2

CHAPTER

Redox Reaction

Oxidation state of an element in a compound represents the

INTRODUCTION number of electrons lost or gained during its change from free
elemental state into that compound.
Redox reactions shows vital role in non renewable energy sources.
In cell reactions where oxidation and reduction both occurs Some important points concerning oxidation number
simultaneously will have redox reaction for interconversion of energy. 1. Oxidation number of an element may be positive or negative.
2. Oxidation number may be zero, whole number or a fractional
REDOX REACTION IN TERM OF value
ELECTRON TRANSFER REACTIONS Ex. Ni(CO)4 ⇒ O.S of Ni = 0
(MODERN IDEA) N3H ⇒ O.S of N = –1/3
HCl ⇒ O.S of Cl = –1
Oxidation 3. Oxidation state of same element can be different in same or
™ De-electronation different compounds.
™ Oxidation process is those process in which one or more e– Ex. H2S ⇒ O.S of S = –2
are lost by an atom, ion or molecule. H2SO3 ⇒ O.S of S = +4
Example: Zn → Zn+2 + 2e–
H2SO4 ⇒ O.S of S = +6
M → Mn+ + ne–

Reduction
™ Electronation ™ Electronegativity: P > H   C > H   S > C   Cl > N
™ Reduction process is those process in which one or more e–
are gained by an atom, ion or molecule. Some helping rules for calculating oxidation number:
Example: Cu+2 + 2e– → Cu ™ The oxidation state of an element in its free (elemental) state
Mn+ + ne– → M is zero. Example: Oxidation state of Na, Cu, I, Cl, O etc., are
zero.
Redox Reaction (Oxidation-Reduction): Many chemical ™ Oxidation state of an element in any of its allotropic form
reactions involve transfer of electrons from one chemical (eg. CDiamond, CGraphite, SMonoclinic, SRhombic) is zero.
substance to another. These electron-transfer reactions are ™ Oxidation state of all the components of an alloy are 0
termed as oxidation-reduction or redox reactions. (A) In case of covalent bond:
or (i) For homoatomic molecule
Those reactions which involve oxidation and reduction both A – A A = A A≡A
simultaneously are known as oxidation reduction or redox
↓↓ ↓↓ ↓↓
reactions.

or 00 00 00
Those reactions in which increase as well as decrease in (ii) For heteroatomic molecule (EN of B>A)
oxidation number of same or different atoms occurs are A – B A = B A≡B
known as redox reactions. ↓↓
↓↓ ↓↓
+1 –1 +2 –2 +3 –3
Oxidation State: Oxidation state of an atom in a molecule or
ion is the hypothetical or real charge present on an atom due to (iii) Oxidation state of atoms present in homoatomic molecules
electronegativity difference. is zero
or Ex. H2, O2, N2, P4, S8 = zero

 (iv) In complex compounds, oxidation state of some neutral (B) In case of co-ordinate bond (EN of B>A):
molecules (ligands) is zero. Example CO, NO, NH3, H2O A → B B → A
(v) Oxidation state of fluorine in all its compounds is –1 ↓  ↓ ↓  ↓
(vi) Oxidation state of group 1 & 2 elements are +1 and +2 +2 –2 (neglected)
respectively in their compounds. (C) In case of Ionic bond:
(vii) Oxidation state of hydrogen in most of its compounds is +1 Oxidation state of monoatomic ions is equal to the charge
except in metal hydrides (–1)
present on the ion.
Ex. NaH LiH CaH2 MgH2
Ex. Mg2+ → Oxidation state = +2
↓↓ ↓↓ ↓↓ ↓↓
e.g., Charge on cation = O.S of cation
+1 –1 +1 –1 +2 –1 +2 –1
Charge on anion = O.S of anion
(viii) Oxidation state of oxygen in most of its compounds is –2
Ex: NaCl → Na+ + Cl–
except in:
↓ ↓
(a) Peroxides ( O ) → Oxidation state (O) = –1
2−
2 +1 –1
Ex. H2O2, BaO2
MgCl2 → Mg2+ + 2Cl–
( )
(b) Super Oxides O12− → Oxidation state (O) = –1/2 ↓ ↓
+2 –1
Ex.  KO2

(c) Ozonide ( O ) → Oxidation state (O) = –1/3
1−
3 OXIDISING AND REDUCING AGENT
Ex. KO3
™ Oxidising agent or Oxidant: Oxidising agents are those
(d) OF2(Oxygen difluoride) Oxidation state (O) = +2
compounds which can oxidise others and reduce itself
F–O–F
during the chemical reaction. Those reagents in which for
(e) O2F2 (dioxygen difluoride) Oxidation state (O) = +1 an element, oxidation number decreases or which undergoes
(ix) The algebric sum of oxidation state of all the atoms present gain of electrons in a redox reaction are termed as oxidants.
in a polyatomic neutral molecule is 0.
e.g. KMnO4 , K2Cr2O7 , HNO3, conc.H2SO4 etc. are powerful
Ex. H2SO4
oxidising agents.
If O.S of S is x then
™ Reducing agent or Reductant: Reducing agents are those
2(+1) + x + 4 (–2) = 0 compounds which can reduce other and oxidise itself
x – 6 = 0 during the chemical reaction. Those reagents in which
x = +6 for an element, oxidation number increases or which
Ex. H2SO3 undergoes loss of electrons in a redox reaction are termed
If O.S of S is x then as reductants.
2(+1) + x + 3 (–2) = 0 e.g. KΙ, Na2S2O3 etc. are the powerful reducing agents.
x – 4 = 0
x = +4 TYPES OF REDOX REACTION
(x) The algebraic sum of oxidation state of all the atoms in a
polyatomic complex ion is equal to the charge present on Type of Redox Reaction
the ion. (i) Intermolecular redox reaction
Ex. SO 42− (ii) Intramolecular redox reaction
If O.S of S is x then (iii) Disproportionation reaction
x + 4(–2) = –2 (iv) Comproportionation reaction
x – 8 = –2 (i) Intermolecular redox reaction: A redox reaction in
x = +6 which oxidising agent and reducing agent are two different
Ex. HCO3− compounds.
If O.S of C is x then +2 +7
e.g. 10 FeSO 4 + 2KM nO 4 + 8H2SO4 →
+1 + x + 3 (–2) = –1 +3 +2
x – 5 = –1 5 Fe 2 ( SO 4 )3 + 2 Mn SO 4 + K2SO4 + 8H2O

x = +4 It is intermolecular redox reaction.

Redox Reaction 33
 (ii) Disproportionation Reaction: A redox reaction in
which same element present in a particular compound in
a definite oxidation state is oxidized as well as reduced
simultaneously is a disproportionation reaction.
Disproportionation reactions are a special type of redox
reactions. One of the reactants in a disproportionation
reaction always contains an element that can exist in at
least three oxidation states. The element in the form of
reacting substance is in the intermediate oxidation state and
both higher and lower oxidation states of that element are
formed in the reaction. For example:
−1 −2 0
2H 2O 2 (aq) → 2H 2O () + O 2 (g)
0 −2 +2
S8 (s) + 12 OH − (aq) → 4S2 − (aq) + 2S2 O32 − (aq)+ 6H 2 O ()
0 +1 −1
Cl2 (g) + 2OH¯(aq) → ClO − (aq) + Cl− (aq) + H O ()
2
+5 +7 –1
4KClO3 → 3KClO 4 + KCl
(iii) Intra molecular redox reaction:
Here both elements undergoing oxidation & reduction
belongs to same compound.
2KClO3 → 2KCl + 3O2
KClO3 plays a role of oxidant and reductant both. Here,
Cl present in KClO3 is reduced and O present in KClO3 is
oxidized. Since same element is not oxidized and reduced,
so it is not a disproportionation reaction, although it
looks like one.
It is called intra molecular redox reaction.
(iv) Comproportionation reaction:
NH4NO2 → N2 + 2H2O
Nitrogen in this compound has –3 and +3 oxidation number,
which is not a definite value. So it is not a disproportionation
reaction. It is an example of comproportionation reaction,
which is a class of redox reaction in which an element from
two different oxidation state gets converted into a single
oxidation state. Comproportionation reactions are reverse
reactions of disproportionation reactions.
BALANCING OF REDOX REACTIONS
Balancing of Redox Equation
(a) Ion electron method.
(b) Oxidation number change method.
(a) Ion electron method:
The following steps are followed while balancing redox
reaction (equations) by this method.
(i) Write the equation in ionic form.
(ii) Split the redox equation into two half reactions, one
representing oxidation and the other representing reduction.
(iii) Balance these half reactions separately for atoms other than
‘O’ and ‘H’.
(iv) Then balance oxygen atoms by adding H2O molecules to
the side deficient in oxygen. The number of H2O molecules
added is equal to the number of deficiency of oxygen atoms.
34
(v) Balance hydrogen atoms by adding H+ ions equal to the
deficiency on the side which is deficient in hydrogen atoms.
(vi) Finally if the medium of reaction is basic, OH– ions are
added to both sides of balanced equation equal in number
of H+ in balanced equation.
(vii) Balance the charge by adding electrons to the side which is
rich in +ve charges. i.e. deficient in electrons. Number of
electrons added is equal to the deficiency.
(viii) Multiply the half equations with suitable coefficients to
equalize the number of electrons.
(ix) Add these half equations to get an equation which is
balanced with respect to charge and atoms.
(b) Oxidation number change method: In a balanced redox
reaction, total increase in oxidation number must be equal to
total decrease in oxidation number. This equivalence provides
the basis for balancing redox reactions.
The general procedure involves the following steps:
(i) Select the atom in oxidising agent whose oxidation
number decreases and indicate the number of gain of
electrons per molecule.
(ii) Select the atom in reducing agent whose oxidation
number increases and find the number of loss of electrons
per molecule.
(iii) Now cross multiply i.e. multiply oxidising agent by
the number of loss of electrons and reducing agent by
number of gain of electrons.
(iv) Balance the number of atoms on both sides whose
oxidation numbers change in the reaction.
(v) In order to balance oxygen atoms, add required number
of H2O molecules to the side deficient in oxygen. Then
balance the required number of H atoms by adding H+
ions to the side deficient in the hydrogen.
Example 1: Balance the following redox reaction by ion
electron method:
FeSO4 + KMnO4 + H2SO4 → Fe2(SO4)3 + MnSO4 + H2O + K2SO4
Sol. Step-I: Assign the oxidation number to each element
present in the reaction.
+2 +6 −2 +1 + 7 –2 +1 +6 −2 +3 +6 −2 +2 +6 −2 +1 −2
Fe S O4 + K Mn O 4 + H 2 S O 4 → Fe 2 (S O 4 )3 + Mn S O 4 + H 2 O
Step-II: Now convert the reaction in Ionic form by
eliminating the elements or species, which are not
undergoing either oxidation or reduction.
+7
Fe2+ + Mn O −4 → Fe3+ + Mn2+
Step-III: Now identify the oxidation/reduction
occurring in the reaction
undergoes reduction
Fe2+ + MnO4–  Fe3+ + Mn2+
undergoes oxidation
P JEE Dropper Module-1 CHEMISTRY
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 Step-IV: Spilt the Ionic reaction in two half reactions, Now, students are advised to follow step VI to balance
one for oxidation and other for reduction. ‘O’ and ‘H’ atom.
oxidation − Re duction 2+ 2H+ + ClO– → Cl– + H2O
Fe2+ → Fe3+ MnO 4 → Mn 2H2O+ CrO2– → CrO42– +4H+
Step-V: Balance the atom other than oxygen and Now, since we are balancing in basic medium, therefore
hydrogen atom in both half reactions add as many as OH– on both side of equation as there
are H+ ions in the equation.
Fe2+ → Fe3+ MnO4 – → Mn2+
2OH– + 2H+ + ClO– → Cl– + H2O +2OH– ,
Fe & Mn atoms are balanced on both side.
4OH– + 2H2O + CrO2– → CrO42– + 4H+ + 4OH–
Step-VI: Now balance O & H atom by H2O & H+ Finally you will get
respectively by the following way: For one excess
H2O + ClO– → Cl– + 2OH– …(i)
oxygen atom, add one H2O on the other side and two
4OH– + CrO2– → CrO42– + 2H2O …(ii)
H+ on the same side.
Now from step VIII
Fe2+ → Fe3+ (no oxygen atom) ...(i)
+ – 2+ 2e– + H2O + ClO– → Cl– + 2OH– …(i) ×3
8H + MnO4 → Mn + 4H2O...(ii)
4OH– + CrO2– → CrO42– + 2H2O + 3e– …(ii) ×2
Step-VII: Equation (i) & (ii) are balanced atomwise.
Adding:
Now balance both equations chargewise. To balance the
3ClO– + 2CrO2– + 2OH– → 3Cl– + 2CrO42– + H2O
charge, add electrons to the electrically positive side.
oxidation
Example 3: Balance the following reaction by the oxidation
Fe2+  → Fe3+ + e–...(i) number method:
Re duction
5e– + 8H+ + MnO4– → Mn2+ + 4H2O...(ii) Cu + HNO3 → Cu(NO3)2 + NO2 + H2O
Step-VIII: The number of electrons gained and lost in
Sol. Write the oxidation number of all the atoms.
each half-reaction are equalised by multiplying both
0 +1+5–2 +2+5–2 +4 –2 +1 –2
the half reactions with a suitable factor and finally the
half reactions are added to give the overall balanced Cu + HNO3 → Cu(NO3)2 + NO2 + H2O
reaction. There is change in oxidation number of Cu and N.
Here, we multiply equation (i) by 5 and (ii) by 1 and add 0 2 + 5 – 2
them: Cu → Cu(NO3)2 ...........(i) (O xidation number of
Cu is increased by 2)
Fe2+ → Fe3+ + e– ....(i) × 5
+5 +4
5e - + 8H + + MnO 4 - ¾¾ ® Mn 2+ + 4H 2O .........(ii) ´1
+
HNO3 → NO2 .........(ii) (Oxidation number of N
2+ +
5Fe + 8H + MnO 4 ¾¾
-
® 5Fe3+ + Mn 2 + 4H 2O is decreased by 1)
(Here, at this stage, you will get balanced redox reaction To make increase and decrease equal, eq. (ii) is
in Ionic form) multiplied by 2.
Cu + 2HNO3 → Cu(NO3)2 + 2NO2 + H2O
Step-IX: Now convert the Ionic reaction into molecular
Balancing nitrates ions, hydrogen and oxygen, the
form by adding the elements or species, which are
following equation is obtained.
removed in step (2).
Cu + 4HNO3 → Cu(NO3)2 + 2NO2 + 2H2O
Now, by some manipulation, you will get:
This is the balanced equation.
5 FeSO4 + KMnO4 + 4H2SO4 →
5 1
Fe2 (SO4)3 + MnSO4 + 4H2O + K SO
2 2 2 4
or
10FeSO4 + 2KMnO4 + 8H2SO4 → 5Fe2(SO4)3 +
2MnSO4 + 8H2O + K2SO4. 1. The oxidation numbers of C in HCN and HNC,
respectively, are
Example 2: Balance the following redox reaction in basic
(a) +2, +2 (b) +2, +4
medium by ion electron method.
(c) +4, +4 (d) −2, −2
ClO– + CrO2– + OH– → Cl– + CrO42– + H2O 2. What is the oxidation state of Xe in Ba2XeO6?
Sol. By using upto step V, we will get: (a) 0 (b) +4 (c) +6 (d) +8
+1 +3 +6 3. When K2Cr2O7 is converted into K2CrO4, the change
Reduction Oxidation
Cl O − → Cl – ; Cr O −2  → Cr O 24 − in oxidation number of Cr is
(a) 0 (b) 6 (c) 4 (d) 3

