4NH3 + 3O2(g) ⎯→ 2N2(g) + 6H2O(g)
state combines with an aqueous solution Ans. (i) Writing the O.N. of on each atom,
of hydrogen peroxide in acidic medium +1 –1 +1 +5 –2
to give chlorite ion (ClO−2 ) and oxygen 3HCl(aq) + H N O3(aq) ⎯→
gas. (Balance by ion electron method) 0 +3 –2 –1 +1 –2
Ans. (i) MnO4–(aq) + SO2(g) ⎯→ Mn2+(aq) + HSO4–(aq) Cl2(g) + N O Cl(g) + 2H2O(l)
in acidic medium Here, O.N. of Cl increases from –1 (in HCl) to
0 (in Cl2). Therefore, Cl– is oxidised and hence
Refer NCERT Textbook Exercises Q. 18(b). HCl acts as a reducing agent.
(ii) N2H4(l) + ClO3–(aq) ⎯→ NO(g) + Cl–(aq) The O.N. of N decreases from + 5 (in HNO3) to
Refer NCERT Textbook Exercises Q. 19(b). +3 (in NOCl) and therefore, HNO3 acts as an
(iii) Cl2O7(g) + H2O2(aq) ⎯→ ClO2–(aq) + O2(g) + H+ oxidising agent.
Refer NCERT TextBook Exercises Q. 19(c). Thus, reaction (i) is a redox reaction.
Q. 6. Calculate the oxidation number of phosphorus +2 –1 +1 –1 +2 –1 +1 –1
in the following species. (ii) HgCl2(aq) + 2K I(aq) ⎯→ Hg I2(s) + 2K Cl(aq)
(a) HPO32 − and (b) PO34− Here O.N. of none of the atoms undergo a change
Ans. (a) Let O.N. of P be x and therefore, this is not a redox reaction.
H P O32− +3 –2 +2 –2 0 +4 –2
Δ
(iii) Fe2O3(s) + 3CO(g) ⎯⎯
+1 +x +3(–2) = – 2 or x = +3 → 2Fe(s) + 3CO2(g)
(b) P O43− Here, O.N. of Fe decreases from +3 (in Fe2O3) to
x +4(–2) = – 3 or x = +5 0 (in Fe) and therefore, Fe2O3 acts as an oxidising
Q. 7. Calculate the oxidation number of each agent.
sulphur atom in the following compounds : O.N. of C increases from +2 (in CO) to +4 (in
(a) Na2S2O3 (b) Na2S4O6 CO2) and therefore, CO acts as a reducing agent.
(c) Na2SO3 (d) Na2SO4 Thus, this is a redox reaction.
Ans. Let O.N. of S be x +3 – 1 +1 –2 +1 –1 +1 +3 –2
(a) Na2 S2 O3 (iv) PCl3(l) + 3H2O(l) ⎯→ 3HCl(aq) + H3 P O3(aq)
2(+1) + 2(x) + 3(–2) = 0 or 2x = +4 or x = +2
Here O.N. of none of the atoms undergo a change
(b) 2.5, Refer Solved Example 6 (ii) page 10.
and therefore, it is not a redox reaction.
(c) Na2 SO3
–3 +1 0 0 +1 –2
2(+1) + x + 3(–2) = 0 or x = +4
(d) Na2 SO4 (v) 4NH3(g) + 3O2(g) ⎯→ 2N2(g) + 6H2 O(g)
2(+1) + x + 4(–2) = 0 or x = +6 Here O.N. of N increases from –3 (in NH3) to 0 in
Q. 8. Balance the following equations by the (N2) and therefore, NH3 acts as a reducing agent.
oxidation number method. O.N. of O decreases from 0 (in O2) to –2(in H2O)
and therefore, O2 acts as an oxidising agent.
7 ⎯→ Cr
(i) Fe2+ + H+ + Cr2O2– 3+
+ Fe3+ + H2O
Thus, reaction (v) is a redox reaction.
 8/56 MODERN'S abc + OF CHEMISTRY–XI

Q. 10. Balance the following ionic equations MnO–4 + 5e– ⎯⎯→ Mn2+
(i) Cr2O72− + H+ + I– ⎯→ Cr3+ + I2 + H2O MnO–4 + 8H+ + 5e– ⎯⎯→ Mn2+
(ii) Cr2O72− + Fe2+ + H+ ⎯→ Cr3+ + Fe3+ + H2O MnO–4 + 8H+ + 5e– ⎯⎯→ Mn2+ + 4H2O ...(ii)

(iii) MnO−4 + SO32 − + H+ ⎯→ Mn2+ + SO24 − + H2O To balance the electrons, multiply eq. (i) by 5 and
eq. (ii) by 2 and add
(iv) MnO−4 + H+ + Br– ⎯→ Mn2+ + Br2 + H2O
3 + 6H ⎯⎯→ 2Mn
2MnO–4 + 5SO2– + 2+ + 5SO2– + 3H O
4 2

Reduction Reduction

+6 –1 +3 0 +7 –1 +2 0
Ans. (i) Cr2 O72– + H + + I – ⎯⎯ → Cr+3 + I2 + H2 O (iv) MnO4– + H+ + Br – ⎯⎯ → Mn2+ + Br2 + H2 O

Oxidation Oxidation

Dividing the equation into two half reactions : Dividing the equation into two half reactions :
Oxidation half reaction : ⎯⎯→ I2
I– Oxidation half reaction : Br– ⎯⎯→ Br2
7 ⎯⎯→ Cr
Reduction half reaction : Cr2O2– 3+
Reduction half reaction : MnO–4 ⎯⎯→ Mn2+
Balancing oxidation and reduction half reactions Balancing oxidation and reduction half reaction
separately as : separately as :
Oxidation half reaction Oxidation half reaction
I– ⎯⎯→ I2
Br– ⎯⎯→ Br2
2I– ⎯⎯→ I2
2Br– ⎯⎯→ Br2
2I– ⎯⎯→ I2 + 2e– ...(i)
Reduction half reaction 2Br– ⎯⎯→ Br2 + 2e– ...(i)
Reduction half reaction
7 ⎯⎯→
Cr2 O2– Cr3+
Cr2O2–
7 ⎯⎯→ 2Cr3+ MnO4– ⎯⎯→ Mn2+
Cr2O2–
7 + 6e
– ⎯⎯→ 2Cr3+ MnO4– + 5e– ⎯⎯→ Mn2+
Cr2O2– +
7 + 14H + 6e
– ⎯⎯→ 2Cr3+
+ 7H2O ...(ii) MnO4– + 8H+ + 5e– ⎯⎯→ Mn2+
(acidic medium) MnO4– + 8H+ + 5e– ⎯⎯→ Mn2+ + 4H2O ...(ii)
To balance the electrons, multiply eq(i) by 3 and To balance the electrons, multiply eq.(i) by 5 and
add to eq (ii) eq.(ii) by 2 and add
7 + 14H + 6I ⎯⎯→ 2Cr
Cr2O2– + – 3+ + 3I + 7H O
2 2
2MnO–4 + 10Br– + 16H+ ⎯⎯→ 2Mn2+ + 5Br2 + 8H2O
(ii) Refer Solved Example 25 (Page 908).

Reduction Long Answer Questions Carrying 5 marks

+7 +4 +2 +6
(iii) MnO4– + SO32– ⎯⎯ → Mn2+ + SO42– + H2 O
Q. 11. Explain redox reactions on the basis of electron
Oxidation transfer. Give suitable examples.
Dividing the equation into two half reactions : Ans. Refer Text (Page 3–4).
Oxidation half reaction : SO32– ⎯⎯→ SO42– Q. 12. On the basis of standard electrode potential
Reduction half reaction : MnO4– ⎯⎯→ Mn2+ values, suggest which of the following reactions
Balancing oxidation and reduction half reactions would take place ? (Consult the book for E°
separately as : value).
Oxidation half reaction (i) Cu + Zn2+ ⎯→ Cu2+ + Zn
SO32– ⎯⎯→ SO42– (ii) Mg + Fe2+ ⎯→ Mg2+ + Fe
SO32– ⎯⎯→ SO42– + 2e– (iii) Br2 + 2Cl– ⎯→ Cl2 + 2Br–
Since the reaction occurs in acidic medium, (iv) Fe + Cd2+ ⎯→ Cd + Fe2+
SO32– ⎯⎯→ SO42– + 2e– + 2H+ Ans. (i) Cu + Zn2+ ⎯→ Cu2+ + Zn

3 + H2O ⎯⎯→ SO4 + 2H + 2e ....(i)

SO2– E°(Cu2+|Cu) = +0.34V, E°(Zn2+|Zn) = – 0.76V
2– + –

Reduction half reaction Eocell = E°(cathode) – E°(anode)

MnO–4 ⎯⎯→ Mn2+ = – 0.76 – 0.34 = – 1.10V

Since Eocell is –ve, the reaction does not occur.
REDOX REACTIONS 8/57

(ii) Mg + Fe 2+
⎯→ Mg 2+
+ Fe increasing order of oxidation number of
2+ 2+
E°(Mg |Mg) = – 2.37V, E°(Fe |Fe) = – 0.74V chlorine : NaClO4, Na2CO3, NaClO, KClO2, Cl2O7,
ClO3, Cl2O, NaCl, Cl2, ClO2.
Eocell = – 0.74 – (– 2.37) = +1.63V Which oxidation state is not present in any of
the above compounds ?
Since Eocell is +ve, the reaction will take place.
Ans. Let oxidation state of Cl be x
(iii) Br2 + 2Cl– ⎯→ Cl2 + 2Br–
NaClO4 +1 + x + 4(–2) = 0 or x = +7
Eocell = +1.08 – 1.36 = – 0.28V NaClO3 +1 + x + 3(–2) = 0 or x = +5
NaClO +1 + x + –2 = 0 or x = +1
Since Eocell is –ve, this reaction does not occur.
KClO2 +1 + x + 2(–2) = 0 or x = +3
(iv) Fe + Cd2+ ⎯→ Cd + Fe2+
Cl2O7 2x + 7(–2) = 0 or x = +7
Eocell = – 0.44 – (– 0.74) = + 0.30
ClO3 x + 3(–2) = 0 or x = +6
Since Eocell is +ve, therefore, this redox reaction Cl2O 2x – 2 = 0 or x = +1
will occur. NaCl +1 + x = 0 or x = –1
Q. 13.Why does fluorine not show disproportionation Cl2 2x = 0 or x = 0
reaction ?
ClO2 x + 2(–2) = 0 or x = +4
Ans. Fluorine is most electronegative and strongest
oxidising agent and therefore, it does not show None of the compounds have an O.N. of +2.
positive oxidation states. Q. 16. Which method can be used to find out the
Q. 14.Write redox couples involved in the reactions strength of reductant/oxidant in a solution ?
(i) to (iv) given in Q. 12. Explain with an example.

Ans. (i) Cu2+⏐Cu and Zn2+ ⏐ Zn Ans. The method to find out the strength of reductant/
oxidant in a solution, is to connect the redox couple
(ii) Mg2+⏐Mg and Fe2+ ⏐ Fe of that species to normal hydrogen electrode and
(iii) Br ⏐Br– and Cl ⏐ Cl–
2 2 measure its electrode potential.
(iv) Fe2+⏐Fe and Cd2+ ⏐ Cd If E° is +ve, the electrode acts as reductant and if it
Q. 15.Find out the oxidation number of chlorine in is –ve, the electrode acts as oxidant. In this way by
the following compounds and arrange them in measuring the value for different redox couples, the
comparative strength can be determined.

MEMORY TEST

A. Say True or False B. Complete the missing links

1. The oxidation state of oxygen is always –2. 1. The oxidation number of chromium in CrO5 is ………..
2. Oxidation number of an element can be zero but
valency is never zero. 2. Oxidant is a substance in which the oxidation number
3. The decomposition of calcium carbonate to calcium of one of the atoms ………..
oxide and carbon dioxide is a redox reaction.
4. Nitrous acid can act both as an oxidising as well as 3. When the oxidation number of an element is
reducing agent. maximum, it can act only as ………..
5. The reaction : Cr2O72− + H2O  2CrO24− + 2H+ cannot 4. The oxidation number of oxygen in sodium peroxide
be regarded as a redox reaction.
is ………..
6. The oxidation number of each iron atom in Fe3O4 is
same. 5. In an electrochemical cell ……….. acts as a negative
7. The reaction : V2O5 + 5Ca ⎯→ 2V + 5CaO is a metal pole and ……… acts as a positive pole.
displacement reaction.
8. The oxidation number of carbon in CH2Cl2 is +4. 6. A compound in which oxidation number of oxygen is
9. Oxidation number of Mn in MnO4− is more than in +2 is ……….
MnO2. 7. In an electrochemical cell, oxidation occurs at ……….
10. The oxidation number of hydrogen in LiH is –1. and reduction occurs at ……….
 8/58 MODERN'S abc + OF CHEMISTRY–XI

8. Stock notation of chromium trioxide is ………. 4. Oxidation number of phosphorus in Na3PO4 is + 3/+5.
9. Oxidation number of N in ammonium sulphate is 5. The oxidation number of each terminal S atom in
……….. tetrathionate ion is +5/+2.5.
10. Oxidation number of chlorine in Cl2O7 is …….... 6. In the reaction : F2 + 2NaOH ⎯→ 2NaF + OF2 + H2O,
F2 undergoes only reduction/both oxidation and
C. Choose the correct alternative reduction.
7. Copper metal can/cannot be oxidised by Zn2+ ions.
1. In an electrochemical cell reduction occurs at cathode/
anode. 8. Iodine oxidises Na2S2O3 to Na2S4O6. This statement
is true/false.
2. In an oxidation reaction, oxidation number of an atom
increases/decreases. 9. Reductant is a substance in which oxidation number
of one of the atoms decreases/increases.
3. Oxidation number of C in CO2 is more/less than in
CH2Cl2. 10. In the reaction Zn(s) + PbCl2(aq) ⎯→ Pb(s) +
ZnCl2(aq), zinc acts as oxidising/reducing agent.

MEMORY TEST
A. Say True or False B. Complete the missing links

1. False 2. True 1. 5 2. decreases

3. oxidising agent 4. –1
3. False : It is not a redox reaction because oxidation
5. anode, cathode 6. OF2
number of none of the atoms changes.
7. anode, cathode 8. Cr2(III)O3
4. True 5. True 9. – 3 10. +7
6. False : It exists as FeO·Fe2O3 having oxidation number
+2 and +3. C. Choose the correct alternative

7. True 8. False : It is zero. 1. cathode 2. increases 3. more

4. +5 5. +5 6. only reduction
9. True 10. True.
7. cannot 8. true 9. increases
10. reducing

Q. 1.While sulphur dioxide and hydrogen peroxide E° Al 3+|Al = –1.66 V, E° Ag +|Ag = + 0.80 V.
can act as oxidising as well as reducing agents in their
reactions, ozone and nitric acid act as oxidising agents. Ans.Since reduction potential of silver is more than that
Why ? of hydrogen ( E° + , Pt = 0), silver vessel will be suitable to
H |H 2
Ans.The oxidation state of S in SO2 is +4. It can be store 1M HCl. On the other hand, E° Al 3 +|Al is less than that
oxidised to +6 oxidation state or reduced to +2. Therefore, it
acts as a reducing agent as well as oxidising agent. Similarly, of hydrogen ( E°H +|H ,Pt) so that hydrogen will be liberated
2
the oxidation state of oxygen in H2O2 is –1. It can be if stored in aluminium vessel.
oxidised to O2 (zero oxidation state) or reduced to H2O or Q. 3.Can Fe3+ oxidize Br– to Br2 at 1 M concen-
OH–(–2 oxidation state) and therefore acts as reducing as tration?
well as oxidising agent. E°(Fe3+ | Fe2+) = 0.77 V and E°(Br | Br–) = 1.09 V
However, both ozone and nitric acid can only decrease Ans.E°(Fe3+ | Fe2+) is lower than that of E°(Br | Br–).
their oxidation number and therefore, act only as oxidising Therefore, Fe2+ can reduce Br2 but Br– cannot reduce Fe3+.
agents. Thus, Fe3+ cannot oxidise Br– to Br2.
Q. 2.Out of aluminium and silver vessel, which Q.4. Is it safe to stir 1M AgNO3 solution with a
one will be more suitable to store 1 M HCl solution copper spoon ? Given :
and why ? E°Ag+|Ag = 0.80 V, E°Cu2+|Cu = 0.34V.
REDOX REACTIONS 8/59

Ans. No, copper spoon will dissolve as Cu2+ ions because (difference of electrode potentials of the cathode and anode)
copper has more tendency to get oxidised than silver. becomes zero.
Q.5. Consider the following table of standard Q.9. (a) What is the maximum and minimum
reduction potentials : oxidation states of nitrogen in its compounds ? Give one
example each.
Reaction E°(V)
(b) What is the oxidation number of N in each of the
A3+ + 2e– ⎯→ A+ 1.36 following :
B2+ + 2e– ⎯→ B 0.72 (i) NH3 (ii) N2H4 (iii) HN3 (iv) NO2– (v) N2O (vi) HCN
C2+ + 2e– ⎯→ C –0.28 (vii) N2 (viii) NH2OH (ix) HNO3 (x) NO2.
D+ + e– ⎯→ D –1.42 (c) What is the oxidation state of hydrogen in each
of the following :
(a) Which substance is (i) H+ (ii) H2 (iii) LiAlH4 (iv) HCl (v) LiH
(i) strongest oxidising agent ? Ans. (a) +5 equal to group number (e.g. N2O5) and –3
(ii) strongest reducing agent ? equal to the group number minus 8 (e.g. NH3)
(b) Which substance can be oxidised by B2+ ? (b) (i) –3 (ii) –2 (iii) –1/3 (iv) +3 (v) +1 (vi) –3 (vii) 0
(c) Which substance can be reduced by C ? (viii) –1 (ix) +5 (x) +4
(d) Write a balanced chemical equation for the (c) (i) +1 (ii) 0 (iii) –1 (iv) +1 (v) –1
overall cell reaction that gives the highest cell voltage Q.10. (a) Use the following reactions to arrange
and calculate E° for the reaction. the elements A, B, C and D in order of their redox
Ans. (a) (i) A3+ is the strongest oxidising agent. reactivity :
(ii) D is the strongest reducing agent. (i) A + B+ ⎯→ A+ + B
(b) B2+ can oxidise C and D. (ii) B + D+ ⎯→ B+ + D
(c) C can reduce A3+ and B2+. (iii) C+ + D ⎯→ No reaction
(d) A3+ + 2D ⎯→ A+ + 2D+ (iv) B + C+ ⎯→ B+ + C
E° = 1.36 – (–1.42) = 2.78 V (b) On the basis of above redox activity series,
Q.6. Copper dissolves in dilute HNO3 but not in predict which of the following reactions would you
dilute HCl. Explain. expect to occur.
Ans. Since E° of Cu2+|Cu electrode (+0.34 V) is higher (i) A+ + C ⎯→ A + C+ (ii) A+ + D ⎯→ A + D+
1 Ans. (a) The electrochemical series or redox activity is
than that of H+| H2 (0.0V), therefore, H+ ions cannot
2 based on the decreasing order of reduction potentials. This
oxidise Cu to Cu2+ ions and consequently, copper does not means that the species which gets reduced is higher in the
dissolve in dil. HCl. On the other hand, the electrode potential electrochemical series as compared to the other which is to
of NO3– ion, NO3–|NO (+0.97V) is higher than that of copper get oxidised (lose electrons).
electrode and hence, it can oxidise Cu to Cu2+ and hence
In reaction (i), B+ gets reduced by A and therefore B is
copper dissolves in dil. HNO3.
higher than A in electrochemical series.
Q.7. Element A will reduce the cation of element B
(B+) but will not reduce the cation of element C (C+). Will In reaction (ii) D+ gets reduced by B and therefore, D is
element C reduce the cation of element B? Explain. higher in electrochemical series than B. In reaction (iii) C+
does not get reduced by D, therefore, C is lower than D in
Ans. Since A will reduce B+, B has higher reduction
electrochemical series. But according to reaction (iv) C+ gets
potential than A and therefore, B lies above A in the
reduced by B and therefore, C is higher in electrochemical
electrochemical series. Now, A will not reduce C+, C has lower
series than B. Thus, the correct order is
reduction potential than A and therefore, C lies below A in
the electrochemical series. Therefore, C must be below B in D>C>B>A
the series and hence C will reduce B+. (b) Both reactions donot occur because A cannot be
Q.8.Why does an electrochemical cell stops reduced by C as well as D.
working after some time ? Q.11. 40.05 mL of 1.0 M Ce4+ are required to titrate
Ans. The electrode potential of any electrode depends 20.0 mL of 1.0 M Sn2+ to Sn4+. What is the oxidation
upon the concentration of ions. With time as the cell state of cerium in the reduction product ?
operates, the concentrations of ions in different Ans. The reactions occuring are :
compartments change and therefore, the electrode potentials Ce4+ + ne– ⎯→ Ce(4–n)+
also change. For example, in Zn–Cu cell, Sn2+ ⎯→ Sn4+ + 2e–
Zn(s) + Cu2+(aq) ⎯→ Zn2+ + Cu(s) To balance the equations, (the no. of electrons lost = no.
the concentration of the Zn2+ ions in the anode compartment of electrons gained) multiply eq. (i) by 2 and eq. (ii) by n and
increases and hence the electrode potential of anode also add
increases. At the same time, the concentration of Cu2+ ions 2Ce4+ + nSn2+ ⎯→ Ce(4–n)+ + Sn4+
in the cathode compartment decreases and hence the
Moles of Ce4+ in 40.05 mL of 1.0 M solution,
electrode potential of the cathode also decreases. Ultimately,
the electrode potential of the two electrodes become equal 1.0
= × 40.05 = 40.05 × 10–3 mol
and at this stage, the cell stops working because E cell 1000
 8/60 MODERN'S abc + OF CHEMISTRY–XI

Now 2 mol of Ce4+ will oxidise n mole of Sn2+ 11.70 = 19.5 – 3.90 n
40.05 × 10–3 mol of Ce4+ will oxidise Sn2+ or 3.90 n = 19.5 – 11.7 = 7.8
n n = 7.8 = 2
= × 40.05 × 10 −3 mol = 20.02 n × 10–3 mol 3.9
2 ∴ Value of n = 2
But moles of Sn2+ in 20.0 mL of 1.0 M solution Q. 13. 15.0 mL of 0.05 M SeO2 reacts with 30.6 mL
of 0.1 M CrSO4 solution. If during the reaction CrSO4
1.0
= × 20.0 = 20.0 × 10–3 mol gets oxidised to Cr2(SO4)3, to what oxidation state
1000 does selenium get converted ?
∴ 20.02 n × 10–3 mol = 20.0 × 10–3 mol Ans. Moles of Se4+ ions present in 15.0 mL of 0.05
∴ n=1 0.05
Hence 1 mol of electrons are required in the reduction M= × 15.0 = 7.5 × 10 −4 mole
1000
of each mol of Ce4+ ion.
Moles of Cr2+ ions present in 30.6 mL of 0.1 M solution
∴ Ce4+ + e– ⎯→ Ce3+
Ce3+ is the reduction product. 0.1
= × 30.6 = 3.06 × 10 −3 mole
Q.12. 3.90 × 10–3 moles of a solution containing an 1000
ion An+ require 2.34 × 10–3 moles of MnO4– for the The oxidation reduction reactions are :
oxidation of An+ to AO3– in acidic medium. What is Cr2+ ⎯→ Cr3+ + e– ...(i)
the value of n ? Se4+ + ne– ⎯→ Se(4–n)+ ...(ii)
Ans. Oxidation and reduction reactions are :
Reduction : Multiply eqn. (i) by n and add to eqn. (ii)
MnO4– + 8H+ + 5e– ⎯→ Mn2+ + 4H2O ...(i) nCr2+ + Se4+ ⎯→ 4Cr3+ + Se(4–n)+
Oxidation : According to the reaction
An+ + 3H2O ⎯→ AO3– + 6H+ + (5 – n)e– ...(ii)
n mole of Cr2+ will reduce 1 mole of Se4+
In a redox reaction, no. of electrons lost must be equal
to no. of electrons gained, therefore, multiply eq. (i) by 3.06 × 10–3 mole of Cr2+ will reduce Se4+
(5–n) and eq(ii) by 5 so that
1
(5 – n) MnO4– = 5An+ = × 3.06 × 10 −3 mole
∴ (5 – n) moles of MnO4– will oxidise 5 moles of An+ n
or 2.34 × 10–3 moles of MnO4– will oxidise An+ But Se4+ actually reduced = 7.5 × 10–4 mole
5
= × 2.34 × 10 −3 moles 3.06 × 10−3
5−n ∴ = 7.5 × 10−4
But number of moles of An+ actually oxidised = 3.90 × n
10–3 moles
5 3.06 × 10−3
∴ × 2.34 × 10−3 = 3.90 × 10–3 or n= =4
5−n 7.5 × 10−4
or 5 × 2.34 = (5 – n) × 3.90 ∴ Reduction of 1 mole SeO2 requires 4 electrons.
Hence, Se4+ is reduced to Se0.