Redox Reaction 35
 (b) Non-metal displacement: The non-metal displacement
2− −
4. In the reaction: 3Br2 + 6CO3 + 3H2O → 5Br− + BrO3 + redox reactions include hydrogen displacement and a
−
6HCO3 rarely occurring reaction involving oxygen displacement.
(a) Bromine is oxidized and carbonate is reduced. 0 +1 − 2 +1 − 2 +1 0
e.g., 2Na(s) + 2H 2 O() → 2NaOH(aq) + H 2 (g)

(b) Bromine is oxidized and water is reduced.
+1 − 2 0 +1 −1 0
(c) Bromine is both oxidized and reduced. 2H 2 O() + 2H 2 O(g) → 4HF(aq) + O 2 (g)
(d) Bromine is neither oxidized nor reduced.
5. Which of the following reaction is not a APPLICATIONS OF OXIDATION NUMBER
disproportionation reaction?
2– – – –
(a) Br2 + CO3 + H2O → Br + BrO3 + HCO3 (a) To compare the strength of oxyacid:
–
(b) P4 + OH + H2O → PH3 + H2PO2
– Strength of oxyacid ∝ Oxidation Number
(c) H2S + SO2 → S + H2O Example: Order of acidic strength in HClO, HClO2, HClO3,
HClO4 will be
(d) H2O2 → H2O + O2
Sol. Oxidation Number of chlorine
6. For the redox reaction,
−
Zn + NO3 → Zn2+ + NH4
+ HClO (Hypo chlorous acid) +1
in basic medium, the coefficients of Zn, NO3 and
− HClO2 (Chlorous acid) +3
OH− in the balanced equation, respectively, are: HClO3 (Chloric acid) +5
(a) 4, 1, 7 (b) 7, 4, 1 HClO4 (Perchloric acid) +7
(c) 4, 1, 10 (d) 1, 4, 10  Strength of oxyacid ∝ Oxidation Number
So the acidic strength order will be:
HClO4 > HClO3 > HClO2 > HClO
TYPES OF REDOX REACTIONS (b) To determine the oxidising and reducing nature of the
substances:
1. Combination reactions
Highest O.S. +4 +5 +5 +6 +7 +6 +7 +8 +8 +2 +1
A combination reaction may be denoted in the manner:
Elements C N P S Cl Cr Mn Os Ru O H
A+B→C
Lowest O.S. –4 –3 –3 –2 –1 0 0 0 0 –2 –1
Either A and B or both A and B must be in the elemental
form for such a reaction to be a redox reaction. All combustion (i) If effective element in a compound is present in maximum
reactions, which make use of elemental dioxygen, as well as oxidation state then the compound acts as oxidising agent.
other reactions involving elements other than dioxygen, are redox Example:
reactions. KMnO 4 K 2Cr2O7 H 2SO 4 SO3 H3PO 4 HNO3 HClO 4
0 0 +4 − 2
e.g., C(s) + O (g)  ∆
→ CO 2 (g) ↓ ↓ ↓ ↓ ↓ ↓ ↓
2
+7 +6 +6 +6 +5 +5 +7
2. Decomposition reactions
Decomposition reactions are the opposite of combination reactions. (ii) If effective element in a compound is present in minimum
Precisely, a decomposition reaction leads to the breakdown of a oxidation state then the compound acts as reducing agent.
compound into two or more components at least one of which PH3 NH3 CH 4
must be in the elemental state.
↓ ↓ ↓
+1 − 2 0 0
e.g., 2H 2 O(l)  ∆
→ 2H 2 (g) + O 2 (g) −3 −3 −4
(iii) If effective element in a compound is present in
All decomposition reactions are not redox reactions. intermediate oxidation state then the compound can act
+2 + 4 − 2 +2 − 2 +4 − 2
e.g., CaCO (s) 
∆ as oxidising agent as well as reducing agent.
3 → CaO(s) + CO 2 (g)
HNO 2 H3PO3 SO 2 H 2O 2
3. Displacement reactions ↓ ↓ ↓ ↓
In a displacement reaction, an ion (or an atom) in a compound is +3 +3 +4 –1
replaced by an ion (or an atom) of another element.
X + YZ →XZ + Y Key Note
(a) Metal displacement: A metal in a compound can be
displaced by another metal in the uncombined state. ™ Max. O.S. = No of valence e–
(for an element)
+2 + 6 − 2 0 0 +2 + 6 − 2 ™ Min. O.S. = 8 – (no. of valence e–)
e.g., CuSO (aq) + Zn(s) → Cu(s) + ZnSO (aq)
4 4

36 P JEE Dropper Module-1 CHEMISTRY

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(c) To calculate the equivalent weight of compounds: The (ii) Equivalent weight of a reducant
equivalent weight of an oxidising agent or reducing agent is Molecular weight
that weight which accepts one mole electrons in a chemical =
No.of electrons lost by one molecule
reaction or loses one mol electron in chemical reaction.
(i) Equivalent weight of oxidant M
=
Molecular weight Total change in O.N. per molecule
=
No.of electrons gained by one molecule
In acidic medium, C2O 42−  → 2CO 2 + 2e −
M M
= Equivalent weight of C2O42– =
Total change in O.N. per molecule 2
Example: In acidic medium (iii) In different conditions a compound may have different
6e–+ Cr2O72– +14H+ → 2Cr3++7H2O equivalent wts. Because, it depends upon the number of
Here atoms which undergoes reduction is Cr. Its O.S. is electrons gained or lost by that compound in that reaction.
decreasing from +6 to +3 (d) To determine the possible molecular formula of compound:
Equivalent weight of K2Cr2O7 Since the sum of oxidation number of all the atoms present
Molecular weight of K 2Cr2O7 M in a compound is zero, so the validity of the formula can be
= =
3× 2 6 confirmed.

Table: Some important oxidising & reducing agents.

No. of electrons
Species Changed to Reaction exchanged or Eq. wt.
change in O.N.

Mn +2 M
MnO −4 (O.A.) In acidic medium
MnO 4− + 8H + + 5e − → Mn 2 + + 4H 2 O 5 E=
5
MnO 2
M
MnO −4 (O.A.)
In neutral medium
or weak alkaline medium
MnO −4 + 3e − + 2H 2O → MnO 2 + 4OH − 3 E=
3

MnO 24 − M
MnO −4 (O.A.)
Strongly basic medium
MnO 4− + e − → MnO 24− 1 E=
1

Cr 3+ M
Cr2O72− (O.A.) In acidic medium
CrO72− + 14H + + 6e − → 2Cr 3+ + 7H 2O 6 E=
6

Mn 2 + M
MnO 2 (O.A.) In acidic medium
MnO 2 + 4H + + 2e − → Mn 2+ + 2H 2O 2 E=
2

M
Cl2 (O.A.) Cl– Cl2 + 2e − → 2Cl− 2 E=
2

CuSO 4 (O.A.) M
in iodometric titration Cu+ Cu 2+ + e − → Cu + 1 E=
1

S2O32− (R.A.) 2 2M
S4O62− 2S2O32− → S4O62− + 2e − E
= = M
(for two molecules) 2
(Hypo)
M
H 2O 2 (O.A.) H2O H 2O 2 + 2H + + 2e − → 2H 2O 2 E=
2

H 2O 2 → O 2 + 2H + + 2e − M
H 2O 2 (R.A.) O2 2 E=
O.N. of oxygen in H 2O is –1 per atom 2

Redox Reaction 37
 No. of electrons
Species Changed to Reaction exchanged or Eq. wt.
change in O.N.