9. Calculate the oxidation number of lead in Pb3O4.

Very Short
Short Answer
Answer Questions
Questions carrying 1 mark
10. Identify the oxidising and reducing agent in the
1. Define oxidant and reductant. following reaction :
2. Define oxidation and reduction. 3CuO + 2NH3 ⎯⎯→ 3Cu + N2 + 2H2O
11. Give an example of a compound in which the oxidation
3. What is the oxidation number of Mn in MnO2 ? number is fractional.
4. In the following reaction, predict the oxidising agent 12. Calculate the oxidation number of phosphorous in
and reducing agent Mg2P2O7.
Cr2O72– + 6 Fe2+ + 14 H+ ⎯⎯→ 2Cr3+ + 6Fe3+ + 7H2O 13. Indicate the oxidizing and reducing agents in the
following reaction :
5. What is the average oxidation number of carbon in
acetone (CH3COCH3) ? 2Cu2+ + 4I– ⎯→ 2CuI + I2
6. Can oxidation number be zero ? Illustrate. 14. Calculate the oxidation number of N in NO3–.
7. Will oxidation number increase or decrease in a 15. The oxidation number of B in Na2 B4O7 is +3. Is the
reduction reaction ? statement correct ?
8. What is the oxidation number of oxygen in H2O2 ? 16. What is the oxidation number of Cr in CrO2Cl2 ?
17. Calculate the oxidation number of C in C6H12O6.
REDOX REACTIONS 8/61
18. Identify oxidant and reductant in the following 9. State the maximum and minimum oxidation state of
reaction : each of the following :
I2 (aq) + 2S2O32– (aq) ⎯→ 2I– (aq) + S4O62– (i) Ta (ii) V (iii) S (iv) N
19. In the reaction : 10. Calculate the oxidation number of the underlined atom :
MnO2 + 4HCl ⎯→ MnCl2 + Cl2 + 2H2O, which species (i)K Mn O4 (ii) P2O5 (iii) Fe2 O3 (iv) Xe OF4
is oxidized ? (v)S2 O32– (vi) Cr2 O72–.
20. Name a compound each in which the oxidation state of
11. In the following reactions, label the oxidising agent and
O is (i) +2 and (ii) –2.
the reducing agent :
21. Name the type of reactions that occur at cathode in an
(a) MnO2 + 4HCl ⎯⎯→ MnCl2 + Cl2 + 2H2O
electrochemical cell. Give one example.
22. The reduction potentials are : (b) PbS(s) + 4H2O2(aq) ⎯⎯→ PbSO4(s) + 4H2O(l)
Cl2 + 2e– = 2 Cl– E° = 1.36 V (c) 2Al + 3F2(g) ⎯⎯→ 2AlF3(s).
F2 + 2e– = 2 F– E° = 2.87 V 12. How will you differentiate between oxidation number
Which is a better oxidising agent ? and valency ?
23. What is the oxidation number of S in the reactants and 13. Arrange the following in the decreasing order of
the products : oxidation number of Mn :
2 Na2 S2 O3 + I2 ⎯⎯→ Na2S4O6 + 2NaI (i) KMnO4 (ii) MnO2 (iii) Mn2O3
24. Can we store 1 M AgNO3 in a copper vessel ? Given (iv) Mn (v) K2 MnO4
E°Cu 2+ | Cu = + 0.34 V, E° Ag+ | Ag = + 0.80 V 14. Define oxidation and reduction according to electronic
concept. Comment “oxidation and reduction always go
side by side”.
Short Answer Questions carrying 2 or 3 marks
15. Balance the following redox reaction by oxidation
1. Define the terms : oxidation, reduction, oxidising agent number method :
and reducing agent according to electronic concept. Cr(OH)3 + IO3– ⎯⎯→ I – + CrO42– (basic medium)
2. Comment on the statement : oxidation and reduction 16. Consider the reaction :
go side by side.
2HBr + Cl2 ⎯⎯→ 2HCl + Br2
3. Which of the following reactions is oxidation and which
is reduction ? Identify the substance
(i) 2H2O + 2 e– ⎯⎯→ 2OH– + H2 (i) getting reduced (ii) getting oxidised
(ii) Al ⎯⎯→ Al3+ + 3e– (iii) acting as reducing agent
(iii) Fe3+ ⎯⎯→ Fe2+ – e– (iv) acting as oxidising agent.
(iv) 2O + C ⎯⎯→ CO2 + 4e–
2–
Long Answer Questions
Short carrying 5 marks
(v) Br– ⎯⎯→ 1/2 Br2 + e–
(vi) 2H2O – 4e– ⎯⎯→ 4H+ + O2 1. Balance the following equations using oxidation number
4. In the following reactions, explain which reactant is method :
oxidised and which is reduced. Give reasons for your (i) MnO4– + H+ + Fe2+ ⎯⎯→ Mn2+ + Fe3+ + H2O
answer : (ii) Zn + NO3– + H+ ⎯⎯→ Zn2+ + H2O
(i) 2H2S + SO2 ⎯⎯→ 2H2O + 3S (iii) H2SO3 + I2 + H2O ⎯⎯→ H2SO4 + HI
(ii) MnO2 + 4HCl ⎯⎯→ MnCl2 + H2O + Cl2
(iv) HNO3 + I2 ⎯⎯→ HIO3 + NO2 + H2O
(iii) 2KI + Cl2 ⎯⎯→ 2KCl + I2 (v) MnO4– + H2O2 ⎯⎯→ MnO4 2– + O2
(iv) CuO + CO ⎯⎯→ CO2 + Cu (in alkaline medium)
5. Calculate the oxidation number of :
2. Balance the following equations by oxidation number
(i) S in Na2S2O3 (ii) Cl in HClO4 method :
(iii) Mn in MnO2 (iv) Boron in Na2B4O7 (i) H2S + HNO3 ⎯⎯→ H2O + NO + S
(v) Cr in K2Cr2O7
(ii) NH3 + O3 ⎯⎯→ NO + H2O
6. What is the oxidation number of S in the following :
(iii) Cu + HNO3 ⎯⎯→ Cu(NO3)2 + NO + H2O.
(i) SO2 (ii) Na2S2 (iii) S2–
3. Balance the following equations by ion electron (half
(iv) CS2 (v) S2Cl2
reaction) method :
7. What is the oxidation number of hydrogen in the
following: (i) H2S + MnO4– + H+ ⎯⎯→ S + Mn2+ + H2O
(i) H+ (ii) NaH (iii) H2 (iv) LiAlH4 (ii) Cr2O72– + H+ + Fe2+ ⎯⎯→ Cr3+ + Fe3+ + H2O
8. Calculate the oxidation number of underlined atom in
(iii) AsO33– + IO3– ⎯⎯→ AsO43– + I–
the following :
(i) NaAuCl4 (ii) OF2 (iii) Ca(ClO2)2 (iv) SnO2 + C ⎯⎯→ Sn + CO.
(iv) NH2OH (v) SeO32– 4. What are redox reactions ? Discuss with examples. Give
important applications of redox reactions.
8/62 MODERN'S abc + OF CHEMISTRY–XI

5. Write short notes on : dioxide gas in acidic medium to produce Mn2+ and
hydrogen sulphate ion.
(a) Electrochemical series
(Balance by ion electron method)
(b) Redox titrations
(c) Abnormal oxidation number and structures of (ii) Reaction of liquid hydrazine (N2H4) with chlorate
compounds. ion (ClO3–) in basic medium produces nitric oxide
gas and chloride ion in gaseous state.
6. Identify the redox reactions out of the following
reactions and identify the oxidising and reducing agents (Balance by oxidation number method)
in them. (iii) Dichlorine heptaoxide (Cl2O7) in gaseous state
(i) 3HCl(aq) + HNO3 (aq) ⎯⎯→ combines with an aqueous solution of hydrogen
peroxide in acidic medium to give chlorite ion
Cl2 (g) + NOCl (g) + 2H2O (l) (ClO2–) and oxygen gas.
(ii) HgCl2 (aq) + 2KI (aq) ⎯⎯→HgI2 (s) + 2KCl (aq) (Balance by ion electron method)
Δ
(iii) Fe2O3 (s) + 3CO (g) ⎯⎯→ 2Fe (s) + 3CO2 (g) 8. Balance the following equations by the oxidation
(iv) PCl3 (l) + 3H2O (l) ⎯⎯
→ 3HCl (aq) + H3 PO3 (aq) number method.

(v) 4NH3 + 3O2 (g) ⎯⎯

→ 2N2 (g) + 6H2O (g) (i) Fe2+ + H+ + Cr2O2–
7
⎯⎯
→ Cr3+ + Fe3+ + H2O

7. Write balanced chemical equation for the following (ii) I2 + NO3– ⎯⎯

→ NO2 + IO3
–

reactions :
(iii) I2 + S2O2–
3
⎯⎯
– 2–
→ I + S4O 6
–
(i) Permanganate ion (MnO ) reacts with sulphur
4
(iv) MnO2 + C2O2–
4
⎯⎯
2+
→ Mn + CO2

3. + 4 5. 4/3 6. Yes 7. decrease

1. (i) MnO4– + 8H+ + 5Fe2+ ⎯→ Mn2 + 5Fe3+ + 4H2O
8. – 1 9. + 8/3 11. Na2S4O6 12. + 5
(ii) 4Zn + NO3– + 10H+ ⎯→4Zn2+ + NH4+ + 3H2O
13. Cu2+ : Oxidizing agent, I– : reducing agent
14. + 5. 15. Correct 16. + 6 (iii) H2SO3 + I2 + H2O ⎯→ H2SO4 + 2HI
(iv) 10HNO3 + I2 ⎯→ 2HIO3 + 10NO2 + 4H2O
(v) 2MnO4– + 2OH– + H2O2 ⎯→ 2MnO42– + O2 + 2H2O
3. Reduction reaction (i), (iii) and oxidation reaction
2. (i) 3H2S + 2HNO3 ⎯→ 2NO + 3S + 4H2O
(ii), (iv), (v), (vi)
4. (i) SO2 is reduced and H2S is oxidised. (ii) 4NH3 + 5O2 ⎯→ 4NO + 6H2O
(ii) MnO2 is reduced and HCl is oxidised. (iii) 3Cu + 8HNO3 ⎯→ 3Cu(NO3)2 +2NO+4H2O
(iii) Cl2 is reduced and KI is oxidised. 3. (i) 5H2S + 2MnO4– + 16H+ ⎯→ 5S + 2Mn2+ + 8H2O
(iv) CuO is reduced and C is oxidised.
(ii) 6Fe2+ + Cr2O72– + 14H+ ⎯→ 6Fe3+ + 2Cr3+ + 7H2O
5. (i) +2 (ii) +7 (iii) +4 (iv) +3 (v) +6
3 + IO3 ⎯→ 3AsO4 + I
3AsO3–
(iii) – 3– –
10. (i) +7 (ii) +5 (iii) +3 (iv) +6 (v) +2 (vi) +6
13. KMnO4, K2MnO4, MnO2, Mn2O3, Mn (iv) SnO2 + 2C ⎯→ Sn + 2CO
REDOX REACTIONS 8/63

OBJECTIVE TYPE QUESTIONS

cwise MULTIPLE CHOICE QUESTIONS A11. The oxidation states of V and Br in V(BrO2)2 are
i
Top
respectively
(a) 2 and 2 (b) 2 and 1
Select the correct answer : (c) 4 and 2 (d) 2 and 3.
A12. The oxidation state of N in HN3 is
Oxidation, Reduction and Oxidation Number (a) +3 (b) –3 (c) –1/3 (d) +1/3
A1. Reduction involves : A13. In which of the following S has highest oxidation state?
(a) gain of electrons (a) Na2S4O6 (b) S2Cl2
(b) addition of oxygen (c) S8 (d) H2SO4
(c) increase in oxidation number A14. Which of the following rules for oxidation number is
(d) loss of electrons. not correct ?
A2. Oxidation number of P in PO43– ion is : (a) The algebraic sum of all the oxidation numbers
(a) – 3 (b) + 7 in a compound is zero.
(c) + 5 (d) + 3. (b) An element in the free or the uncombined state
A3. Oxidation number of Mn in MnO4– ion is : bears oxidation number zero.
(a) +1 (b) –7 (c) The oxidation number of hydrogen is always +1.
(c) –1 (d) +7. (d) In all its compounds, the oxidation number of
A4. Oxidation number of C in CH3OH, CH2O, HCOOH and fluorine is –1.
C2H2 is respectively :
A15. In the reaction :
(a) –2, 0, +2, –1 (b) +2, 0, +2, –2
(c) –2, 0, +2, 0 (d) –2, –4, +2, –2 3CuO + 2NH3 ⎯→ N2 + 3H2O + 3Cu
A5. What is the oxidation state of S in Na2S2 ? the change of NH3 to N2 involve
(a) +1 (b) –2 (a) Loss of 6 electrons per mol of N2
(c) –1 (d) 0. (b) Loss of 3 electrons per mol of N2
A6. The oxidation state of S in Caro’s acid (permono (c) Gain of 6 electrons per mol of N2
sulphuric acid) H2SO5 is (d) Gain of 3 electrons per mol of N2
(a) +8 (b) +6
A16. Which of the following statement is not correct ?
(c) +5 (d) +4
(a) Oxidant is a substance which increases the
A7. Oxidation number of sodium in sodium amalgam
oxidation number of other substance.
(Na/Hg) is
(b) Reductant is a substance which decreases the
(a) 0 (b) +1 oxidation number of other substance.
(c) –1 (d) +2
(c) The oxidation number of oxidant decreases.
A8. In the reaction : Cl2 + 2OH– ⎯→ OCl– + Cl– + H2O
(d) In oxidation there is decrease in oxidation number.
(a) OH– is oxidising and Cl– is reducing agent
A17. When phosphorus reacts with caustic soda, the products
(b) Cl2 is oxidising and OH– is reducing agent
are PH3 and NaH2 PO2. The reaction is an example of
(c) OH– is both oxidising and reducing agent
(d) Cl2 is both oxidising and reducing agent. (a) oxidation (b) reduction
A9. The oxidation state of S in S2O82– is (c) disproportionation (d) none of these.
(a) +2 (b) +4 A18. Which of the following is not an example of redox
(c) +6 (d) +7 reaction ?
A10. In which of the following compounds, the oxidation (a) CuO + H2 ⎯⎯ → Cu + H2O
number of carbon is not zero ?
(b) Fe2O3 + 3CO ⎯⎯ → 2Fe + 3CO2
(a) C12H22O11 (b) HCHO
(c) 2K + F2 ⎯⎯ → 2KF
(c) CH3CHO (d) CH3COOH.
(d) BaCl2 + H2SO4 ⎯⎯ → BaSO4 + 2HCl