M
Fe 2+ (R.A.) Fe3+ Fe 2+ → Fe3+ + e − 1 E=
1

M
C2O42– (RA) CO2 C2O42– → 2CO2 + 2e– 2 E=
2

FeC2O4 (RA) M
Fe3+ + CO2 Fe C2O4 → Fe3+ + 2CO2 + 3e– 3 E=
(ferrous oxalate) 3

CONCEPT OF n-FACTOR OR REDOX TITRATION

VALENCY FACTOR Titrations based on redox processes are called redox titrations. In
1. nf = Number of e– exchanged per molecule these titrations titrate/titrant are oxidising/ reducing agents. The
calculations made in redox titrations are again based on law of
= Total change in ON per molecule
chemical equivalence.
M
2. E = Titrate + Titrant → Products
nf
Meq. of titrate = meq. of titrant (at equivalent point),
3. Number of eqv. = Number of moles × nf
Example: Suppose that there are three atoms A, B, C and their or N1V1 = N2V2
oxidation number are 6, –1, –2, respectively. Then the molecular
formula of compound will be
Titration Using Acidified KMnO4
Use of KMnO4 as oxidising agent in redox titrations was first made
Sol. Since, the total charge on a free compound is zero. So
for the titration of Fe2+ ions. It is readily available and colour of its
+6 = (–1×4) + (–2) solution is too intense that an indicator is not ordinarily required
+6 = –6 – –
and MnO4 ions act as self indicator. Titrations of MnO4 are usually
or +6 = (–1×2) + (–2×2) carried out in acid medium.
So molecular formula, AB4C or AB2C2. Among the common mineral acids H2SO4, HCl and HNO3
only H2SO4 is useful for providing acidic medium. HCl
LAW OF EQUIVALENCE cannot be used since Cl¯ are oxidised to Cl2 by KMnO4. On
the other-hand HNO3 itself acts as strong oxidising agent.
The law states that one equivalent of an element combine with – –
2MnO4 + 10Cl + 16 H+ → 2Mn2+ + 5Cl2 + 8H2O
one equivalent of the other, and in a chemical reaction same no. of
Some important titrations using KMnO4 are given below:
equivalent (or mill equivalent) of reactants react to give same no.
of equivalent (or milli equivalents) of products separately. (a) KMnO4 vs. oxalic acid:
– 2–
According: 2MnO4 + 5C2O4 + 16 H+ → 2Mn2+ + 10 CO2 + 8H2O
–
(i) aA + bB → mM + nN End point: Light pink colour of MnO4 solution, KMnO4

m.eq of A = m.eq of B = m.eq of M = m.eq of N acts as self indicator.
(ii) In a compound MxNy At equivalence point:
m.eq of MxNy = m.eq of M = m.eq of N (i) 2m-mol KMnO4 reacts with 5m–mol oxalic acid.
(ii) meq. of KMnO4 = meq. of oxalic acid
Key Note NKMnO × VKMnO = Noxalic acid × Voxalic acid
4 4

™ For Acid-base (Neutralization reaction) or redox 1 1

(iii) × MKMnO × VKMnO = × Moxalic acid × VOxalic acid
reaction: 2 4 4 5
N1V1 = N2V2 is always true
(b) KMnO4 vs. Fe2+ ions:
But M1V1= M2V2 (may or may not be true) –
Fe2+ is readily oxidised by MnO4 to Fe3+. The reaction which
M1×n1×V1 = M2×n2×V2 (always true where n terms
takes place is given below:
represent n-factor) –
5Fe2+ + MnO4 + 8H+ → 5Fe3+ + Mn2+ + 8H2O

38 P JEE Dropper Module-1 CHEMISTRY

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In the laboratory, for practical purposes ferrous ammonium
sulphate is taken as a source of Fe2+ ions. In the determination
of Fe content in iron ores, the whole iron content present in a
definite amount of its solution is first converted into Fe2+ by
using suitable reducing agent like SnCl2.
–
End point: MnO4 acts as self indicator and light pink colour
(b) Iodometry: In iodiometric titrations an oxidising agent is
allowed to react with excess of KI (or I¯) solution.
It includes the estimations of following species
2MnO4¯ + 10I¯ + 16H+  Mn+2 + 5I2 + 8H2O
IO3¯ + 5I¯ + 6H+  3I2 + 3H2O
The I2 liberated is titrated with hypo solution (Na2S2O3).
2–
I2 + 2S2O3 → 2I¯ + S4O6
2–

of solution indicates end point. I2, though insoluble in water, remains in solution containing
At equivalent point : KI as KI3.
–
(i) 1mol MnO4 reacts with 5 mol Fe2+.
– On addition of starch after the liberation of iodine from the
(ii) Meq. of MnO4 = Meq. of Fe2+
reaction of Cu2+ ions on iodide ions, an intense blue colour
or NKMnO × VKMnO = NFe2+ × VFe2+
4 4 appears. This colour disappears as soon as the iodine is
or 5 × MKMnO × VKMnO = 1 × MFe2+ × VFe2+ consumed by the thiosulphate ions. Thus, the end-point can
4 4
( NKMnO = 5 × MKMnO , NFe2+ = MFe2+) easily be tracked and the rest is the stoichiometric calculation
4 4
only.
(c) Estimation of Fe2+ and Fe3+
ions in a solution:
In this estimation, the solution is titrated twice. First without
reduction in which only Fe2+ reacts and Fe 3+ remains
unreacted. In second step same volume of solution is taken.
Fe3+ ions are reduced to Fe2+ and then titrated. Here
(i) In I step : Meq. of KMnO4(let x) = Meq. of Fe2+ Example 4: Calculate the normality of a solution containing
(ii) In II step : Meq. KMnO4(y) = Meq. of Fe2+ + Meq. of Fe3+ 15.8 g of KMnO4 in 50 mL acidic solution.
(d) Analysis of sample containing oxalic acid and sodium oxalate: W × 1000
Sol. Normality (N) =
Same volume of solution are titrated separately with NaOH E × V(mL)
and KMnO4 solution where W=15.8 g, V=50 mL
Meq. of NaOH = Meq. of oxalic acid Molar mass of KMnO 4
E= = 158/5 = 31.6
and Meq. of KMnO4 = Meq. of oxalic acid +Meq. of sodium Valence factor
oxalate So, N=10
Titration Using Acidified K2Cr2O7 Example 5: Calculate the normality of a solution containing
2– 50 mL of 5M solution K2Cr2O7 in acidic medium.
In volumetric analysis Cr2O7 is also used commonly as oxidant
–
yet weaker than MnO4 , Ce4+ etc. In most of its applications, it is Sol. Normality (N) = Molarity × Valence factor = 5 × 6 = 30N
3+
reduced to Cr . Example 6: Find the number of moles of KMnO4 needed to
2–
Cr2O7 + 14H+ + 6e¯ → 2Cr3+ + 7H2O oxidise one mole Cu2S in acidic medium.
M Cr O2– 296 The reaction is KMnO4 + Cu2S → Mn2+ + Cu2+ + SO2
E Cr= 2– = = 49
2 7
Sol. From law of equivalence
2O7
6 6
These titrations are made in 1–2 N acid solution. In neutral equivalents of Cu2S = equivalents of KMnO4
or alkaline medium, it is not used. In alkaline medium orange moles of Cu2S × v.f. = moles of KMnO4 × v.f.
2– 2–
Cr2O7 changes to yellow CrO4 . 1 × 8 = n2 × 5
Iodometric and lodimetric Titration 8
n 2= = 1.6
Iodine acts as mild oxidising agent 5
These titrations fall into two categories : Example 7: In a reaction vessel, 1.184 g of NaOH is
required to be added for completing the reaction. How
(a) Iodimetry: In these titrations, standard I2 solution is
many millilitre of 0.15 M NaOH should be added for this
used to titrate easily oxidisable substances. It includes the
requirement?
estimations of thiosulphates, sulphite arsenite etc.
2–
2S2O3 + I2 → S4O62– + 2I¯ Sol. Amount of NaOH present in 1000 mL of 0.15 M
2– 2– NaOH = 0.15 × 40 = 6 g
SO3 + I2 + H2O → SO4 + 2H+ + 2I¯
∴ 1 mL of this solution contain NaOH = 6 × 10–3 g
3– 2–
AsO3 + I2 + H2O → AsO4 + 2H+ + 2I¯ ∴ 1.184 g of NaOH will be present in
H2S + I2 → S + 2I¯ + 2H+ 1
= × 1.184= 197.33 mL
Sn2+ + I2 → Sn4+ + 2I¯ 6 × 10−3
N2H4 + 2I2 → N2 + 4H+ + 4I¯

Redox Reaction 39
 Example 8: Which of the following is/are correct ? 8. How many moles of KMnO4 are needed to oxidise a
(a) g mole wt. = mol. wt. in g = wt. of 6.022 × 1023 molecules mixture containing 1 mole of each FeSO4 & FeC2O4
(b) mole = NA molecule = 6.02 × 1023 molecules in acidic medium?
(c) mole = g-molecules
(d) None of the above 4 5
(a) (b)
Sol. (a) g mole wt. = mol. wt. in g = wt. of 6.022 × 1023 5 4
molecules
3 5
(b) mole = NA molecule = 6.02 × 1023 molecules (c) (d)
(c) mole = g-molecules 4 3
Example 9: Find the average and individual oxidation 9. Equivalent weight of K2CrO4 when it reacts with
number of Fe & Pb in Fe3O4 & Pb3O4, respectively, which
AgNO3 to give Ag2CrO4 is:
are mixed oxides.
Sol. (a) Infinite (b) M
(i) Fe3O4 is mixture of FeO & Fe2O3 in 1 : 1 ratio M M
so, individual oxidation number of Fe = +2 & +3 (c) (d)
2 3
1(+2) + 2(+3)
& average oxidation number = = 8/3
3
(ii) Pb3O4 is a mixture of PbO & PbO2 in 2 : 1 molar ratio
so, individual oxidation number of Pb are +2 & +4
& average oxidation number of
MISCELLANEOUS
2(+2) + 1(+4) 1. nf for species undergoes disproportionation
Pb = = 8/3
3
nR × no
= (where nR & no are nf for Reduction & Oxidation
nR × no
processes)

2. Oxidation states:

7. The number of moles of oxalate ion oxidized by one H 2SO5  CrO5 } Cr(+6)
mole of Cr2O72– ion in acidic medium.  δ(+6)
H SO
2 2 8  K 3CrO5 } Cr(+5)
6 2 3 5
(a) (b) (c) (d)
2 5 5 3 CaTiO 4 } Ti(+4)

40 P JEE Dropper Module-1 CHEMISTRY

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 AARAMBH (SOLVED EXAMPLES)
1. Which of the following reaction represents the oxidising Sol. (a) 6H+ + 5H2O2 + 2MnO4– → 2Mn+2 + 5O2 + 8H2O
behaviour of H2SO4? (b) 4Zn + 10HNO3 (dil) → 4Zn(NO3)2 + 3H2O
(a) 2PCl5 + H2SO4 → 2POCl3 + 2HCl + SO2Cl2 + NH4NO3
(c) 2CrΙ3 + 64KOH + 27Cl2 → 2K2CrO4 + 6KΙO4
(b) 2NaOH + H2SO4 → Na2SO4 + 2H2O
+ 54KCl + 32H2O.
(c) NaCl + H2SO4 → NaHSO4 + HCl (d) 6P2H4 → 8PH3 + P4
(d) 2HI + H2SO4 → I2 + SO2 + 2H2O (e) 2Ca3 (PO4)2 + 6SiO2 + 10C → 6CaSiO3 + P4 + 10CO
Sol. Oxidising nature  O.S. decreases 6. The number of electrons required to balance the following
+6 +4 equation are:
2HI + H2SO4  I2 + SO2 + 2H2O
Reduction NO3– + 4H+ → 2H2O + NO
(a) 2 on right side (b) 3 on left side
Therefore, option (d) is the correct answer.
(c) 3 on right side (d) 5 on left side
2. In which of the following reaction H2O2 acts as reducing agent: +5 +2
(a) 2FeCl2 + 2HCl + H2O2 → 2FeCl3 + 2H2O Sol. N O3– + 4H + → 2H 2O + N O
+5 +2
(b) Cl2 + H2O2 → 2HCl + O2 So, 3e – + N → N
(c) 2HI + H2O2 → 2H2O + I2 Add 3 electrons on left side.
(d) H2SO3 + H2O2 → H2SO4 + H2O Therefore, option (b) is the correct answer.
7. 2KMnO4+5H2S+6H+→2Mn2+ + 2K+ + 5S + 8H2O. In the
Oxidation above reaction, how many moles of electrons would be
–1 0
Sol. Cl2 + H2O2  2HCl + O2 involved in the oxidation of 1 mole of reductant?

 Reducing nature  O.S. Increases (a) Two (b) Five
Therefore, option (b) is the correct answer. (c) Ten (d) One
+7 –2 +
+2 2+ +
0
3. A sulphur containing species that can not be a reducing agent is: Sol. 2KMnO4  5H2S + 6H  2Mn + 2K + 5S + 8H2O
Oxidation
(a) SO2 (b) SO3−2 (c) H2SO4 (d) S2O32−
H2S  R.A.  Reductant
+6
Sol. H 2SO 4 –2 O
So, S → S + 2e –
H2SO4 because sulphur has its maximum O.S. i.e. + 6
2 moles of electrons are involved in oxidation of 1 mole of
Therefore, option (c) is the correct answer. reductant.
4. Which of the following reaction involves neither oxidation Therefore, option (a) is the correct answer.
nor reduction?
8. In redox reaction:
(a) CrO42– → Cr2O72– (b) Cr → CrCl3 Fe + HNO3 → Fe(NO3)2 + NH4NO3 + H2O
(c) Na → Na+ (d) 2S2O32– → S4O62– the coefficient of HNO3, Fe(NO3)2, NH4NO3 is:
+6 +6 (a) 1 : 10 : 4 (b) 10 : 4 : 1
Sol. CrO 2 − → Cr O 2 − (c) 4 : 10 : 1 (d) 10 : 1 : 4
4 2 7
No change in O.S. Sol. Fe + HNO3 → Fe(NO3)2 + NH4NO3 + H2O
Therefore, option (a) is the correct answer. Half reaction method:
5. Balance the following equations: Fe → Fe2+ + 2e– ....(1) × 4
(a) H2O2 + MnO4– → Mn+2 + O2 (acidic medium) NO3− + 10H ⊕ + 8e  → NH ⊕
4 + 3H 2 O ...(2)

(b) Zn + HNO3 (dil.) → Zn(NO3)2 + H2O + NH4NO3 Equation (1) × 4 + (2)

(c) CrI 3 + KOH + Cl 2 → K 2 CrO 4 + KIO 4 + KCl → 4Fe2+ + NH ⊕
4Fe + NO3− + 10H ⊕  4 + 3H 2 O
+ H2O n
Add of spectator ion
(d) P2H4 → PH3 + P4 4Fe + 10HNO3 → 4Fe(NO3)2 + NH4NO3 + 3H2O
(e) Ca3 (PO4)2 + SiO2 + C → CaSiO3 + P4 + CO Therefore, option (b) is the correct answer.

Redox Reaction 41
 9. Calculate the normality of a solution containing 13.4 g of g
Sodium oxalate in 100 mL solution.
⇒ × 1000 =
7.5
87 / 2
wt. in g / eq.wt
Sol. Normality = (MnO2 + 4H+ → Mn2+ + 2H2O + 2e–)
vol. of solution in litre

⇒ g = 0.326
Here, eq. wt. of Na2C2O4 = 134/2 = 67
0.326
13.4 / 67 % MnO2 = × 100 =
65.25%
so N = = 2N 0.5
100 /1000
10. What volume of 6 M HNO3 is needed to oxidize 8 g of Fe2+ 13. The neutralization of a solution of 1.2 gm of mixture of
to Fe3+, where HNO3 gets converted to NO? H2C2O4. 2H2O and KHC2O4.H2O and some impurities which
(a) 8 mL (b) 7.936 mL are neutral, consumed 40.0 mL of 0.25 N NaOH. On the other
(c) 32 mL (d) 64 mL hand, on titration with KMnO4 in acidic medium, 0.4 gm of
mixture required 40.0 mL of 0.125 N KMnO4. Find the molar
Sol. Meq. of HNO = Meq. of Fe2+ n-factor = 3
3 ratio of the components.
8 Sol. Note that the mass of two samples is different in two titrations.
or 6 × 3 × =
V ×1000
56 +5   2+ Let x = mmoles of H2C2O4. 2H2O 
V = 7.936 mL (NO3– → NO)  in 0.4 g sample
and y = mmoles of KHC2O4. H2O 
11. In the reaction, 2S2O32– + I2 → S4O62– + 2I–, the eq. wt. of So mmoles of oxalic acid in 1.2gm sample = 3x and mmoles
Na2S2O3 is equal to its: of bioxalate in 1.2 gm sample = 3y
(a) Mol. wt. (b) Mol. wt./2 1. Neutralisation with NaOH :
(c) 2 x Mol. wt. (d) Mol. wt./6
meq of H2C2O4. 2H2O + meq of KHC2O4. H2O = meq of
Sol. 2S2O3 + I2
2–
S4O62– + 2I NaOH
O.N. = 2 O.N. = 2.5
2 × 3x + 1 × 3y = 0.25 × 40
v.f. = (0.5) × 2 = 1 [oxalic acid has 2 H+ ions while bioxalate has only 1 H+]
Μ ol.wt. 10
⇒ Eq. wt. (S2O32–) =
⇒ 2x + y = ...(i)
1 3
Therefore, option (a) is the correct answer. 2. Redox reaction with KMnO4:
12. A sample of Pyrolusite (MnO2) weighs 0.5 gm. To this meq of H2C2O4.2H2O + meq of KHC2O4. H2O = meq of
solution, 0.594 gm of As2O3 and a dil. acid are added. After KMnO4
the reaction has ceased, As 3+ in As 2O 3 is titrated with 2 × x + 2 × y = 0.125 × 40
45 mL of M/50 KMnO4 solution. Calculate the % of MnO2 –
[HC2O4 → 2CO2 + H+ + 2e–]
in pyrolusite. (Molar mass of Ar2O3 = 198) 2–
Sol. MnO2 + As2O3 → Mn2+ + AsO4
3– [C2O4 → 2CO2 + 2e–]
0.5 gm 0.594 gm ⇒ x + y = 2.5 ...(ii)
For excess of As2O3 5 5
Solve for x and y to get : x = and y =
–
As2O3 + MnO4 → Mn2+ + AsO4
3–
6 3
EAs O = ? ⇒x:y=1:2
2 3
(As2O3 + 5H2O → 2AsO43– + 10 H+ + 4e–) 14. KMnO4 solution is to be standardised by titration against
198 As2O3(s).A 0.1097 g sample of As2O3 (M = 198) requires

⇒ E As2 O3 =
4 26.10 ml of the KMnO4 solution for its titration. What are
0.594 the molarity and normality of the KMnO4 solution?
meq of As2O3 taken = × 1000 =
12
198 / 4 Sol. Mn7++ 5e¯ → Mn2+(Reduction)
meq of excess As2O3 = meq of KMnO4 As23+ → 2 As5++ 4e¯ (oxidation)
1 \ Meq. of As2O3 = meq of KMnO4
= 45 × × 5 = 4.5
50
0.1097
– × 1000 = 26.10 × N
MnO4 + 5e– + 8H+ → Mn2+ + 4H2O 198
(EAs O = M/4)
Note that the number of electron transfer for As2O3 in two 4 2 3

reactions is same. \ NKMnO = 0.085

4
so meq. of As2O3 used for MnO2 = 12 – 4.5 = 7.5 0.085
\ MKMnO = = 0.017
meq of MnO2 = 7.5 4 5

42 P JEE Dropper Module-1 CHEMISTRY

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 15. 100 ml solution of FeC2O4 and FeSO4 is completely oxidized 0.84X
by 60 ml of 0.02 M KMnO4 in acid medium.The resulting × 1000 =
X.N. ⇒ N = 0.15
100 × 56
solution is then reduced by Zn and dil.HCl. The reduced
SK = N × E = 0.15 × 49 = 7.35 g/L
solution is again oxidized completely by 40ml 0.02 M 2Cr2O7

KMnO4. Calculate normality of FeC2O4 and FeSO4 in 294

=
( E = 49 ) (E = equivalent)
mixture. 6

Sol. Consider the redox reaction 17. What mass of K2Cr2O7 is required to produce 5.0 litre CO2
at 75ºC and 1.07 atm pressure from excess of oxalic acid.
FeC2O4: Fe2+ → Fe3+ + e¯ (Oxidation)
Also report the volume of 0.1 N NaOH required to neutralise
(N1) C23+ → 2C4+ + 2e¯ (Reduction) the CO2 evolved.
________________________________________ 6+
Sol. Cr2 + 6e¯ → 2Cr3+
FeC2O4 → Fe3+ + 2CO2 + 3e¯ (V.f. = 3) 3+
C2 → 2C4+ + 2e¯
FeSO4 : Fe2+ → Fe3+ + e¯ (V.f. = 1)
meq. of K2Cr2O7 = meq. of CO2 formed
(N2)
= mole of CO2 × 1000 × 1 (V.f for CO2 = 1)
KMnO4 : Mn7+ + 5e¯ → Mn2+
PV 1.07 × 5 × 1000
100 (N1 + N2) = 60 × 0.02 × 5 = × 1× 1000= = 187.3
RT 0.0821× 348
(N1 + N2) = 3 × 0.02 ...(i)
w K 2Cr2O7
The resulting solution now contains only Fe3+ ions because \ × 1000 =
187.3
M/6
CO2 escapes out. The solution is reduced to Fe2+ by Zn and
187.3 × M 187.3 × 294
dil.HCl.KMnO4 oxidises these Fe2+ again, therefore meq. or wK = =
2Cr2O7 6 × 1000 6 × 1000
of Fe2+ from FeC2O4 + meq. of Fe2+ from FeSO4 = meq. of
w = 9.18 g (MK = 294)
KMnO4 2Cr2O7
CO2 + 2NaOH → Na2CO3 + H2O (V.f. for CO2 = 2)
N 
100  1 + N 2  =40 × 0.02 × 5 Also meq. of NaOH = meq. of CO2
 3 
0.1 × V = 187.3 × 2 ⇒ V = 3.746 L
 N1 
 + N2  =
2 × 0.02 18. 2.480 g of KClO3 are dissolved in conc.HCl and the solution

3  ...(ii)
was boiled. Chlorine gas evolved in the reaction was then
2N1 passed through a solution of KI and liberated iodine was
= 0.02
3 titrated with 100 ml of hypo.12.3 ml of same hypo solution
N1 = 0.03, N2 = 0.03 required 24.6ml of 0.5 N iodine for complete neutralization.
Calculate % purity of KClO3 sample.
16. 0.84 g iron containing X percent of iron was taken in a
Sol. 2KClO3 + 12 HCl → 2KCl + 6H2O + 6Cl2
solution containing all the iron in ferrous state. The solution
required X ml of a potassium dichromate solution for Cl2 + 2KI → 2 KCl + I2
oxidation of iron content to ferric state. Calculate the strength Also meq. of I2 = meq. of hypo = 100 × 1
(in g/L) of potassium dichromate solution. [ NHypo × 12.3 = 24.6 × 0.5, ∴ NHypo = 1]
Valencefactor = 2 Valence factor =1
Sol. Fe → Fe2+ + 2e¯  → 100
by Cr O 2–
2 7 Also m M of Cl2 = mM of I2 = = 50
Fe3+ + e¯ 2
2 × mM of Cl2 2 × 50 50
(Oxidation) Also mM of KClO3 = = =
6 6 3
6e¯ + Cr26+ → 2Cr3+(Reduction)
w KClO3 50
0.84X \ × 1000 =⇒ wKClO = 2.042
WFe = 122.5 3 3
100 (Given)
2.042
Meq. of Fe2+ in solution (V.f. = 1) = meq. of K2Cr2O7 \ % KClO3= × 100= 82.34%
2.48