A1. (a) A2. (c) A3. (d) A4. (a) A5. (c) A6. (b) A7. (a) A8. (d) A9. (c) A10. (c)
A11. (d) A12. (c) A13. (d) A14. (c) A15. (a) A16. (d) A17. (c) A18. (d)
 8/64 MODERN'S abc + OF CHEMISTRY–XI

A19. The oxidation state of Cr in Cr(CO)6 is A30. On the basis of standard electrode potential of redox
(a) 0 (b) +2 couples given below find out which of the following is
(c) –2 (d) +6. the strongest oxidising agent.
A20. The oxidation state of oxygen in H2O2 is E°values : Fe3+|Fe2+ = + 0.77; I2(s)|I– = +0.54;
(a) –1 (b) +2 Cu2+|Cu = + 0.34; Ag+|Ag = + 0.80V
3+
(c) –2 (d) +1. (a) Fe (b) I2(s)
A21. The oxidation state of phosphorus in Ba(H2PO2)2 is (c) Cu2+ (d) Ag+
(a) +3 (b) +2 A31. The coefficients x, y and z in the following balanced
(c) +1 (d) –1 equation :
A22. The oxidation number of S in S8, S 2F2 and H 2S
x Zn + yNO3– ⎯→ zZn2+ + NH4+ (in basic medium) are
respectively are :
(a) 0, +1, –2 (b) +2, +1, –2 (a) 4, 1, 4 (b) 2, 2, 2
(c) 0, +1, +2 (d) +2, +1, –2 (c) 4, 2, 4 (d) 4, 4, 4
A23. In the reaction : A32. The following four colourless salt solutions are placed
3Br2 + 6CO32– + 3H2O ⎯→ 5Br– + BrO3– + 6HCO3– in separate test tubes and a strip of a copper is placed
(a) Br2 is oxidised and carbonate is reduced. in each. Which of the following solutions will finally
(b) Bromine is reduced and water is oxidised. turn blue ?
(c) Bromine is neither reduced nor oxidised (a) NaCl (b) AgNO3
(d) Bromine is both reduced and oxidised. (c) ZnSO4 (d) Cd(NO3)2.
A24. Oxidation state of Fe in Fe3O4 is A33. In a standard hydrogen electrode, the concentration
(a) +2 (b) +3 of H+ is :
(c) +8/3 (d) +2/3 (a) 0.1 M (b) 1 M
A25. In Br3O8 compound, oxidation number of bromine is (c) 10 M (d) Not fixed.
(a) 16/13 (b) 26/3 A34. In a galvanic cell, which of the following statement
(c) 24/3 (d) 16/3 is correct ?
A26. Which is the best description of the behaviour of bromine (a) anode is negatively charged
in the reaction (b) cathode is positively charged
H2O + Br2 ⎯→ HOBr + HBr (c) reduction occurs at anode
(a) Proton acceptor only (d) standard e.m.f of the cells is always zero.
(b) Both oxidised and reduced A35. For the redox reaction :
MnO4– + Fe2+ + H+ ⎯→ Mn2+ + Fe3+ + H2O
(c) Oxidised only
The correct coefficients of the reactants in the balanced
(d) Reduced only reaction are :
A27. The oxidation number of H in LiAlH4 is MnO4– Fe2+ H+
(a) –1 (b) +1 (c) 0 (d) +3 (a) 1 5 8
A28. The oxidation states of sulphur in the anions SO32– , (b) 2 5 8
S2O42– and S2O62– follow the order : (c) 4 5 16
(a) S2O42– < SO32– < S2O62– (d) 2 5 16
(b) SO32– < S2O42– < S2O62– A36. The standard reduction potential values of the three
metallic cations X, Y and Z are 0.52, –3.03 and –1.18
(c) S2O42– < S2O62– < SO32– V respectively. The order of reducing power of the
(d) S2O62– < S2O42– < SO32– corresponding metal is ?
Balancing Redox Reactions and Electrochemical Cells (a) Y > Z > X (b) X > Y > Z
(c) Z > Y > X (d) Z > X > Y
A29. E°values of some redox couples are given below. On
A37. A gas at 1 atm is bubbled through a solution containing
the basis of these values choose the correct option. 1M Y– and 1 M Z– at 25° C. If the reduction potential
E°values : Br2|Br– = + 1.90; Ag+|Ag(s) = + 0.80 of Z > Y > Z, then
Cu2+|Cu(s) = + 0.34; I2(s)|I– = + 0.54 (a) Y will oxidize X and not Z
(a) Cu will reduce Br– (b) Cu will reduce Ag (b) Y will oxidise Z and not X
(c) Cu will reduce I– (d) Cu will reduce Br2 (c) Y will oxidize both X and Z
(d) Y will reduce both X and Z.

A19. (a) A20. (a) A21. (c) A22. (a) A23. (d) A24. (c) A25. (d) A26. (b) A27. (a) A28. (a)
A29. (d) A30. (d) A31. (a) A32. (b) A33. (b) A34. (c) A35. (a) A36. (a) A37. (a)
REDOX REACTIONS 8/65

A38. Standard electrode potentials are : (c) Fe2+/Fe3+ remains unchanged

Fe2+| Fe (E° = –0.44 V), Fe3+ | Fe2+ (E° = 0.77 V) (d) Fe2+ decreases
Fe2+, Fe3+ and Fe blocks are kept together, then A39. For decolourization of 1 mole of KMnO4, the moles of
(a) Fe3+ increases H2O2 required is
(b) Fe3+ decreases (a) 1/2 (b) 3/2
(c) 5/2 (d) 7/2

38. (b) 39. (c)

B6. In the redox reaction

B MULTIPLE CHOICE QUESTIONS xKMnO4 + NH3 ⎯→ yKNO3 + MnO2 + KOH + H2O

from competitive examinations (a) x = 4, y = 6 (b) x = 8, y = 6
(c) x = 3, y = 8 (d) x = 8, y = 3
AIPMT & Other State Boards’ (DUMET 2009)
Medical Entrance B7. Which of the following have been arranged in
decreasing order of oxidation number of sulphur ?
B1. Which of the following is a redox reaction ?
(a) Na2S4O6 > H2S2O7 > Na2S2O3 > S8
(a) 2CuSO4 + 4KI ⎯→ Cu2I2 + 2K2SO4 + I2
(b) SO2 + H2O ⎯→ H2SO3 (b) H2SO4 > SO2 > H2S > H2S2O8
(c) Na2SO4 + BaCl2 ⎯→ BaSO4 + 2NaCl (c) SO2+
2
> SO2–
4
> SO2–
3
> HSO4–
(d) CuSO4 + 4NH3 ⎯→ [Cu(NH3)4]SO4 (d) H2SO5 > H2SO3 > SCl2 > H2S
(A.M.U. Med 2010)
(e) C12H22O11 + H2O ⎯→ C6H12O6 + C6H12O6
B8. The average oxidation state of sulphur in Na2S4O6 is
(Kerala P.M.T. 2007) (a) + 2.5 (b) + 2
B2. Oxidation number of iodine in IO–3, IO–4, KI and I2 (c) + 3.0 (d) + 3.5
respectively are (e) + 4 (Kerala PMT 2010)
(a) –1, –1, 0, +1 (b) +3, +5, +7, 0
B9. Standard electrode potential of three metals X, Y and
(c) +5, +7, –1, 0 (d) –1, –5, –1, 0
Z are – 1.2 V, +0.5 V and – 3.0 V respectively. The
(e) –2, –5, –1, 0 (Kerala PMT 2008) reducing power of these metals will be
B3. In the balanced chemical equation,
(a) Y > Z > X (b) Y > X > Z
IO3– + aI– + bH+ ⎯→ cH2O + dI2
a, b, c and d respectively correspond to (c) Z > X > Y (d) X > Y > Z (A.I.P.M.T. 2011)
(a) 5, 6, 3, 3 (b) 5, 3, 6, 3 B10. In which of the following compounds, nitrogen exhibits
(c) 3, 5, 3, 6 (d) 5, 6, 5, 5 highest oxidation state ?
(AFMC 2009) (a) N2H4 (b) NH3
B4. Number of moles of MnO4– required to oxidise one (c) N3H (d) NH3OH (A.I.P.M.T. 2012)
mole of ferrous oxalate completely in acidic medium B11. A mixture of potassium chlorate, oxalic acid and
will be : sulphuric acid is heated. During the reaction which
(a) 0.6 moles (b) 0.4 moles element undergoes maximum change in the oxidation
(c) 7.5 moles (d) 0.2 moles number ?
(CBSE Med. 2008) (a) S (b) H
B5. On the basis of following E° values, the strongest
(c) Cl (d) C (A.I.P.M.T. 2012)
oxidising agent is
[Fe(CN)6]4– ⎯→ [Fe(CN)6]3– + e– E° = – 0.35 V B12. In acidic medium, H2O2 changes Cr2O72– to CrO5 which
Fe2+ ⎯→ Fe3+ + e– E° = – 0.77 V has two (—O—O—) bonds. Oxidation state of Cr in
CrO5 is
(a) [Fe(CN)6]4– (b) Fe2+
(c) Fe3+ (d) [Fe(CN)6]3– (a) +5 (b) +3
(CBSE Med 2008) (c) +6 (d) –10 (A.I.P.M.T. 2014)

B1.(a) B2. (c) B3. (a) B4. (a) B5. (c) B6. (d) B7. (d) B8. (a) B9. (c) B10. (c)
B11. (c) B12. (c)
 8/66 MODERN'S abc + OF CHEMISTRY–XI

B13. Choose the disproportionation reaction among the (d) a = 1, b = 4, c = 6 and x = 2, y = 6, z = 3

following redox reactions. (e) a = 1, b = 6, c = 4 and x = 6, y = 2, z = 3
(a) 3Mg(s) + N2(g) ⎯→ Mg3N2(s) (Kerala P.E.T.2004)
(b) P4(s) + 3NaOH(aq) + 3H2O(l) ⎯→ PH3(g) + B19.Consider the following E° values
3NaH2PO2(aq) E° (Fe3+| Fe2+) = + 0.77 V ; E° (Sn2+|Sn) = – 0.14 V
(c) Cl2(g) + 2KI(aq) ⎯→ 2KCl(aq) + I2(s) Under standard conditions, the potential for the
(d) Cr2O3(s) + 2Al(s) ⎯→ Al2O3(s) + 2Cr(s) reaction:
(e) 2NaH(s) ⎯→ 2Na(s) + H2(g) (Kerala P.M.T. 2015) Sn (s) + 2Fe3+ (aq) ⎯⎯→ 2Fe2+(aq) + Sn2+ (aq) is
B14. Which of the following processes does not involve (a) 0.19 V (b) 0.140 V
oxidation of iron?
(c) 1.68 V (d) 0.63 V (A.I.E.E.E. 2004)
(a) Formation of Fe(CO)5 from Fe
B20. In a cell that utilizes the reaction :
(b) Liberation of H2 from steam by iron at high
Zn(s) + 2H+ (aq) ⎯⎯→ Zn2+(aq) + H2(g)
temperature.
addition of H2SO4 to cathode compartment will
(c) Rusting of iron sheets.
(a) increase the E and shift equilibrium to the right
(d) Decolourisation of blue CuSO4 solution by iron
(A.I.P.M.T. 2015) (b) lower the E and shift equilibrium to the right
B15. Assuming complete ionization, same moles of which of (c) lower the E and shift equilibrium to the left
the following compounds will require the least amount (d) increase the E and shift equilibrium to the left
of acidified KMnO4 for complete oxidation?
(A.I.E.E.E. 2004)
(a) FeC2O4 (b) Fe(NO2)2 B21. a K2Cr2O7 + b KCl + c H2SO4 ⎯→
(c) FeSO4 (d) FeSO3 (A.I.P.M.T. 2015) x CrO2Cl2 + y KHSO4 + zH2O
B16. For the redox reaction The above equation balances when
(a) a = 2, b = 4, c = 6 and x = 2, y = 6, z = 3
4 + H → Mn + CO2 + H2O
MnO–4 + C2O2– + 2+
(b) a = 4, b = 2, c = 6 and x = 6, y = 2, z = 3
The correct coefficients of the reactants for the balanced
(c) a = 6, b = 4, c = 2 and x = 6, y = 3, z = 2
equation are
(d) a = 1, b = 4, c = 6 and x = 2, y = 6, z = 3
MnO–4 C2O2–
4 H+ (e) a = 1, b = 6, c = 4 and x = 6, y = 2, z = 3
(a) 16 5 2 (Kerala P.E.T. 2004)
(b) 2 5 16 B22.What products are expected from the dispro-
(c) 2 16 5 portionation reaction of hypochlorous acid ?
(d) 5 16 2 (a) HClO and HClO4
(NEET 2018) (b) HCl and Cl2O
(c) HCl and HClO3
JEE (Mains) & Other State Boards’
Engineering Entrance (d) HClO3 and Cl2O (A.I.E.E.E. 2006)
B23.What is the oxidation number of carbonyl carbon in
B17. When KMnO4 acts as an oxidising agent and ultimately
forms MnO42–, MnO2, Mn2O3 and Mn2+, then the number methanal ?
of electrons transferred in each case is (a) +3 (b) +2
(a) 4, 3, 1, 5 (b) 1, 5, 3, 7 (c) +4 (d) 0 (Gujarat C.E.T. 2007)
B24.The standard oxidation potentials of Zn, Cu, Ag and Ni
(c) 1, 3, 4, 5 (d) 3, 5, 7, 1 (A.I.E.E.E.2002)
electrodes are +0.76, –0.34, –0.80 and +0.25 V
B18. aK2Cr2O7 + bKCl + cH2SO4 ⎯→ respectively. Which of the following reaction will
xCrO2Cl2 + yKHSO4 + 3H2O provide maximum voltage ?
The above equation balances when (a) Cu + 2Ag+(aq) ⎯→ Cu2+(aq) + 2Ag
(a) a = 2, b = 4, c = 6 and x = 2, y = 6, z = 3 (b) Zn + 2Ag+(aq) ⎯→ Zn2+(aq) + 2Ag
(b) a = 4, b = 2, c = 6 and x = 6, y = 2, z = 3 (c) H2 + Ni2+(aq) ⎯→ 2H+(aq) + Ni
(c) a = 6, b = 4, c = 2 and x = 6, y = 3, z = 2 (d) Zn + Cu2+(aq) ⎯→ Zn2+(aq) + Cu
(e) Zn + 2H+(aq) ⎯→ Zn2+(aq) + H2
(Kerala C.E.T. 2007)