Redox Reaction 43
 PRARAMBH (TOPICWISE)

OXIDATION NUMBER, REDOX REACTIONS, 13. Which one of the following is not a redox reaction?
REDUCING AGENT AND OXIDISING AGENT (a) CaCO3 → CaO + CO2
(b) 2H2 + O2 → 2H2O
1. In Ni(CO)4, the oxidation state of Ni is:
1
(a) 4 (b) 0 (c) 2 (d) 8 (c) Na + H2O → NaOH + H2
2
2. The oxidation number of C in CH4, CH3Cl, CH2Cl2, CHCl3 1
and CCl4 are respectively: (d) MnCl3 → MnCl2 + Cl2
2
(a) +4, +2, 0, –2, –4 (b) +2, +4, 0, –4, –2
(c) –4, –2, 0, +2, +4 (d) –2, –4, 0, +4, +2 14. In the reaction: MnO −4 + SO32– + H+ → SO42– + Mn2++ H2O
– −
3. The oxidation number of Pt in [Pt(C2H4)Cl3] is: (a) MnO 4 and H+ both are reduced
(a) +1 (b) +2 (c) +3 (d) +4 −
(b) MnO 4 is reduced and H+ is oxidised
4. Oxidation number of C in HNC is: −
(c) MnO 4 is reduced and SO32– is oxidised
(a) +2 (b) –3 (c) +3 (d) Zero
−
5. Oxidation number of carbon in carbon suboxide (C3O2) is: (d) MnO 4 is oxidised and SO32– is reduced
+2 +4 −4 15. I2 + KI → KI3
(a) (b) (c) +4 (d)
3 3 3 In the above reaction:
6. Oxidation number of sulphur in Na2S2O3 would be: (a) Only oxidation takes place
(a) +2 (b) +4 (c) –2 (d) 0 (b) Only reduction takes place
−1 (c) Both the above
7. oxidation state of nitrogen will be obtained in case of: (d) None of the above
3
(a) Ammonia (NH3) (b) Hydrazoic acid (N3H) 16. Match List-I (compound) with List-II (Oxidation state of N) and
(c) Nitric oxide (NO) (d) Nitrous oxide (N2O) select the correct answer using the codes given below the list:

8. Which one of the following is a redox reaction? List-I List-II

(a) H2 + Br2 → 2HBr A. KNO3 (p) – 1/3
(b) 2NaCl + H2SO4 → Na2SO4 + 2HCl
B. HNO2 (q) – 3
(c) HCl + AgNO3 → AgCl + HNO3
(d) NaOH + HCl → NaCl + H2O C. NH4Cl (r) 0
9. Which of the following change represents a dispro­ D. NaN3 (s) +3
portionation reaction (s)?
(t) +5
(a) Cl2 + 2OH– → ClO– + Cl– + H2O
(b) Cu2O + 2H+ → Cu + Cu2+ + H2O (a) (A-t), (B-s), (C-q), (D-p) (b) (A-t), (B-q), (C-s), (D-p)
dilution with (c) (A-s), (B-t), (C-p), (D-r) (d) (A-q), (B-r), (C-s), (D-t)
(c) 2HCuCl2  → Cu + Cu2+ + 4Cl– + 2H+
Water 17. In the conversion of Br2 to BrO3– the oxidation state of
(d) All of the above bromine changes from:
10. The reaction H2S + H2O2 → S + 2H2O manifests: (a) 0 to 5 (b) 1 to 5 (c) 0 to –3 (d) 2 to 5
(a) Oxidising action of H2O2 18. The sum of oxidation states of sulphur in H2S2O8 is:
(b) Reducing nature of H2O2 (a) +2 (b) +6 (c) +7 (d) +12
(c) Acidic nature of H2O2 19. When H2 reacts with Na, here H2 acts as:
(d) Alkaline nature of H2O2 (a) Oxidising agent (b) Reducing agent
11. The compound that can work both as an oxidising as well (c) Both (d) None of these
as reducing agent is: 20. Which one is the oxidising agent in the reaction given below?
(a) KMnO4 (b) H2O2 2CrO42– + 2H+ → Cr2O7–2 + H2O
(c) Fe2(SO4)3 (d) K2Cr2O7 (a) H+ (b) Cr2O 7−2
(c) Cr ++ (d) None of these
12. Select the example of disproportionation reaction
(a) BaCl2 + H2SO4 → BaSO4 + 2HCl 21. The oxidation number of arsenic atom in H3AsO4 is:
(b) NH4NO3 → N2O + 2H2O (a) –1 (b) –3 (c) +3 (d) +5
(c) 4H3PO3 → PH3 + 3H3PO4 22. In substance Mg(HXO3), the oxidation number of X is:
(d) AgCl + 2NH3 → Ag(NH3)2Cl (a) 0 (b) +2 (c) +3 (d) +4

44 P JEE Dropper Module-1 CHEMISTRY

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23. In the reaction: C + 4HNO3 → CO2 + 2H2O + 4NO2 32. In the following reaction the value of ‘X’ is
HNO3 acts as: H2O + SO32– → SO42– + 2H+ + X
(a) An oxidising agent (b) An acid (a) 4e– (b) 3e– (c) 2e– (d) 1e–
(c) A reducing agent (d) None of these
33. In the reaction: A–n2 + xe– → A–n1, here x will be
24. The oxidation number of iron in potassium ferricyanide
K3[Fe (CN)6] is: (a) n1 + n2 (b) n2 – n1 (c) n1 – n2 (d) n1 . n2
(a) Two (b) Six (c) Three (d) Four
25. Iodine shows the highest oxidation state in the compound:
USE OF VALENCY FACTOR (n-FACTOR)
(a) KI (b) KI3 (c) IF5 (d) KIO4 34. The number of mole of oxalate ions oxidised by one mole
26. Zn + H2SO4 → ZnSO4 + H2. Here Zn undergoes: of MnO4– is:
(a) Reduction (a) 1/5 (b) 2/5 (c) 5/2 (d) 5
(b) Oxidation 35. How many moles of KMnO4 are reduced by 1 mole of ferrous
(c) Both oxidation and reduction oxalate in acidic medium?
(d) None of these 1 5 1 3
27. In the following reaction (a) (b) (c) (d)
5 3 3 5
2FeCl3 + H2S → 2FeCl2 + 2HCl + S
(a) FeCl3 is oxidant EQUIVALENT WEIGHT
(b) FeCl3 & H2S are oxidised
36. Equivalent weight of N2 in the change N2 → NH3 is
(c) FeCl3 is oxidised & H2S is reduced
28 28 28
(d) None of these (a) (b) 28 (c) (d)
6 2 3
BALANCING OF REDOX REACTIONS 37. Equivalent weight of NH3 in the change N2 → NH3 is:
28. Choose the set of coefficients that correctly balances the
following equation: x Cr2O72– + yH+ + z e– → a Cr+3 + bH2O 17 17 17
(a) (b) 17 (c) (d)
x y z a b 6 2 3
(a) 2 14 6 2 7 38. The eq. wt. of iodine in, I2 + 2S2O32– → 2I– + S4O62– is
(b) 1 14 6 2 7 (a) Mol. wt. (b) Mol. wt./2
(c) 2 7 6 2 7 (c) Mol. wt./4 (d) None of these
(d) 2 7 6 1 7 39. Molecular weight of KBrO3 is M. What is its equivalent
29. The value of n in: MnO −4 +8H++ ne– → Mn2++ 4 H2O is weight, if the reaction is: BrO3– → Br– (acidic medium)
(a) 5 (b) 4 (c) 3 (d) 2 (a) M (b) M/4 (c) M/6 (d) 6M
30. What is the value of n in the following equation: 40. Equivalent wt. of H3PO4 in each of the reaction will be
Cr(OH) −4 + OH– → CrO42– + H2O + ne– ? respectively:
(a) 3 (b) 6 (c) 5 (d) 2 H3PO4 + OH– → H2PO4– + H2 O
31. For the redox reaction H3PO4 + 2OH– → HPO42– + 2H2 O
Zn + NO3− → Zn2+ + NH4+ in basic medium, coefficients of H3PO4 + 3OH– → PO43– + 3H2 O
Zn, NO3− and OH– in the balanced equation respectively are: (a) 98, 49, 32.67 (b) 49, 98, 32.67
(a) 4, 1, 7 (b) 7, 4, 1 (c) 4, 1, 10 (d) 1, 4, 10 (c) 98, 32.67, 49 (d) 32.67, 49, 98

PRABAL (JEE MAIN LEVEL)

1. Oxidation number of S in H2SO5 is 6. This is observed,
because:
(a) There are five oxygen atoms in the molecule.
(b) The hydrogen atom is directly linked with non-metal.
(c) There is peroxide linkage in the molecule.
(d) The sulphur atom shows co-ordinate linkage.
2. Oxygen has an oxidation state of +2 in the compound:
(a) H2O2 (b) CO2 (c) H2O (d) F2O
3. Oxidation number of Fe in Fe3O4 is fractional because:
(a) It is a mixed [Fe(+2), Fe(+4)] oxide.
(b) It is a non-stoichiometric compound.
(c) It is a mixed [Fe(+2), Fe(+3)] oxide.
(d) None of the above.
4. The following equations are balanced atomwise and
chargewise.
(i) Cr2O72– + 8H+ + 3H2O2 → 2Cr3+ + 7H2O + 3O2

Redox Reaction 45
 (ii) Cr2O72– + 8H+ + 5H2O2 → 2Cr3+ + 9H2O + 4O2 15. In the reaction xHI + yHNO3 → NO + Ι2 + H2O, upon
(iii) Cr2O72– + 8H+ + 7H2O2 → 2Cr3+ + 11H2O + 5O2 balancing with whole number coefficients:
The precise equation/equations representing the oxidation (a) x = 3, y = 2 (b) x = 2, y = 3