B13. (b) B14. (a) B15. (c) B16. (b) B17. (c) B18. (d) B19. (a) B20. (a) B21. (d) B22. (c)
B23. (d) B24. (b)
REDOX REACTIONS 8/67

B25.Oxidation number of Mn atom in KMnO4 is B33.The oxidation number of Fe in brown ring

(a) 6 (b) 7 [Fe(H2O)5NO]2+ is
(a) 0 (b) +1
(c) 14 (d) 5 (B.H.U. 2007)
(c) +2 (d) +3 (Orissa JEE 2008)
B26.When sulphur dioxide is passed in an acidified K2Cr2O7
B34.Amount of oxalic acid present in a solution can be
solution, the oxidation state of sulphur is changed
determined by its titration with KMnO4 solution in
from
the presence of H 2 SO 4 . The titration gives
(a) +4 to +6 (b) +6 to +4 unsatisfactory results when carried out in the presence
(c) +4 to 0 (d) +4 to +2 of HCl because HCl
(Karnataka C.E.T. 2008) (a) oxidises oxalic acid to carbon dioxide and water
B27.Hydrogen gas is not liberated when the following metal (b) gets oxidised by oxalic acid to chlorine
is added to dil. HCl (c) furnishes H+ ions in addition to those from oxalic
(a) Mg (b) Sn acid.
(c) Ag (d) Zn (Karnataka C.E.T. 2008) (d) reduces permanganate to Mn2+ (AIEEE 2008)
B28. Which one of the following reactions involves B35.The oxidation number of sulphur atoms in
disproportionation? peroxomonosulphuric acid (H2SO5) and peroxodi-
(a) 2H2SO4 + Cu ⎯→ CuSO4 + 2H2O + SO2 sulphuric acid (H2S2O8) are respectively
(b) As2O3 + 3H2S ⎯→ As2S3 + 3H2O (a) +8 and +7 (b) +3 and +3
(c) 2KOH + Cl2 ⎯→ KCl + KOCl + H2O (c) +6 and +6 (d) +4 and +4 (J & K 2009)
(d) Ca3P2 + 6H2O ⎯→ 3Ca (OH)2 + 2PH3 B36.Oxidation states of Fe in Mohr's salt is
(a) +1 (b) +2
(e) 4NH3 + 3O2 ⎯→ 2N2 + 6H2O (Kerala PET 2008)
(c) +3 (d) +4 (Orissa-JEE 2009)
B29.In which of the following the oxidation number of oxygen
B37.Oxidation state of S in S4O62– from left to right are
has been arranged in increasing order?
(a) OF2 < KO2 < BaO2 < O3 O O
|| ||
(b) BaO2 < KO2 < O3 < OF2 −
O — S — S — S — S — O−
(c) BaO2 < O3 < OF2 < KO2 || ||
O O
(d) KO2 < OF2 < O3 < BaO2
(e) OF2 < O3 < KO2 < BaO2 (Kerala PET 2008) (a) +6, 0, 0, +6 (b) +5, 0, 0, +5
B30.Electrode potential of hydrogen electrode is ... volt (c) +3, +1, +1, +3 (d) +4, +1, +1, +4
(a) 0 (b) +1 (Orissa-JEE 2009)
(c) –1 (d) None of these B38.Oxidation number of P in PO43–, S in SO42– and that of
(Orissa JEE 2008) Cr in Cr2O72– are respectively
(a) +3, +6 and +5 (b) –3, +6 and +6
B31.The reaction
(c) +5, +3 and +6 (d) +5, +6 and +6
P4 + 3 NaOH + 3H2O ⎯→ 3NaH2PO2 + PH3
(Orissa-JEE 2009)
is an example of
B39. The oxidation state of S in H2SO4 is
(a) Disproportionation reaction (a) + 2 (b) + 4
(b) Neutralisation reaction (c) + 6 (d) + 7 (Orissa JEE 2010)
(c) Double decomposition reaction B40. In chromite ore, the oxidation number of iron, and
chromium are respectively
(d) Pyrolytic reaction (Orissa JEE 2008)
(a) + 3, + 2 (b) + 3, + 6
O O (c) + 2, + 6 (d) + 2, + 3
B32.Oxidation state of chromium in Cr is (Karnataka CET 2010)
O O B41. Which of the following species can function both as
O oxidizing as well as reducing agent ?
(a) +10 (b) +6 (a) Cl – (b) ClO4–
(c) +3 (d) +2 (Orissa JEE 2008) (c) ClO –
(d) MnO4–
(e) NO3– (Kerala PET 2010)

B25. (b) B26. (a) B27. (c) B28. (c) B29. (b) B30. (a) B31. (a) B32. (b) B33. (b) B34. (d)
B35. (c) B36. (b) B37. (c) B38. (d) B39. (c) B40. (d) B41. (c)
 8/68 MODERN'S abc + OF CHEMISTRY–XI

B42.If the molecular wt. of Na2S2O3 and I2 are M1 and M2 The cell voltage will be
respectively, then what will be the equivalent wt. of (a) 2.71 V (b) 2.03 V
Na2S2O3 and I2 in the following reaction ?
(c) – 2.71 V (d) – 2.03 V
2S2O32− + I2 ⎯→ S4O62− + 2I– (J.K. C.E.T. 2013)
B47. Given
(a) M1, M2 (b) M1, M2/2 –
E0 (Cr3+|Cr) = – 0.74 V, E0 (MnO4 |Mn2+) = 1.51 V
(c) 2M1, M2 (d) M1, 2M2 E Cr2O |Cr3+ = 1.33 V, E Cl|Cl– = 1.36 V
0 2– 0
7
(WB JEE 2011) Based on the data given above, strongest oxidising
B43.In the reaction : H2S + H2O2 ⎯→ S + 2H2O agent will be
–
(a) Cl (b) Cr3+
(a) H2S is an acid and H2O2 is a base.
(c) Mn2+ (d) MnO4–
(b) H2S is a base and H2O2 is an acid.
(JEE. Main 2013)
(c) H2S is an oxidising agent and H2O2 is a reducing B48. Consider the following reaction :
agent
– z
(d) H2S is a reducing agent and H2O2 is oxidising x MnO4 + y C2O42– + zH+ ⎯→ x Mn2+ + 2y CO2 + HO
2 2
agent.
The values of x, y and z in the reaction are
(e) H2S is hydrolysed to S. respectively
(Kerala PET 2011) (a) 5, 2 and 16 (b) 2, 5 and 8
B44. 1M solution each of Cu(NO3)2, AgNO3, Hg2(NO3)2 (c) 2, 5 and 16 (d) 5, 2 and 8
and Mg(NO3)2 is electrolysed using Pt-electrodes. (JEE. Main 2013)
The values of standard electrode potentials in B49. In the redox reaction,
volts are :
5
MnO4– + 8H+ + 5Br– ⎯→ Mn2+ + 4H2O + Br
Ag+|Ag = + 0.80 V, Cu2+|Cu = + 0.34V 2 2
Hg22+|Hg = + 0.79 V, Mg2+|Mg = – 2.37 V Which one is the reducing agent?
The sequence of deposition of metals on the (a) H+ (b) MnO4–
cathode will be (c) Br– (d) Mn2+
(a) Mg, Ag, Cu (b) Mg, Cu, Ag (A.M.U. Engg. 2014)
(c) Ag, Hg, Cu (d) Cu, Hg, Ag B50. Potassium dichromate is a good oxidizing agent, in
acidic medium. The oxidation state of chromium
(A.M.U. Engg. 2012)
changes by
B45. In the reaction, (a) 2 (b) 3
2FeSO4 + H2SO4 + H2O2 ⎯→ Fe2(SO4)3 + 2H2O, (c) 4 (d) 5
the oxidising agent is (M.H-C.E.T. 2015)
(a) FeSO4 B51. One mole of hydrazine (N2H4) loses 10 moles of
electrons in a reaction to form a new compound X.
(b) H2SO4
Assuming that all the nitrogen atoms in hydrazine
(c) H2O2 appear in the new compound, what is the oxidation
(d) both H2SO4 and H2O2 state of nitrogen in X?
(Karnataka C.E.T. 2013) (Note: There is no change in the oxidation state of
B46. An electrochemical cell has two half cell reactions hydrogen in the reaction).
as: (a) –1 (b) –3
A2+ + 2e– ⎯→ A ; E0A2+|A = 0.34 V (c) +3 (d) +5

X ⎯→ X2+ + 2e– ; E0X2+|X = – 2.37 V (e) +1 (Kerala PET 2016)

B42. (b) B43. (d) B44. (c) B45. (c) B46. (a) B47. (d) B48. (c) B49. (c) B50. (b) B51. (c)
REDOX REACTIONS 8/69

B52. 3ClO– (aq) ⎯→ ClO–3 + 2Cl– is an example of titration. Some half reactions and their standard
(a) oxidation reaction potentials are given below :
(b) reduction reaction MnO4–(aq) + 8H+ (aq) + 5e– ⎯⎯→ Mn2+(aq) + 4H2O (l)
(c) disproportionation reaction
E° = 1.51 V
(d) decomposition reaction (Karnataka CET 2017)
Cr2O72–(aq) + 14H+(aq) + 6e– ⎯⎯→ 2Cr3+(aq) + 7H2O(l)
B53. How many electrons are involved during the
oxidation reaction of KMnO4 in acidic medium? E° = 1.38 V
(a) 1 (b) 3 Fe3+(aq) + e– ⎯⎯→ Fe2+ (aq) E° = 0.77 V
(c) 5 (d) 4 Cl2(g) + 2e– ⎯⎯→ 2Cl– (aq) E° = 1.40 V
(J.K. CET 2018)
Identify the only incorrect statement regarding the
B54. For the redox reaction:
quantitative estimation of aqueous Fe(NO3)2.
xMnO–4 + yH2C2O4 + zH+ → mMn2+ + nCO2 + pH2O.
The values of x, y, m and n are (a) MnO4– can be used in aqueous HCl
(a) 10, 2, 5, 2 (b) 2, 5, 2, 10 (b) Cr2O72– can be used in aqueous HCl
(c) 6, 4, 2, 4 (d) 3, 5, 2, 10 (c) MnO4– can be used in aqueous H2SO4
(Karnataka CET 2018)
(d) Cr2O72– can be used in aqueous H2SO4
B55. Iodine reacts with concentrated HNO3 to yield Y along
with other products. The oxidation state of iodine in Y, is (I.I.T. 2002)
(a) 7 (b) 1 B58. The pairs of compounds having metals in their
(c) 5 (d) 3 (JEE Main 2019) highest oxidation state is
(a) MnO2, FeCl3
JEE (Advance) for IIT Entrance
(b) MnO4–, CrO2Cl2
B56. For the electrochemical cell M|M+ || X–| X,
(c) [Fe(CN)6]3–, Co(CN)3
E0M+|M = 0.44 V, E 0X|X– = 0.33 V
(d) [NiCl4]2–, [CoCl4]–
(a) M + X ⎯⎯→ M+ + X– is the spontaneous reaction
(I.I.T. 2004)
(b) M+ + X– ⎯⎯→ M + X is the spontaneous reaction
B59. Which ordering of compounds is according to the
(c) E°cell = 0.77V. decreasing order of the oxidation state of nitrogen ?
(d) E°cell = –0.77V. (a) HNO3, NO, NH4Cl,N2
(I.I.T. 2000) (b) HNO3, NO, N2, NH4Cl
B57. Standard electrode potential data are used for (c) HNO3, NH4Cl, NO, N2
understanding the stability of an oxidant in a redox (d) NO, HNO3, NH4Cl, N2 (I.I.T. J.E.E. 2012)

B52. (c) B53. (c) B54. (b) B55. (c) B56. (b) B57. (a) B58. (b) B59. (b)

MULTIPLE CHOICE QUESTIONS

C with more than one correct answer s
C2. In which of the following the oxidation number of atom
is/are correctly given ?
C1. Which of the following are redox reactions ? (a) C6H12O6 : C = 0
(a) BaCl2 + H2SO4 ⎯→ BaSO4 + 2HCl (b) Na4[Fe(CN)6] : Fe = + 3
(b) Zn + 2HCl ⎯→ ZnCl2 + H2 (c) HCOOH : C = + 4
(c) 6CO2 + 6H2O ⎯→ C6H12O6 + 6O2 (d) HCHO : C = 0

(d) KCN + AgCN ⎯→ K[Ag(CN)2]

C1. (b, c) C2. (a, d)