of H2O2 is/are: (c) x = 6, y = 2 (d) x = 6, y = 1
(a) (i) only (b) (ii) only 16. For the redox reaction MnO4– + C2O42– + H+ → Mn2+
(c) (iii) only (d) All the three + CO2 + H2O, the correct whole number stoichiometric
coefficients of MnO4–, C2O42– and H+ are respectively:
5. Oxidation number of cobalt in [Co(NH3)6]Cl2Br is: (a) 2, 5, 16 (b) 16, 5, 2
(a) + 6 (b) Zero (c) + 3 (d) + 2 (c) 5, 16, 2 (d) 2, 16, 5
6. State which of the following reactions is neither oxidation 17. An example of redox process is:
nor reduction:
(a) CuSO4 + Fe → FeSO4+ Cu
(a) Na → NaOH (b) Cl2 → Cl– + ClO–3
(b) Ca(OH)2 + 2HCl → CaCl2 + 2H2O
(c) P2O5 → H4P2O7 (d) Zn + H2SO4 → ZnSO4 + H2
(c) CaO + 2HCl → CaCl2 + H2O
7. Select the pair of oxidation processes, (d) CaCO3 → CaO + CO2
(A) 2Cu2+ → Cu22+ 18. Consider the following statement in the reaction
(B) MnO4¯ → Mn2+ KIO3 + 5KI + 6HCl → 3I2 + 6KCl + 3H2O
(C) [Fe(CN)6]–4 → [Fe(CN)6]–3 (A) KI is oxidised to I2
(D) 2I¯→ I2 (B) KIO3 is oxidised to I2
(a) A, B (b) C, D (c) A, D (d) B, C (C) KIO3 is reduced to I2
8. Phosphorus has the oxidation state of +3 in: (D) Oxidation number of I increases from (–1) in KI to zero
(a) Ortho phosphoric acid (H3PO4) in I2
(b) Phosphorus acid (H3PO3) Among these statements
(c) Meta phosphoric acid (HPO3) (a) A, C and D are correct. (b) A, B and D are correct.
(d) Pyrophosphoric acid (H4P2O7) (c) B and D are correct. (d) A alone is correct.
9. Which one of the following statements is not correct? 19. Balance the following equation and choose the quantity
which is the sum of the coefficients of reactants and products:
(a) Oxidation state of S in (NH4)2S2O8 is +6
KMnO4 +....... H2O2 +....... H2SO4 → ....... MnSO4 +.......
(b) Oxidation number of Os in OsO4 is +8
O2 +....... H2O +....... K2SO4
(c) Oxidation state of S in H2SO5 is +8
(a) 26 (b) 23 (c) 28 (d) 22
1
(d) Oxidation number of O in KO2 is – 20. In the redox reaction:
2
x MnO + y PbO2 + z HNO3 → a HMnO4 + b Pb(NO3)2
10. Oxidation state of nitrogen is incorrectly given for:
+ c H2O
Compound Oxidation State
(a) x = 2, y = 5, z = 10 (b) x = 2, y = 7, z = 8
(a) [Co(NH3)5Cl]Cl2 –3
(c) x = 2, y = 5, z = 8 (d) x = 2, y = 5, z = 5
(b) NH2OH –1
21. In the redox reaction:
(c) (N2H5)2SO4 +2
10FeC2O4 + x KMnO4 + 24H2SO4 →
(d) Mg3N2 –3
5Fe2 (SO4)3 + 20CO2 + y MnSO4 + 3 K2SO4 + 24H2O.
+
11. H MoO → MoO . In the process, H MoO
2 4 2 2 4 The values of x and y are respectively:
(a) Acts as a reducing agent. (a) 6, 3 (b) 3, 6 (c) 3, 3 (d) 6, 6
(b) Acts as an oxidising agent.
22. The number of electrons lost or gained during the change:
(c) Acts both as a reducing and oxidising agent.
3Fe + 4H2O → Fe3O4 + 4H2
(d) None of these.
(a) 2 (b) 4 (c) 6 (d) 8
12. Two oxidation states for chlorine are found in the compound: 23. (NH4)2 Cr2 O7 → Cr2O3 + N2 + 4H2O
(a) CaOCl2 (b) KCl (c) KClO3 (d) Cl2O7 In the above reaction the oxidation state of N and
13. One mole of iron, when oxidised to +2 oxidation state gives up: chromium changes respectively as:
(a) 1NA electron (b) 2NA electron (a) – 3 to 0 and + 6 to + 3 (b) + 3 to 0 and + 3 to + 6
(c) 3NA electron (d) 0.5 mole of electron (c) – 4 to 0 and + 6 to + 2 (d) Unpredictable
14. In which of the following compounds iron has lowest 24. How many electrons should A2H3 liberate so that in the
oxidation state? new compound A shows –1/2 oxidation number- (E.N. of
A > E.N. of H)
(a) FeSO4(NH4)2SO4.6H2O (b) K4Fe(CN)6
(a) 2 (b) 3 (c) 4 (d) 5
(c) Fe(CO)5 (d) Fe0.94O

46 P JEE Dropper Module-1 CHEMISTRY

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 25. Number of moles of electrons produced per mole of 34. Which of the following reaction is spontaneous oxidation–
FeCr2O4 in the following redox reaction is ...... reduction reaction?
FeCr2O4 + KOH + O2 → K2CrO4 + Fe2O3 (a) Mn+2+ 5Fe+3 + 4H2O → MnO4– + 5Fe+2 + 8H+
(a) 6 (b) 1 (c) 7 (d) 3 (b) MnO4– + 5Fe+3 + 8H+ → Mn+2 + 5Fe+2 + 4H2O
26. x(g) of the metal gave y g of its oxide. Hence equivalent (c) MnO4– + 5Fe+2 + 8H+→ Mn+2 + 5Fe+3 + 4H2O
weight of the metal (d) Mn+2+5Fe+2 + 4H2O → MnO4– + 5Fe+3 + 8H+
y−x x x x+y 35. A compound contains atoms A, B and C. The oxidation
(a) × 8 (b) × 8 (c) × 8 (d) ×8 number of A is +2, of B is +5 and of C is –2. The possible
x (y − x) y x
formula of the compound is:
27. Equivalent weight of Mn3+ in the following reaction is (a) ABC2 (b) B2(AC3)2 (c) A3(BC4)2 (d) A3(B4C)2
(Mn = 55) Mn3+ → Mn2+ + MnO2
36. The molar mass of CuSO4.5 H2O is 249. Its equivalent mass
(a) 27.5 (b) 55 (c) 110 (d) 165
in the reaction (a) and (b) would be
28. Equivalent weight of FeC2O4 in the change, (A) Reaction CuSO4 + KI → product.
FeC2O4 → Fe3+ + CO2 is (B) Electrolysis of CuSO4 solution.
(a) M/3 (b) M/6 (c) M/2 (d) M/1 (a) (A) 249 (B) 249 (b) (A) 124.5 (B) 124.5
29. In the ionic equation, 2K+BrO3– + 12H+ + 10e– → Br2 + (c) (A) 249 (B) 124.5 (d) (A) 124.5 (B) 249
6H2O + 2K+, the equivalent weight of KBrO3 will be
(where M = molecular weight of KBrO3): INTEGER TYPE QUESTIONS
(a) M/5 (b) M/2 (c) M/6 (d) M/4 37. A solution containing 2.68 × 10–3 mol of An+ ions requires
30. If one mole of H2SO4 reacts completely with one mole of 1.61 × 10–3 mol of MnO −4 for the complete oxidation of An+
NaOH, equivalent weight of H2SO4 will be: to AO3− in acidic medium. What is the value of n?
(a) 98 (b) 49 (c) 96 (d) 48 38. 10 moles of Mohr’s salt and Fe2(SO4)3 mixture requires one
31. The equivalent weight of a metal is double that of oxygen. litre of 1 M K2Cr2O7 for complete oxidation. The number of
How many times is the weight of its oxide greater than weight mole of Mohr’s salt in mixture is___________
of the metal? 39. 40 mL of X mol/litre formic acid is oxidised completely
(a) 1.5 (b) 2 (c) 0.5 (d) 3 with 16 mL of 0.25 M oxidant. What is pH of formic acid?
32. (NH4)3PO4 gets converted into NO3¯ and PH3 on reacting Assume 100% ionisation of acid.
with KMnO4 in acidic medium. If 50 ml of 0.2 M (NH4)3PO4 40. 10 mL of 0.2 M solution of KxH(C2O4)y requires 8 mL of
solution reacts completely with 16 ml of KMnO4 solution, 0.2 M acidified KMnO4 solution. The value of x is ______
then normality of KMnO4 solution is 41. Find out the % of oxalate ion in given sample of oxalate salt
(a) 5 (b) 8 (c) 10 (d) 20 of which 0.3 g present in 100 mL of solution required 90 mL
33. The number of moles of NaOH required to completely react of (N/20) KMnO4 for complete oxidation.
with 20 ml of 0.1 M NaH2PO3 solution and 40 ml of 0.1 M 42. What is the coefficient for OH– when the equation __Br2
NaHCO3 is ....... + __OH– → __ Br– + __BrO–3 + __H2O is balanced with
(a) 8 × 10–3 (b) 2 × 10–3 (c) 4 × 10–3 (d) 6 × 10–3 the smallest integer coefficients?

PARIKSHIT (JEE ADVANCED LEVEL)

SINGLE CORRECT TYPE QUESTIONS 4. 1 litre solution of KIO3 of unknown molarity is given to
titrate with KI in strong acid medium. 50 mL solution of
1. Which of the following compound does not decolourize an KIO3 requires 10 mL of 0.1 M KI for complete reduction to
acidified solution of KMnO4? I2. The molarity of KIO3 solution is:
(a) SO2 (b) FeCl3 (c) H2O2 (d) FeSO4 (a) 4 × 10–3 M (b) 4 × 10–4 M (c) 4 × 10–5 M (d) 4 × 10– 2 M
2. What is equivalent mass of (NH4)2Cr2O7 in the change 5. Hg5(IO6)2 oxidizes KI to I2 in acid medium and the other
(NH4)2Cr2O7 → N2 + Cr2O3 + 4H2O ? product containing iodine is K2HgI4. If the I2 liberated in
the reaction requires 0.004 mole of Na2S2O3, the number of
M M M M moles of Hg5(IO6)2 that have reacted is:
(a) (b) (c) (d)
2 3 4 6 (a) 10– 3 (b) 10– 4 (c) 2.5 × 10– 4(d) 2.5 × 10– 2
3. Excess of KI reacts with CuSO4 solution and then Na2S2O3 6. If M represents molecular mass of Mn3O4 then what will
solution is added to it. Which of the statements is incorrect be its equivalent mass if it undergoes disproportionation
in this reaction? reaction as shown: Mn3O4 → MnO4– + Mn2+
(a) Evolved I2 is reduced (b) CuI2 is formed M M 15M 26M
(c) Na2S2O3 is oxidised (d) Cu2I2 is formed (a) (b) (c) (d)
13 2 26 15