 8/70 MODERN'S abc + OF CHEMISTRY–XI

C3. Which of the following act both as an oxidising as well C7. Which of the following statements are wrong ?
as reducing agent ? (a) Reduction involves gain of electrons.
(a) HNO3 (b) H2O2 (c) HNO2 (d) H2S (b) The oxidation number of reducing agent decreases.
(c) Oxidising agent helps to increase the oxidation
C4. In which of the following the oxidation number of the number of reducing agent.
underlined atom is maximum ?
(d) Oxidation involves gain of electrons.
(a) H4P2O7 (b) KAl(SO4)2.12H2O C8. Consider the redox reaction :
(c) K2MnO4 (d) Na2SO3 2S2O32– + I2 ⎯→ S4O62– + 2I–
C5. Oxidation number of Cr in CrO5 is same as of S in (a) 2S2O32– gets oxidised to S4O62–
(b) I2 gets oxidised to I–
(a) H2SO5 (b) Na2S4O6 (c) Na2S2O7 (d) H2SO3
(c) there is increase in oxidation number of iodine
C6. Which of the following statements are not correct for during the reaction
the following reaction :
(d) The total increase in oxidation number of sulphur
2MnO4– + 6I– + 4H2O ⎯→ 2MnO2 + 3I2 + 8OH– is +1 during the reaction
(a) Oxidation number of Mn in MnO4– and MnO2 are C9. For the reaction:
same I - + ClO3- + H2SO4 ⎯→ Cl- + HSO4- + I2
(b) MnO4– acts as an oxidising agent The correct statement(s) in the balanced equation is/are
(c) H2O has been reduced (a) stoichiometric coefficient of HSO – is 6
4
(d) Oxidation number of iodide has increased from I– (b) iodide is oxidised
to I2.
(c) sulphur is reduced
(d) H2O is one of the products. (JEE advance 2014)

C3. (b, c) C4. (b, c) C5. (a, c) C6. (b, d) C7. (b, d) C8. (a, d) C9. (a, b, d)

(b) Bromine is neither oxidised nor reduced

(c) Bromine is oxidised and water is reduced
(d) Bromine is both reduced and oxidised
D3. When copper is treated with concentrated nitric acid,
Passage I.
nitric oxide and nitrogen dioxide are produced in equal
Oxidation and reduction reactions ocurring simultaneously volumes according to the following reaction :
are called redox reactions. Oxidation involves loss of xCu + yHNO3 ⎯→ Cu(NO3)2 + NO + NO2 + H2O
electrons while reduction involves gain of electrons. As a
result, oxidation number of an atom increases during The coefficients x and y are
oxidation and decreases during reduction. The redox reaction (a) 1 and 3 (b) 2 and 3
may involve combination of atoms or molecules, (c) 2 and 6 (d) 3 and 8
displacement of metals or non-metals and disproportiona- D4. A compound contains atoms of three elements A, B
tion reactions. Redox reactions may be balanced by oxidation
and C. If the oxidation number of A is +2, B is +5 and
number method or ion-elecron method.
that of C is –2, then the possible formula of the
Answer the following questions : compound is
D1. Which of the following represents oxidation ? (a) A3(BC4)2 (b) A3(B4C)2
(a) [Fe(CN)6]3– + e– ⎯→ [Fe(CN)6]4– (c) ABC2 (d) A3(BC3)2 (CBSE P.M.T.2000)
(b) S + 2e– ⎯→ S2– D5. In which of the following the change of oxidation
states is not correctly represented ?
(c) 2Cl– – 2e– ⎯→ Cl2
(a) KMnO4 + 5e– ⎯→ Mn2+
(d) Sb5+ + 2e–⎯→ Sb3+
D2. In the reaction : 1
(b) KMnO4 + 2e– ⎯→ Mn2O3
3Br2 + 6CO32– + 3H2O ⎯→ 5Br– + BrO3– + 6HCO3
– 2
(c) KMnO4 + 3e– ⎯→ MnO2
(a) Bromine is oxidised and carbonate is reduced
(d) KMnO4 + e– ⎯→ MnO42–

Passage I. D1. (c) D2. (d) D3. (d) D4. (d) D5. (d)
REDOX REACTIONS 8/71

Passage II. (a) O2 oxidises Mn2+ to Mn3+

(b) O2 oxidises both Mn2+ to Mn3+ and Fe2+ to Fe3+
Redox reactions play pivotal role in chemistry and biology.
(c) Fe3+ oxidises H2O to O2
The values of standard redox potential (E°) of two half-cell
reactions decide which way the reaction is expected to (d) Mn3+ oxidises H2O to O2
proceed. A simple example is Daniel cell in which zinc goes D8. Sodium fusion extract, obtained from aniline, on
into solution and copper gets deposited. Given below are a treatment with iron (II) sulphate and H2SO4 in the
set of half-cell reactions (acidic medium) along with their presence of air gives a prussian blue precipitate.
Hence, the blue colour is due to the formation of
E° (V with respect to normal hydrogen electrode) values.
(a) Fe4[Fe(CN)6]3 (b) Fe3[Fe(CN)6]2
Answer the following questions : (c) Fe4[Fe(CN)6]2 (d) Fe3[Fe(CN)6]3
I2 + 2 e– ⎯⎯⎯→ 2I – E° = 0.54 (I.I.T. 2007)
Passage III.
Cl2 + 2 e– ⎯⎯⎯→ 2Cl – E° = 1.36
Bleaching powder and bleach solution are produced on a
Mn3+ + e– ⎯⎯⎯→ Mn2+ E° = 1.50 large scale and used in several household products. The
effectiveness of bleach solution is often measured iodometry.
Fe3+ + e– ⎯⎯⎯→ Fe2+ E° = 0.77
Answer the following questions :
O2 + 4H+ + 4e– ⎯⎯⎯→ 2H2O E° = 1.23 D9. Bleaching powder contains a salt of an oxoacid as one
Using these data, obtain the correct explanation for the of its components. The anhydride of that oxoacid is
following questions. (a) Cl2O (b) Cl2O7 (c) ClO2 (d) Cl2O6
D6. Among the following, identify the correct statement. D10. 25 mL of household bleach solution was mixed with
(a) Chloride ion is oxidised by O2 30 mL of 0.50 M KI and 10 mL of 4 N acetic acid. In
(b) Fe2+ is oxidised by iodide the titration of the liberated iodine, 48 mL of 0.25 N
Na2S2O3 was used to reach the end point. The molarity
(c) Iodide ion is oxidised by chlorine
of the household bleach solution is
(d) Mn2+ is oxidised by chlorine (a) 0.48 M (b) 0.96 M
D7. While Fe3+ is stable, Mn3+ is not stable in acid solution
(c) 0.24 M (d) 0.024 M (I.I.T. 2012)
because

Passage II. D6. (c) D7. (d) D8. (a) Passage III. D9. (a) D10. (c)

Assertion Reason Type Questions 2. Assertion : Oxidation number of C in HCHO is zero.

Reason : Formaldehyde is a covalent compound.
The questions given below consist of an Assertion 3. Assertion : Oxygen has oxidation state of –2 in both
and the Reason. Use the following key to choose the O2 and O3.
appropriate answer. Reason : Oxygen is assigned an oxidation state of
– 2 in almost all its compounds.
(a) If both assertion and reason are CORRECT and 4. Assertion : Oxidation number of phosphorus in P4 is
reasson is the corect explanation of the assertion. zero.
(b) If both assertion and reason are CORRET, but reason Reason : Phosphorus has oxidation state zero in
is NOT THE CORRECT explanation of the assertion. all its compounds.
(c) If assertion is CORRECT, but reason is INCORRECT. 5. Assertion : Redox reactions are also called
(d) If assertion is INCORRECT, but reason is CORRECT. neutralisation reactions.
(e) If both assertion and reason are INCORRECT. Reason : The number of electrons gained or lost in
1. Assertion : Oxidation state of hydrogen in H2O is +1 the reaction are balanced.
and in CaH2 it is –1. 6. Assertion : 3ClO– ⎯→ ClO3– + 2Cl– is an example of
Reason : CaH2 is metal hydride and for hybrides, dissociation reaction.
hydrogen is assigned the oxidation state Reason : ClO– gets oxidised as well as reduced.
of –1.

1. (a) 2. (b) 3. (d) 4. (c) 5. (d) 6. (d)

8/72 MODERN'S abc + OF CHEMISTRY–XI

7. Assertion : A substance which gets reduced can act as Reason : Oxidation potential of zinc anode
reducing agent. decreases and that of copper cathode
Reason : An oxidising agent itself gets oxidised. increases. (AIIMS 2013)
8. Assertion : Copper sulphate solution is not stored in 10. Assertion : In iodometric titrations, starch is used as
zinc vessel. an indicator.
Reason : Zinc forms complex with copper sulphate. Reason : Starch is a polysaccharide.
9. Assertion : The Daniell cell becomes dead after
sometime.

7. (e) 8. (c) 9. (a) 10. (b)

Integer Type Questions 4. The oxidation number of S in H2SO5 is + x. The value of

x is
Integer Type : The answer to each of the following 5. The number of compounds among the following having
question is a single-digit-integer ranging from
O.N. of S as +6 is
0 to 9.
1. The difference in oxidation number of two types of S2O72–, Na2S2O3, H2SO3, HSO–4, (NH4)2 SO4, H2SO4,
sulphur atoms in Na2S4O6 is HSO –3, S4O62–
(I.I.T. 2011) 6. Reaction of Br2 with Na2CO3 in aqueous solution gives
sodium bromide and sodium bromate with the
2. How many moles of ‘iodine’ are liberated when 2 moles
evolution of CO2 gas. The number of sodium bromide
of KMnO4 react with KI in acidic medium?
molecules involved in the balanced chemical equation
is (I.I.T. 2011)
3. The value of n in the molecular formula BenAl2Si6 O18 is
(I.I.T. 2010)

1. (5) 2. (5) 3. (3) 4. (6) 5. (4) 6. (5)

NCERT Exemplar Problems

Objective Questions
1. Which of the following is not an example of redox below find out which of the following is the strongest
reaction ? oxidising agent.

(a) CuO + H2 ⎯→ Cu + H2O E° values : Fe3+ | Fe2+ = +0.77; I2(s) | I– = + 0.54;

(b) Fe2O3 + 3CO ⎯→ 2Fe + 3CO2 Cu2+ | Cu = +0.34; Ag+ | Ag = + 0.80V

(a) Fe3+ (b) I2(s)
(c) 2K + F2 ⎯→ 2KF
2+
(c) Cu (d) Ag+
(d) BaCl2 + H2SO4 ⎯→ BaSO4 + 2HCl
3. E° values of some redox couples are given below. On
2. The more positive the value of E°, the greater is the the basis of these values choose the correct option.
tendency of the species to get reduced. Using the E° values : Br2 | Br– = + 1.09; Ag+ | Ag(s) = + 0.80
standard electrode potential of redox couples given Cu2+ | Cu(s) = + 0.34; I2(s) | I– = + 0.54
(a) Cu will reduce Br– (b) Cu will reduce Ag
(c) Cu will reduce I– (d) Cu will reduce Br2

1. (d) 2. (d) 3. (d)

REDOX REACTIONS 8/73

4. Using the standard electrode potential, find out the (c) An element in the free or the uncombined state
pair between which redox reaction is not feasible. bears oxidation number zero.
E° values : Fe3+ | Fe2+ = + 0.77; I2 | I– = + 0.54; (d) In all its compounds, the oxidation number of
Cu2+
| Cu = + 0.34; Ag | Ag = + 0.80 V.
+ fluorine is –1.
(a) Fe3+ and I– (b) Ag+ and Cu 7. In which of the following compounds, an element
3+ 3+ exhibits two different oxidation states ?
(c) Fe and Cu (d) Ag and Fe
(a) NH2OH (b) NH4NO3
5. Thiosulphate reacts differently with iodine and
(c) N2H4 (d) N3H
bromine in the reactions given below :
8. Which of the following arrangements represent
2S2O32− + I2 ⎯→ S4O62− + 2I –
increasing oxidation number of the central atom ?
S2O32− + 2Br2 + 5H2O ⎯→ 2SO24− + Br– + 10H+
(a) CrO2− , ClO3− , CrO24− , MnO4−
Which of the following statements justifies the above
(b) ClO3− , CrO24− , MnO4− , CrO2−
dual behaviour of thiosulphate ?
(a) Bromine is a stronger oxidant than iodine. (c) CrO2− , ClO3− , MnO4− , CrO24−
(b) Bromine is a weaker oxidant than iodine. (d) CrO24− , MnO4− , CrO2− , ClO3−
(c) Thiosulphate undergoes oxidation by bromine and 9. The largest oxidation number exhibited by an element
reduction by iodine in these reactions. depends on its outer electronic configuration. With
which of the following outer electronic configurations
(d) Bromine undergoes oxidation and iodine undergoes
the element will exhibit largest oxidation number ?
reduction in these reactions.
(a) 3d14s2 (b) 3d34s2 (c) 3d54s1 (d) 3d54s2
6. The oxidation number of an element in a compound is
10. Identify disproportionation reaction
evaluated on the basis of certain rules. Which of the
(a) CH4 + 2O2 ⎯→ CO2 + 2H2O
following rules is not correct in this respect ?
(b) CH4 + 4Cl2 ⎯→ CCl4 + 4HCl
(a) The oxidation number of hydrogen is always +1.
(c) 2F2 + 2OH– ⎯→ 2F– + OF2 + H2O
(b) The algebraic sum of all the oxidation numbers (d) 2NO2 + 2OH– ⎯→ NO2− + NO3− + H2O
in a compound is zero. 11. Which of the following elements does not show
disproportionation tendency ?
(a) Cl (b) Br (c) F (d) I