Redox Reaction 47
 7. The CO in a 20.3 L sample of gas was converted to CO2 by 16. Choose the correct statement(s):
passing the gas over iodine pentoxide heated to 150° C: (a) 1 mole of MnO4– ion can oxidise 5 moles of Fe2+ ion
I2O5 (s) + 5 CO(g) → 5 CO2(g) + I2(g) in acidic medium.
The iodine distilled at this temperature and was collected in (b) 1 mole of Cr2 O72– ion can oxidise 6 moles of Fe2+ ion
an absorber containing 8.25 mL of 0.01101 M Na2S2O3. The in acidic medium.
excess hypo was back-titrated with 2.16 mL of 0.00947 M (c) 1 mole of Cu2S can be oxidised by 1.6 moles of MnO4–
I2 solution. The milligrams of CO in 1 L of the original gas ion in acidic medium.
sample was therefore: (d) 1 mole of Cu2S can be oxidised by 1.33 moles of Cr2O72–
ion in acidic medium.
(a) 0.172 mg (b) 0.283 mg
17. A quantity of 0.5 g of a metal nitrate gave 0.43 g of metal
(c) 0.349 mg (d) 0.506 mg sulphate.
8. In the following conversion of sulphide of phosphorous (a) The equivalent weight of the metal is 38.
P4S3 → P2O5 + SO2 (b) The equivalent weight of the metal is 76.
Equivalent weight of P4S3 (molecular weight = M) is: (c) The atomic weight of metal may be 76.
M M M M (d) The atomic weight of metal may be 19.
(a) (b) (c) (d)
14 18 32 38 18. Which of the following samples of reducing agents is /
9. Equivalent mass of Ba(MnO4)2 in acidic medium is: (where are chemically equivalent to 25 mL of 0.2 N KMnO4 to be
M stands for molar mass) reduced to Mn2+ and water?
(a) M/5 (b) M/6 (c) M/10 (d) M/2 (a) 25 mL of 0.2 M FeSO4 to be oxidized to Fe3+
10. Equivalent mass of Fe0.9 O in reaction with acidic K2Cr2O7 (b) 50 mL of 0.1 M H3AsO3 to be oxidized to H3AsO4
is: (M = Molar mass) (c) 25 mL of 0.1 M H2O2 to be oxidized to H+ and O2
(a) 7 M/10 (b) 10 M/7 (c) 7 M/9 (d) 9 M/7 (d) 25 mL of 0.1 M SnCl2 to be oxidized to Sn4+
11. Equivalent weight of oxalic acid salt in following reaction 19. 250 ml of 1M I2 is separately reacted with 0.5 M Cu2S
is: (Atomic masses: O = 16, C = 12, K = 39) solution, 0.5 M CuS solution and 0.5 M S2O32– solution,
causing production of Cu+2 and SO42– in the first two and
H2C2O4 + Ca(OH)2 → CaC2O4 + H2O
S4O62– in the last case along with iodide ions. Which of the
(a) 90 (b) 45 following options is /are correct assuming 100% completion
(c) 64 (d) 128 of the reaction?
(a) 100 ml of Cu2S solution will be consumed.
MULTIPLE CORRECT TYPE QUESTIONS (b) 125 ml of CuS solution will be consumed.
12. Substances which may be oxidized as well as reduced are (c) 500 ml of S4O62– solution will be consumed.
(a) HCl (b) HClO (d) Equivalent weight of I2 in each of the reactions will be 127.
(c) HClO3 (d) HClO4
13. Which of the following is a non-redox process? COMPREHENSION TYPE QUESTIONS
2− 2− 2−
(a) SO4 → SO3 (b) Cr2O7 → CrO4 Comprehension (Q. 20 to 22): For the reaction: MnBr2 + PbO2
3− 4− 2− + HNO3 → HMnO4 + Pb(BrO3)2 + Pb(NO3)2 + H2O
(c) PO4 → P2O7 (d) C2O4 → CO2
(Atomic masses: Mn = 55, Br = 80, Pb=208)
14. If mass of KHC2O4 (potassium acid oxalate) required to
20. The equivalent weight of MnBr2 is
reduce 100 mL of 0.02 M KMnO4 in acidic medium is x g
and to neutralise 100 mL of 0.05 M Ca(OH)2 is y g, then (a) 107.5 (b) 215 (c) 12.65 (d) 19.55
which of the following options may be correct : 21. The equivalent weight of PbO2 is:
(a) If x is 1 g then y is 2 g (a) 120 (b) 240 (c) 14.11 (d) 21.82
(b) If x is 5.5g then y is 11 g 22. The equivalent weight of HNO3 is:
(c) If x is 2 g then y is 1 g (a) 63 (b) 55.6
(d) If x is 11 g then y is 5.5 g (c) 31.5 (d) 111.18
15. In the titration of K2Cr2O7 and ferrous sulphate, following
data is obtained: MATCH THE COLUMN TYPE QUESTIONS
V 1 mL of K 2 Cr 2 O 7 solution of molarity M 1 requires 23. Container–I may contain 1 mol K2Cr2O7 or 1 mol KMnO4
V2 mL of FeSO4 solution of molarity M2. in acidic medium. This container–I is mixed with other
Which of the following relations is/are true for the above Container–II, III, IV or V, due to which compound present
titration: in these containers undergo following half reaction.
(a) 6 M1V1 = M2V2 (b) M1V1 = 6 M2V2 KI → IO3− , K2C2O4 · 3H2C2O4 · 3H2O → CO2
(c) N1V1 = N2V2 (d) M1V1 = M2V2 Cu2S → Cu2+ + SO2

48 P JEE Dropper Module-1 CHEMISTRY

W
 NH4SCN → SO 24− + HCN INTEGER TYPE QUESTIONS
24. A 458 g sample containing Mn3O4 was dissolved and all
manganese was converted to Mn 2+. In the presence of
KMnO4
or KI Cu2S fluoride ion, Mn2+ is titrated with 3 lit of KMnO4 solution
K2Cr2O7 (which was 1.25 N against oxalate in acidic medium), both
reactants being converted to a complex of Mn(III). What
Container-I Container-II Container-III was the % of Mn3O4 in the sample?
25. 80 gm of a sample of Anhydrous CuSO4 was dissolved in
K2C2O4 water and volume made upto 250ml. 25 ml of this solution
3H2C2O4 NH4SCN after taking usual precautions was treated with a little
3H2O excess of KI solution. A white ppt. of Cu2I2 and iodine was
produced. The iodine so evolved required 40 ml of 1 M of
Container-IV Container-V hypo solution. What is the approximate percentage purity
Column–I represents the two container which are mixed. of CuSO4 solution? [Mol. wt. of CuSO4 = 160]
Column–II represents the number of moles of substance which 26. Find the value of 2 × Ratio of moles of oxidant to reductant
reacts with 1 mol of substance (may be KMnO4 or K2Cr2O7) in the following reaction.
present in container–I. CrI3 + Cl2 + KOH → K2CrO4 + KIO4 + KCl

Match the Column–I with Column–II. 27. A mixture of NaHC2O4 and KHC2O4 . H2C2O4 is required for
complete neutralization by 0.12 NaOH and 0.04 M KMnO4
Column-I Column-II separately. The molar ratio of NaHC2O4 and KHC2O4 .
A. Container–I + p. 3 H2C2O4 is:
Container–III 4 28. A 1.100 g sample of copper ore is dissolved and the Cu2+
of it is treated with excess KI. The liberated I2 requires
B. Container–II + q. 5 12.12 mL of 0.10 M Na2S2O3 solution for titration. What is
Container–I 8 % copper by mass in the ore? (At mass of Cu = 63.6)
C. Container–I + r. 1
Container–V NUMERICAL TYPE QUESTIONS
D. Container–IV + s. 5 29. What mass (in g) of Na2S2O3 . 5H2O is needed to make 500
cm3 of 0.200 N solution for the reaction:
Container–I 6
2S2O32– + I2 → S4O62– + 2I– ? (Upto one decimal place)

(a) A → p,q; B → r,s; C → r,s; D → p,q
(b) A → s,r; B → p,q; C → r,s; D → p,q
(c) A → r,q; B → r,s; C → p,s; D → p,q
(d) A → s,q; B → r,p; C → r,s; D → p,q
30. 2.5 g sample of copper is dissolved in excess of H2SO4
to prepare 100 mL of 0.02 M CuSO4 (aq.). 10 mL of this
solution is iodometrically titrated and requires 2 mL of 0.1
M hyposolution. Calculate percentage purity of sample.
 (Upto two decimal place)

PYQ's (PAST YEAR QUESTIONS)

OXIDATION NUMBER AND ITS 4. In neutral or faintly alkaline medium, KMnO 4 being
APPLICATION a powerful oxidant can oxidize, thiosulphate almost
quantitatively, to sulphate. In this reaction, overall change
1. In Chromyl chloride, the oxidation state of chromium is (+).
in oxidation state of manganese will be:
 [15 April, 2023 (Shift-I)]
2. A sample of a metal oxide has formula M0.83O1.00 .The metal [29 July, 2022 (Shift-I)]
M can exist in two oxidation states +2 and +3 . In the sample (a) 5 (b) 1
of M0.83O1.00 , the percentage of metal ions existing in +2
(c) 0 (d) 3
oxidation state is _____ % (nearest integer)
5. The difference in oxidation state of chromium in chromate
[31 Jan, 2023 (Shift-II)]
and dichromate salts is________.
3. In ammonium-phosphomolybdate, the oxidation state of Mo
is + (_____) [6 April, 2023 (Shift-I)] [24 June, 2022 (Shift-I)]

Redox Reaction 49
 6. In the titration of KMnO4 and oxalic acid in acidic medium, 15. Which of the given reactions is not an example of
the change in oxidation number of carbon at the end points disproportionation reaction? [26 July, 2022 (Shift-I)]
_____________. [27 July, 2022 (Shift-I) (a) 2H2O2  2H2O + O2
7. The common positive oxidation states for an element with (b) 2NO2 + H2O  HNO3 + HNO2
atomic number 24, are: [17 March, 2021 (Shift-II) (c) MnO4 + 4H+ + 3e  MnO2 + 2H2O
2
(a) +1 and +3 to + 6 (b) +1 and +3 (d) 3MnO4  + 4H+  2MnO4 + MnO2 + 2H2O
16. Match the List-I with List-II. [1 Sept, 2021 (Shift-II)]
(c) +2 to +6 (d) +1 to + 6
List-I List-II
8. Identify the process in which change in the oxidation state
is five: [25 July, 2021 (Shift-II) A. Hydrolysis I. 2AuCl3 + 3HCHO + 3H2O →
(a) CrO42− → Cr3+ (b) MnO−4 → Mn2+ 2Au(sol) + 3HCOOH + 6HCl

(c) Cr2O72− → 2Cr3+ (d) C2O42− → 2CO2 B. Reduction II. As2O3 + 3H2S → As2S3(sol) +
3H2O
9. Oxidation number of potassium in K2O, K2O2 and KO2
C. Oxidation III. SO2 + 2H2S → 3S(sol) + 2H2O
respectively is [7 Jan, 2020 (Shift-I)
1 D. Double IV. FeCl3 + 3H2O →
(a) +1, +2 and +4 (b) +1, +1 and + Decomposition
2 Fe(OH)3(sol) + 3HCl
(c) +1, +1 and +1 (d) +1, +4 and +2 Choose the most appropriate answer from the options given
10. The compound that cannot act both as oxidising and reducing below.
agent is: [9 Jan, 2020 (Shift-I) (a) (A)-(IV), (B)-(II), (C)-(III), (D)-(I)
(a) HNO2 (b) H3PO4 (b) (A)-(I), (B)-(II), (C)-(IV), (D)-(III)
(c) H2SO3 (d) H2O2 (c) (A)-(I), (B)-(III), (C)-(II), (D)-(IV)
11. Consider the following molecules : Br3O8, F2O, H2S4O6, (d) (A)-(IV), (B)-(I), (C)-(III), (D)-(II)
H2S5O6, and C3O2. Count the number of atoms existing in 17. The species given below that does NOT show disproportionation
their zero oxidation state in each molecule. Their sum is____. reaction is: [20 July, 2021 (Shift-I)]
 [JEE Adv 2023] (a) BrO – (b) BrO3 – (c) BrO2– (d) BrO4–
18. The reaction of sulphur in alkaline medium is given below
TYPES OF REDOX REACTIONS AND S8(s) + aOH– (aq) → bS2– (aq) + cS2O32– (aq) + dH2O(l)
BALANCING OF REDOX REACTIONS The values of ‘a’ is ____________. (Integer answer)
12. 2IO3– + xl– + l2H+ → 6I2 + 6H2O. What is the value of x?  [24 Feb, 2021 (Shift-I)]
[8 April, 2023 (Shift-I)] 19. The redox reaction among the following is:
(a) 12 (b) 2  [7 Jan, 2020 (Shift-II)]
(c) 6 (d) 10 (a) Reaction of [Co(H2O)6]Cl3 with AgNO3
13. Which of the following options are correct for the reaction (b) Formation of ozone from atmospheric oxygen in the
presence of sunlight
2[Au(CN)2]–(aq) + Zn(s) → 2Au(s) + [Zn(CN)4]–2(aq)?
(c) Combination of dinitrogen with dioxygen at 2000 K
[6 April, 2023 (Shift-I)]
(d) Reaction of H2SO4 with NaOH
A. Redox reaction B. Displacement reaction 20. Consider the following equations:
C. Decomposition reaction D. Combination reaction 2Fe2+ + H2O2 → x A + y B (in basic medium)
Choose the correct answer from the options given below: (in acidic medium)
(a) A and B only 2MnO4– + 6H+ + 5H2O2 → x’C + y’D + z’E
(b) A only (in acidic medium) [4 Sept, 2020 (Shift-II)]
(c) C and D only The sum of the stoichiometric coefficients x, y, x′, y′ and
z′ for products A, B, C, D and E, respectively, is ________
(d) A and D only
14. Which one of the following is an example of disproportionation 21. An example of a disproportionation reaction is:
reaction? [26 June, 2022 (Shift-II)]  [12 April, 2019 (Shift-I)]
(a) 3MnO42– + 4H+ → 2MnO4– + MnO2 + 2H2O (a) 2KMnO4 → K2MnO4 + MnO2 + O2
(b) MnO4– + 4H+ + 4e– → MnO2 + 2H2O (b) 2MnO–4 + 10I– +16H+ → 2Mn2+ + 5I2 + 8 H2O
(c) 10I– + 2MnO4– + 16H+ → 2Mn2+ + 8H2O + 5I2 (c) 2CuBr → CuBr2 + Cu
(d) 8MnO4– + 3S2O32– + H2O → 8MnO2 + 6SO42– + 2OH– (d) 2NaBr + Cl2 → 2NaCl + Br2