4. (d) 5. (a) 6. (a) 7. (b) 8. (a) 9. (d) 10. (d) 11. (c)

configuration of its atom. Atom(s) having which of the

following outermost electronic configurations will
12. Which of the following statement (s) is/are not true about exhibit more than one oxidation state in its compounds.
the following decomposition reaction. (a) 3s1 (b) 3d14s2
2KClO3 ⎯→ 2KCl + 3O2 2 2
(c) 3d 4s (d) 3s23p3
(a) Potassium is undergoing oxidation 15. Identify the correct statements with reference to the
(b) Chlorine is undergoing oxidation given reaction
(c) Oxygen is reduced P4 + 3OH– + 3H2O ⎯→ PH3 + 3H2PO2−
(d) None of the species are undergoing oxidation or (a) Phosphorus is undergoing reduction only.
reduction (b) Phosphorus is undergoing oxidation only.
13. Identify the correct statement (s) in reflection to the (c) Phosphorus is undergoing oxidation as well as
following reaction : reduction.
(d) Hydrogen is undergoing neither oxidation nor
Zn + 2HCl ⎯→ ZnCl2 + H2
reduction.
(a) Zinc is acting as an oxidant 16. Which of the following electrodes will act as anodes,
(b) Chlorine is acting as a reductant when connected to Standard Hydrogen Electrode ?
(c) Hydrogen ion is acting as an oxidant (a) Al/Al3+ E° = – 1.66 V
(d) Zinc is acting as a reductant 2+
(b) Fe/Fe E° = – 0.44 V
14. The exhibition of various oxidation states by an
element is also related to the outer orbital electronic (c) Cu/Cu2+ E° = + 0.34 V
–
(d) F2(g)/2F (aq) E° = + 2.87 V

12. (a, b, c, d) 13. (c, d) 14. (b, c, d) 15. (c, d) 16. (a, b)
 8/74 MODERN'S abc + OF CHEMISTRY–XI

Q. 18. Match the items in Column I with relevant

items in Column II.
Q. 17. Match Column I with Column II for the Column I Column II
oxidation states of the central atoms.
(i) Ions having positive charge (a) +7
Column I Column II (ii) The sum of oxidation number of (b) –1
all atoms in a neutral molecule
(i) Cr2O72− (a) + 3
(iii) Oxidation number of hydrogen (c) +1
(ii) MnO4− (b) +4 ion (H+)
(iii) VO3− (c) +5 (iv) Oxidation number of fluorine in (d) 0
(iv) FeF63− (d) +6 NaF
(e) +7 (v) Ions having negative charge (e) Cation
(f) Anion

17. (i) – (d); (ii) – (e); (iii) – (c); (iv) – (a) 18. (i) – (e); (ii) – (d); (iii) – (c); (iv) – (b), (v) – (f)

20. Assertion (A) : In the reaction between potassium

permanganate and potassium iodide, permanganate
In the following questions a statement of ions act as oxidising agent.
assertion (A) followed by a statement of reason Reason (R) : Oxidation state of manganese changes
(R) is given. Choose the correct option out of from +2 to +7 during the reaction.
the choices given below each question.
21. Assertion (A) : The decomposition of hydrogen
(a) Both A and R are true and R is the correct peroxide to form water and oxygen is an example of
explanation of A. disproportionation reaction.
(b) Both A and R are true but R is not the correct
Reason (R) : The oxygen of peroxide is in –1 oxidation
explanation of A.
state and it is converted to zero oxidation state in O2
(c) A is true but R is false. and –2 oxidation state in H2O.
(d) Both A and R are false.
22. Assertion (A) : Redox couple is the combination of
19. Assertion (A) : Among halogens fluorine is the best oxidised and reduced form of a substance involved in
oxidant.
an oxidation or reduction half cell.
Reason (R) : Fluorine is the most electronegative o
atom. Reason (R) : In the representation EFe3+ /Fe2+ and
o 3+ 2+ 2+
ECu 2+
/Cu , Fe /Fe and Cu /Cu are redox couples.

19. (b) 20. (c) 21. (a) 22. (b)

s & Explanations for

Hint Difficult Objective Type Questions
A6. (b) : H2SO5 has one peroxide bond as

A2. (c) : x – 2 × 4 = – 3 ∴ x = +5
A3. (d) : x – 8 = –1 ∴ x = +7
A4. (a) : CH3OH : x+3–2+1 ∴ x = –2
CH2O : x+2–2 ∴x=0 So, it may be written as
HCOOH : +1 + x – 4 + 1 ∴ x = +2 H2S(O2)O3
C2H2 : 2x + 2 ∴ x = –1 +2 + x – 2 + 3(–2) = 0 ∴ x = +6
A5. (c) : Na2S2 + 2 + 2x = 0 ∴ x = –1 A7. (a) : Sodium exists in elemental form.
REDOX REACTIONS 8/75

A8. (d) : Cl2 + 2 OH– ⎯→ OCl– + Cl– + H2O

O.N. of Cl changes from 0 to +1 (in OCl–) and –1 in
(Cl–). B3. (a) : IO3– + 5I– + 6H+ ⎯→ 3H2O + 3I2
A9. (c) : S2O82– has structure B4. (a) : 5FeC2O4 + 3MnO4– + 24 H+ ⎯→ 5Fe3+ + 10CO2
O O + 3Mn2+ + 12H2O
5 mol of FeC2O4 ≡≡ 3 mol of MnO4–
– –
O S O O S O 3
∴ 1 mol of FeC2O4 ≡≡ mol of MnO4–
5
O O ≡≡ 0.6 mol of MnO4–
2 O atoms have peroxide linkage so it may be B5. (c) : Higher the reduction potential, larger is its
written as S2(O2) O62– tendency to get reduced and hence stronger is the
∴ 2x – 2 + 6(–2) = –2 ∴ x = +6 reducing agent.
+8 +4 +2 −2
A10. (c) : In CH3CHO, 2x + 4 – 2 = 0 ∴ x = –1 B7. (d) : H2 S O5 > H2 S O3 > S Cl2 > H2 S
A11. (d) : V(+2), Br + 3 in (BrO2)– so it exists as VII (BrIIIO2)2 B9. (c) : As the electrode potential decreases, reducing
A12. (c) : HN3 1 + 3x = 0 ∴ x = –1/3 power decreases.
A13. (d) : a (+2.5), b (+1), c (0), d (+7) Z>X>Y
B10. (c) : N2H4 ⇒ 2x + 4 (+ 1) or 2x + 4 = 0 ∴ x = – 2
+3 0
A15. (a) : CuO + 2NH 3 ⎯⎯→ N 2 + 3H2O + Cu NH3 ⇒ x + 3 (+1) = 0 or x + 3 = 0 ∴ x = – 3
N3H ⇒ 3x + 1 (+1) = 0 or 3x + 1 = 0 ∴ x = –1/3
–6e– NH2OH ⇒ x + 2 + (–2) + 1 = 0 or x + 1 = 0
Loss of 6e– for 1 mol of N2 ∴ x = –1
A16. (d) : In oxidation, there is increase in O.N. Thus, highest oxidation state is –1/3.
A17. (c) : O.N. of P changes from zero to –3 in PH3 and +1 B11. (c) :
in NaH2PO2. Therefore, it undergoes dispropor- +1+5 − 2 COOH +6 +6 −1
KClO 3 +⏐ + H2 SO4 ⎯→ K 2 SO4 + KCl + CO2 + H2O
tionation.
COOH
A20. (a) : + 2 + 2x = 0 ∴ x = –1 Maximum change in oxidation number of chlorine
A21. (c) : Ba(H2PO2)2 i.e., from + 5 to – 1.
o −3 +1
+2 +2(+2 + x – 4) = 0 B13. (b) : P4 + 3NaOH + 3H2O ⎯→ PH3 + 3NaH2 PO2
+2 + 4 + 2x – 8 = 0 ∴ x = +1
In this reaction, P is oxidised to NaH2PO2 and
A23. (d) : The O.N. of bromine decreases from 0 to –1 (in Br–) reduced to PH 3. This is disproportionation
and increases from 0 to +5 (in BrO3–).
A25. (d) : The calculated O.N. of Br in Br3O8 is reaction.
16 B14. (a) : Oxidation of iron in Fe(CO)5 is zero.
3x + 8(–2) = 0 or x = There is no change in oxidation number of Fe in
3
Actual O.N. of different Br atoms is Fe + 5CO ⎯→ Fe(CO)5
O Hence, it does not involve oxidation of iron.
O O
+6 +4 +6 B16. (b) : The correct balanced equation is
O Br — Br — Br O
2MnO4– + 5C2O42– + 16H+ ⎯→
O O 2Mn2+ + 10CO2 + 8H2O
O
A26. (b) : The O.N. of Br increases from 0 to +1 in (HOBr) +7 +6
and decreases from 0 to –1 (in HBr). Therefore it B17. (c) : KMnO4 + e– ⎯→ MnO42– (1e)
is oxidised as well as reduced.
+7 +4
A28. (a) : O.N. are SO32–(+4), S2O42–(+3), S2O6–2 (+5) KMnO4 + 3e– ⎯→ MnO2 (3e)
∴ Correct order
+7 +3
S2O42– < SO32– < S2O62–
KMnO4 + 4e– ⎯→ ½Mn2O3(4e)
A31. (a) : The balanced equation is
+7 +2
4 Zn + NO3– + 7H2O ⎯→ 4Zn2+ + NH4+ + 10 OH– KMnO4 + 5e– ⎯→ Mn2+(5e)
A35. (a) : The balanced equation is B18. (d) : The balanced equation is :
MnO4– + 5Fe2+ + 8H+ ⎯→ Mn2+ + 5Fe3+ + 4H2O K2Cr2O7 + 4KCl + 6H2SO4 ⎯→ 2CrO2Cl2 +
A37. (a) : Since the reduction potential of Y is greater than 6KHSO4 + 3H2O
that of X but lower than that of Z. Therefore, Y 3+ 2+ 2+
B19. (a) : E°cell = E° (Fe |Fe ) –E° (Sn |Sn)
will oxidize X but not Z.
= 0.77 – (–0.14) = +0.91 V
 8/76 MODERN'S abc + OF CHEMISTRY–XI

B20. (a) : For the reaction : B33. (b) : Here NO is in +1 oxidation state so that
Zn (s) + 2H+ (aq) ⎯⎯→ Zn2+ (aq) + H2 (g) x + 5 (0) + 1 = +2
∴ x = +1
RT ⎡⎣ Zn 2+ ⎤⎦ ( pH2 ) B34. (d) : KMnO4 can oxidise HCl also into Cl2 and itself
E = E° – ln 2
nF ⎡⎣H + ⎤⎦ gets reduced to Mn2+.
B40. (d) : Chromite ore is FeCr2O4.
On adding H2SO4, the [H+] increases. This will
increase the value of E and, therefore, reaction Change in O.N. per mol
proceeds more to the right. =1×2=2

B21. (d) :K2Cr2O7 + 2H2SO4 ⎯→ 2KHSO4 + 2CrO3 + H2O +2 0 +2.5 –1 –

2–
2KCl + H2SO4 ⎯→ 2KHSO4 + 2HCl ] × 2 B42. (b) : 2S2O3 + I2 ⎯→ S4O6 + 2I

CrO3 + 2HCl ⎯→ CrO2Cl2 + H2O ] × 2

Change in O.N. per mol
K2Cr2O7 + 4KCl + 6H2SO4 ⎯→ 2CrO2Cl2 + = 0.5 × 2 = 1
6KHSO4 + 3H2O M1
Equivalent wt. of Na2S2O3 =
B22. (c) : HClO disproportionates as : 1
+1 –1 +5
M2
Equivalent wt. of I2 =
3HOCl ⎯→ 2HCl + HClO3 2
Reduction (Oxidising agent)
O
|| –2 –1 0 –2
B23. (d) : H ⎯ C ⎯ H or HCHO B43. (d) : H2S + H2O2 ⎯→ S + 2 H2O
+1 + x – 2 + 1 = 0
Oxidation (reducing agent)
or x = 0
B44. (c) : Metals get deposited after undergoing reduction
B24. (b) :For (a) E° = – 0.34 + 0.80 = 0.46 V on cathode. Higher the value of reduction potential,
(b) E° = 0.76 + 0.80 = 1.56 V more is the tendency to get reduced. Order of E°
(c) E° = – 0.25 V values : Ag > Hg > Cu.
(d) E° = 0.76 + 0.34 = 1.00 V Hence, sequence of deposition : Ag, Hg, Cu.
(e) E° = 0.76 V B45. (c) : H2O2 gets reduced to H2O and acts as an oxidising
agent.
∴ Correct answer (b). o = Eo o
B46. (a) : Ecell A2+|A – E X2+|X
+4 +6 = 0.34 – (– 2.37) = 2.71 V
B26. (a) :K2Cr2O7 + H2SO4 + 3S O2 → K2SO4 + Cr2(SO4)3 + H2O
B47. (d) : MnO4– is the strongest oxidising agent because it
Oxidation number of S changes from +4 to +6. has highest reduction potential value.
–
B48. (c) : [MnO4 + 8H+ + 5e– ⎯→ Mn2+ + 4H2O] × 2
Oxidation 2–
C2O4 ⎯→ 2CO2 + 2e–] × 5
– 2–
0 –1 +1 2MnO4 + 5C2O4 + 16H+ ⎯→ 2Mn2+ + 10CO2 + 8H2O
B28. (c) : B49. (c) : O.N. of Br has increased from –1 to 0 and it is
Reduction oxidised. Hence, it acts as a reducing agent.
B50. (b) : Cr2O72– + 14H+ + 6e– ⎯→ Cr3+ + 7H2O
Oxidation state of Cr in Cr2O72– = +6
– Oxidation state of Cr in Cr3+ = +3
B31. (a) : Change in oxidation state = 3
B51. (c) : Oxidation state of N in hydrazine:
In this, the same substance undergoes oxidation N2H4
as well as reduction and therefore, it is an example 2x + 4 = 0 or x = –2
of disproportionation reaction.
1 mol of N2H4 loses 10 mol of electrons. Therefore,
–1 –1 one nitrogen loses 5 electrons. Thus, the oxidation
O O
state of N in new compound is = –2 + 5 = + 3
B32. (b) : Cr
–1O O–1 Reduction
O
–2
+1 +5 –1
B52. (c) : 3ClO– ⎯⎯→ –
x–6=0 ClO –3 + 2Cl
∴ x = +6
Oxidation
REDOX REACTIONS 8/77

The oxidation state of Cl decreases from +1 to –1 D8. (a) : Na + C + N ⎯→ NaCN

(reduction) and increases from +1 to +5 (oxidation). Sodium fusion extract
It is a disproportionation reaction. Fe2+ + 6CN – ⎯→ [Fe(CN)6]4–
B53. (c) : MnO–4 + 8H+ + 5e– —→ Mn2+ + 4H2O In the presence of air, Fe2+ ions get oxidised to
B54. (b) : The balanced reaction is : Fe3+ ions.
2MnO–4 + 5H2C2O4 + 6H+ —→ Fe2+ ⎯→ Fe3+ + e– E° = – 0.77 V
2Mn2+ + 10CO2 + 8H2O –
2
+
O + 4H + 4e ⎯→ 2H O E° = –1.23 V
2
Therefore, x = 2, y = 5, m = 2, n = 10
B55. (c) : Conc. HNO 3 oxidises I 2 to iodic acid (HIO 3 ) 4Fe2+ + 4H+ + O2 ⎯→ 4Fe3+ + 2H2O
Oxidation state of iodine in HIO3 is +5 E°Cell = + 0.46 V
B56. (b) : M+ + e– ⎯⎯→ M E° = + 0.44 V ...... (i) Fe3+ ions then combine with [Fe(CN)6]4– ion to form ferric
X + e– ⎯⎯→ X– E° = + 0.33 V ........ (ii)
ferrrocynide which has prussian blue colour.
Subtracting eqn. (ii) from eqn. (i)
M+ + X– ⎯⎯→ M + X E° = +0.11 V 4Fe3+ + 3[Fe(CN)6]4– ⎯→ Fe4 [Fe(CN)6]3
Since E° is positive, the reaction is spontaneous. Prussian blue
B57. (a) : MnO4– will oxidise Cl– ion according to the reaction. D9. (a) : The active constituent of bleaching powder or
2KMnO4 + 16H+ + 16 Cl– → 2Mn2+ + 8H2O + 5 Cl2 bleaching solution is Ca(OCl)2. The anion of this
The corresponding cell is salt is OCl– and therefore, the corresponding acid
Pt|Cl2 (g) |Cl– (aq) || MnO4–(aq), Mn2+, H+ | Pt is HOCl. The anhydride of this acid is Cl2O as
E°cell = E° (cathode) – E° (anode) 2HOCl ⎯→ H2O + Cl2O
= 1.51 – 1.40 = 0.11 V D10. (c) : Applying normality equation,
Since E°cell is +ve, the above reaction is feasible.
N1 V 1 ≡≡ N2 V 2
Therefore, MnO4– will oxidise both Fe2+ and Cl–
ions in aqueous medium. Thus, quantitative Ca(OCl)2 = Na2S2O3
estimation of Fe(NO3)2 is not suitable. N1 × 25 = 0.25 × 48
B58. (b) : MnO4–(+7) and CrO2Cl2(+6) have highest oxidation
states. 0.25 × 48
N1 = = 0.48 N
B59. (b) : Oxidation state of nitrogen in compounds is 25
HNO3 (+5), NO(+2), N2(0), NH4Cl (–3). The reaction is
Ca(OCl)z + 4H+ + 2e– ⎯→ Ca2+ + 2H2O + Cl2 ...(i)
2KI + Cl2 ⎯→ 2KCl + I2
C9. (a, b, d). The balanced chemical equation is: 2Na2S2O3 + I2 ⎯→ Na2S4O6 + 2NaI
–1 +6 +6 0
– – –
6 I + ClO3 + 6H2 SO4 ⎯→ Cl + 6HSO + 3I2 + 3H2O –
4 Ca(OCl)2 + 4H+ + 2e– + 2KI + 2Na2S2O3 ⎯→

Ca2+ + 2H2O + 2KCl + Na2S4O6 + 2NaI ...(ii)

O.N. increases (oxidised)
Since the eqn. (i) involves change of 2e–,
(a) Stoichiometric coefficient of HSO4– is 6.
Mol. wt
(b) O.N. of I– increases from –1 to 0 and hence it is oxidised. Eq. wt. of Ca(OCl)2 =
2
(d) H2O is one of the products.
Normality
∴ Molarity =
2

D6. (c) : On calculating the e.m.f. of the cells, we find that 0.48
= = 0.24
only the e.m.f. of the cell involving oxidation of I- 2
ion by Cl2 is +ve and option (c) is correct. ∴ Molarity of household bleach = 0.24 M
2I– ⎯→ I2 + 2e– E° = –0.54V
Cl2 + 2e– ⎯→ 2Cl– E° = + 1.36V Integer Type Answers

Cl2 + 2I– ⎯→ 2Cl– + I2 E° = 1.36 – 0.54 1. (5) : O.N. of different S atoms in Na2S4O6 is
= 0.82 V
D7. (d) : Only the e.m.f. of the cell involving the oxidation O O
of H2O to O2 by Mn3+ is +ve. +5 0 0
+5
O S S S S O
Mn3+ + e– ⎯→ Mn 2+ ] × 4 E° = +1.50V
2H2O ⎯→ 4H+ + O2 + 4e– E° = –1.23V O O

4Mn3+ + 2H2O ⎯→ 4Mn2+ + O2 + 4H+ Difference in O.N. = 5 – 0 = 5

E° = + 0.27 V
 8/78 MODERN'S abc + OF CHEMISTRY–XI

2. (5) : 2MnO 4– + 10 I– + 16H+ ⎯→ 2Mn2+ + 5I2 + 8H2O

11. (c) : Fluorine being most electronegative exhibits only
Thus, 2 mol of KMnO4 react with KI to liberate 5 –1 oxidation state.
moles of I2.
3. (3) : Ben Al2 Si6 O18 NCERT Exemplar Problems : MCQs Type-II
n(+ 2) + 2(+ 3) + 6(+ 4) + 18(– 2) = 0
+1 +5 –2 +1 –1 0
2n + 6 + 24 – 36 = 0 or 2n = 6 ∴ n = 3 12. (a, b, c, d) : 2KClO3 ⎯→ 2KCl + 3O2
(a) Since O.N. of potassium does not change, it neither
O
undergoes oxidation nor reduction.
H O S O O H (b) O.N. of Cl decreases from +5 (KClO3) to –1 (in KCl),
4. (6) :
therefore, it is undergoing reduction.
O (c) O.N. of O increases from –2 (in KClO3) to zero (in O2),
therefore, O is oxidised.
In peroxide bond, the oxidation state of O is – 1
(d) This statement is not correct because Cl is undergoing
H2S(O2)O3 reduction and O is undergoing oxidation.
+1 –1 +2 –1 0
2(+ 1) + x + 2(– 1) + 3(– 2) = 0 ∴ x=+6 0
13. (c, d) : Zn + 2HCl ⎯→ZnCl2 + H2
5. (4) : O.N. of S is + 6 in S2O 27 –, HSO4–, (NH4)2SO4, H2SO4 (a) The O.N. of Zn increases from 0 to +2 (in ZnCl2)
and therefore, Zn acts as a reductant and not as
6. (5) : 3Br2 + 3Na2CO3 ⎯→ 5NaBr + NaBrO3 + 3CO2
an oxidant. Hence, option is not correct.

NCERT Exemplar Problems : MCQs Type-I (b) The O.N. of Cl does not change and therefore, it
neither acts as a reductant nor an oxidant. Hence,
2. (d) : Ag+|Ag is most positive and therefore, Ag+ is the option is not correct.
strongest oxidising agent. (c) The O.N. of H decreases from +1 in H+ to 0 in H2.
3. (d) : Copper will reduce Br2 because E°(1.09 – 0.34 Therefore H+ acts an oxidant. This option is
= 0.75V) is +ve. correct.
2Cu + 2Br2 ⎯→ 2Cu Br2
(d) Zinc acts as reductant because its O.N. changes
4. (d) : The reaction : Ag + Fe3+ ⎯→ Ag+ + Fe2+ is not
from 0 to +2. This option is correct.
feasible because E° (0.77 – 0.80 = – 0.03) is
14.(b, c, d) : The elements having b, c and d configuration
negative. can exhibit variable oxidation states.
6. (a) : O.N. of hydrogen is not always +1. The O.N. of 0 –2 +1 +1 –2 –3 +1
15. (c, d) : P4 + 3OH + 3H2O ⎯→ P H3 + 3H2 PO 2
– –
hydrogen in hydrides is –1 and in H2, it is zero.
7. (b) : NH4NO3 exists as NH+4 and NO3− ions. The O.N. Because O.N. of P increases from 0(P4) to +1 (H2PO2–)
of N in NH+4 is – 3 and NO3− , O.N. is +5. and decreases from 0(P4) to –3 (PH3), therefore, P
has undergone both oxidation as well as reduction.
+3 +5 +6 +7 Option (c) is correct. Option (d) is also correct because
8. (a) : CrO2− , ClO3− , CrO24− and MnO4−
O.N. of H remains +1 in all the compounds and hence
9. (d) : The element having electronic configuration 3d54s2 hydrogen is undergoing neither oxidation nor
can exhibit maximum O.N. of +7. reduction.
10. (d) : 2NO 2 + 2OH – ⎯→ NO2− + NO3− + H 2O is a 16.(a, b) :The electrodes having negative electrode
disproportionation reaction because N is both potentials are stronger reducing agents than H2
gas and therefore, will act as anodes.
oxidised as well as reduced. O.N. of N increases
from +4 (in NO2) to +3 (in NO2− ).
REDOX REACTIONS 8/79

Time Allowed: 1 Hr. Maximum Marks: 25

1. Calculate the oxidation number of sulphur in S2O82–. (1)

2. Identify the oxidising and reducing agent in the following :
2Cu2+ + 4I– ⎯→ 2CuI + I2 (1)
3. Give one example each in which the oxidation state of oxygen is –1 and +2. (1)
4. Define a disproportionation reaction. (1)
5. Can the reaction:
Cr2O72– + H2O ⎯→ 2CrO42– + 2H+
be regarded as a redox reaction or not ? (1)
6. Out of Al and Ag vessel, which one will be more suitable to store 1M HCl solution and why?
E°(Al3+ | Al) = –1.66 V, E°(Ag+ | Ag) = +0.80 V (2)
7. So that the following reactions are redox reactions :
(i) Fe2O3 + 3 CO ⎯→ 2Fe(s) + 3CO2
(ii) 4NH3(g) + 5O2(g) ⎯→ 4NO(g) + 6H2O(g)
8. The compound AgF2 is unstable compound. However, if formed, the compound acts as a very
strong oxidising agent. Why? (2)
9. Consider the reactions :
2S2O32– (aq) + I2(s) ⎯→ S4O62– (aq) + 2I–(aq)
S2O32– (aq) + 2Br2(l) + 5H2O(l) ⎯→ 2SO42– (aq) + 4Br–(aq) + 10H+(aq)
Why does the same reductant, thiosulphate react differently with iodine and bromine. (2)
10. Depict the galvanic cell in which the reaction:
Zn(s) + 2Ag+(aq) ⎯→ Zn2+(aq) + 2Ag(s)
takes place. Further show
(i) which electrode is negatively charged
(ii) individual reaction at each electrode. (3)
11. Permanganate (VII) ion, MnO4– in basic solution oxidises iodide ion, I– to produce molecular iodine
(I2) and manganese (IV) oxide (MnO2). Write a balanced ionic equation to represent this
redox reaction. (3)
12. Balance the following equations by oxidation number method
(i) Fe2+ + Cr2O72– + H+ ⎯→ Fe3+ + Cr3+ + H2O
(ii) C6H6 + O2 ⎯→ CO2 + H2O (3)
13. (a) Fluorine reacts with ice and results in the following reaction :
H2O(s) + F2(g) ⎯→ HF(g) + HO(g)
Justify that this reaction is a redox reaction.
(b) Calculate the oxidation number of sulphur in H2SO5.
Suggest structure and account for the fallacy. (5)

To check your performance, see HINTS and SOLUTIONS to some questions at the end of
Part II of the book.