50 P JEE Dropper Module-1 CHEMISTRY

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REDOX REACTIONS, ELECTRODE
PROCESSES AND TITRATIONS
22. Given below are two statements:
Statement-I: In redox titration, the indicators used are
sensitive to change in pH of the solution.
Statement-II: In acid-base titration, the indicators used are
sensitive to change in oxidation potential.
[8 April, 2023 (Shift-II)]
In the light of the above statements, choose the most
appropriate answer from the options given below
(a) Both Statement-I and Statement-II are correct.
(b) Statement-I is incorrect but Statement-II is correct.
(c) Statement-I is correct but Statement-II is incorrect.
(d) Both Statement-I and Statement-II are incorrect.
23. 20 mL of calcium hydroxide was consumed when it was
reacted with 10 mL of unknown solution of H2SO4. Also
20 mL standard solution of 0.5 M HCl containing 2 drops
of phenolphthalein was titrated with calcium hydroxide,
the mixture showed pink colour when burette displayed
the value of 35.5 mL whereas the burette showed 25.5  mL
initially. The concentration of H 2SO 4 is ________ M
(Nearest integer) [13 April, 2023 (Shift-I)]
24. Given below are two statements : One is labelled as
Assertion (A) and the other is labelled as Reason (R).
[28 July, 2022 (Shift-II)]
Assertion (A): Permanganate titrations are not performed
in presence of hydrochloric acid.
Reason (R): Chlorine is formed as a consequence of
oxidation of hydrochloric acid.
In the light of the above statements, choose the correct
answer from the options given below
(a) Both (A) and (R) are true and (R) is the correct
explanation of (A)
(b) Both (A) are (R) are true but (R) is NOT the correct
explanation of (A)
(c) (A) is true but (R) is false
(d) (A) is false but (R) is true
25. In base vs acid titration, at the end point methyl orange is
present as [25 July, 2022 (Shift-II)]
(a) Quinonoid form (b) Heterocyclic form
(c) Phenolic form (d) Benzenoid form
26. Given below are two statements : one is labelled as
Assertion (A) and the other is labelled as Reason (R).
[26 July, 2022 (Shift-II)]
Assertion (A): Phenolphthalein is a pH dependent indicator,
remains colourless in acidic solution and gives pink colour
in basic medium.
Reason (R): Phenolphthalein is a weak acid. It doesn’t
dissociate in basic medium.
Redox Reaction
In the light of the above statements, choose the most
appropriate answer from the options given below.
(a) Both (A) and (R) are true and (R) is the correct
explanation of (A).
(b) Both (A) and (R) are true but (R) is NOT the correct
explanation of (A).
(c) (A) is true but (R) is false
(d) (A) is false but (R) is true.
27. 20 mL of 0.02 M K2Cr2O7 solution is used for the titration of
10 mL of Fe2+ solution in the acidic medium. The molarity
of Fe2+ solution is __________ × 10–2 M. (Nearest Integer)
 [27 July 2022 (Shift-I)]
28. Given below are two statements. [26 Aug, 2021 (Shift-I)]
Statement-I: In the titration between strong acid and weak
base, methyl orange is suitable as an indicator.
Statement-II: For titration of acetic acid with NaOH,
phenolphthalein is not a suitable indicator.
In the light of the above statements, choose the most
appropriate answer from the options given below:
(a) Both Statement-I and Statement-II are false
(b) Both Statement-I and Statement-II are true
(c) Statement-I is true but Statement-II is false
(d) Statement-I is false but Statement-II is true
29. In basic medium CrO4 2– oxidises S2O32– to form SO42– and
itself changes into Cr(OH)4–. The volume of 0.154 M CrO42–
required to react with 40mL of 0.25 M S2O32– is ___mL.
(Rounded – off to the nearest integer)
 [25 Feb, 2021 (Shift-I)]
30. 0.4 g mixture of NaOH, Na2CO3 and some inert impurities
N
was first titrated with HCl using phenolphthalein as an
10
indicator, 17.5 mL of HCl was required at the end point.
After this methyl orange was added and titrated. 1.5 mL of
same HCl was required for the next end point. The weight
percentage of Na2CO3 in the mixture is ____. (Rounded – off
to the nearest integer)
 [25 Feb, 2021 (Shift-I)]
31. 10.0 mL of Na2CO3 solution is titrated against 0.2 M HCl
solution. The following titre values were obtained in 5
readings: [18 March, 2021 (Shift-II)]
4.8 mL, 4.9 mL 5.0 mL 5.0 mL and 5.0 mL
Based on these readings, and convention of titrimetric
estimation, the concentration of Na 2 CO 3 solution is
__________ mM. (Round off to the nearest integer).
32. When 10 ml of an aqueous solution of Fe2+ ions was titrated
in the presence of dil H2SO4 using diphenylamine indicator,
15 mL of 0.02 M solution of K2Cr2O7 was required to get
the end point. The molarity of the solution containing Fe2+
ions is x × 10–2 M. The value of x is. (Nearest integer)
 [25 July, 2021 (Shift-I)]
51
 33. 10.0 ml of 0.05 M KMnO4 solution was consumed in (a) Aq. NaOH in a burette and aqueous oxalic acid in a
a titration with 10.0 mL of given oxalic acid dehydrate conical flask
solution. The strength of given oxalic acid solution is (b) Aq. NaOH in a pipette and aqueous oxalic acid in a
__________ × 10–2 g/L [27 July, 2021 (Shift-II)] burette
(Round off to the Nearest Integer). (c) Aq. NaOH in a volumetric flask and concentrated H2SO4
34. When 35 mL of 0.15 M lead nitrate solution is mixed with in a conical flask
20mL of 0.12 M chromic sulphate solution, ________ × 10–5 (d) Aq. NaOH in a burette and concentrated H2SO4 in a
moles of lead sulphate precipitate out. conical flask
(Round off to the nearest integer). 39. Given : [12 April, 2019 (Shift-I)]
 [16 March 2021 (Shift-I)] Co3+ + e– → Co2+; E° = 1.81V
35. 15 mL of aqueous solution of Fe 2+ in acidic medium Pb4 + 2e– → Pb2+; E° = +1.67V
completely reacted with 20 ml. of 0.03 M aqueous Cr2O72–. Ce4+ + e– → Ce3+; E° + 1.61V
The molarity of the Fe2+ solution is _________ × 10–2 M Bi3+ + 3e– → Bi; E° = +0.20V
Oxidizing power of the species will increase in the order
(Round off to the nearest integer).
(a) Ce4+ < Pb4+ < Bi3+ < Co3+
 [17 March 2021 (Shift-I)] (b) Co3+ < Pb4+ < Ce4+ < Bi3+
36. The exact volumes of 1 M NaOH solution required to (c) Bi3+ < Ce4+ < Pb4+ < Co3+
neutralize 50 mL. of 1M H3PO3 solution and 100 mL of 2M (d) Co3+ < Ce4+ < Bi3+ < Pb4+
H3PO2 solution respectively, are: 40. In an acid base titration, 0.1 M HCl solution was added to the
 [16 March, 2021 (Shift-II)] NaOH solution of unknown strength. Which of the following
(a) 100 mL and 50 mL (b) 100 mL and 200 mL correctly shows the change of pH of the titration mixture in
(c) 50 mL and 50 mL (d) 100 mL and 100 mL this experiment? [9 April, 2019 (Shift-II)]
37. While titration dilute HCl solution with aqueous NaOH,
which of the following will not be required? pH pH
(A) (B)
 [2 Sept, 2020 (Shift-I)]
(a) Burette and porcelain tile V(mL) V(mL)
(b) Clamp and phenolphthalein
(c) Pipette and distilled water
(d) Bunsen burner and measuring cylinder pH pH
(C) (D)
38. The strength of an aqueous NaOH solution is most accurately
determined by titrating: (Note : consider that an appropriate V(mL) V(mL)
indicator is used) [8 Jan, 2020 (Shift-I)] (a) B (b) A (c) C (d) D

PW CHALLENGERS

PASSAGE I
A mixture of metallic iron with freshly prepared iron (II) and
iron (III) oxides was heated in a closed vessel in the atmosphere
of hydrogen. An amount of 4.72 g of the mixture when reacted,
yields 3.92 g of iron and 0.90 g of water.
When the same amount of the mixture was allowed to react with
an excess of a copper(II) sulphate solution, 4.96 g of a solid
mixture were obtained.
1. Calculate the volume (in cm3) of 7.3 % hydrochloric acid
(ρ = 1.03 g cm–3) which is needed for a total dissolution
of 4.72 g of the starting mixture.
2. What volume (in dm3) of a gas at STP is released?
Relative atomic masses:
Ar(O) = 16; Ar(S) = 32; Ar(Cl) = 35.5; Ar(Fe) = 56;
Ar(Cu) = 64
PASSAGE II
A sample of 2.3793 g of crystallohydrate of the type MxAy.z
H2O, where M is a metal, reacted with an excess of SOCl2.
Gaseous products formed by the reaction were introduced into
a barium chloride solution containing hydrochloric acid and
hydrogen peroxide. Small quantities of SOCl2 carried by the
gaseous products were removed by freezing out. The mass of the
precipitate that is deposited from the solution, was 14.004 g. It
was found to contain 13.74 mass % of sulphur.
In another experiment, 1.1896 g of the initial substance were
dissolved in water and the solution was diluted to a volume of
100 cm3. One fifth of this solution required to react with 10
cm3 of a 0.2-molar AgNO3 solution. The mass of the precipitate
formed by the titration was 0.28664 g. (The end point of the
titration was determined by the conductometric method.)

52 P JEE Dropper Module-1 CHEMISTRY

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 3. Calculate the molecular formula of the crystallohydrate.
4. If you know that the sample can contain a maximum of
seven moles of water per one mole of the crystallohydrate,
give an example of another possible hydrate that cannot
come into consideration due to the given limitation.
PASSAGE III
The reaction of permanganate ions with hydrogen peroxide in an
acidic solution gives Mn(II) salt and at the same time oxygen is
released:
2 MnO4– + 1H2O2 + 6H+ → 2Mn2+ + 3O2 + 4H2O
2 MnO4– + 3H2O2 + 6H+ → 2Mn2+ + 4O2 + 6H2O
2 MnO4– + 5H2O2 + 6H+ → 2Mn2+ + 5O2 + 8H2O
2 MnO4– + 7H2O2 + 6H+ → 2Mn2+ + 6O2 + 10H2O
5. How much potassium permanganate (in g) is needed
to release 112 cm3 of oxygen at STP conditions from an
excess of hydrogen peroxide in acidic solution?
PASSAGE IV
Amino acids can be determined by measuring the volume of
nitrogen released in their reaction with nitrous acid (Van Slyke’s
method), for example:
CH3CH(NH2)COOH + HNO2 → CH3CH(OH)COOH + N2 +
H2O
Another method consists of the reaction of amino acids with a
volumetric solution of perchloric acid, for example:
CH3CH(NH2)COOH + HClO4 → CH3CH(N+H3)COOH + ClO–4
The excess of the perchloric acid is determined then by titration
with a volumetric solution of sodium acetate (carried out in a
non-aqueous solution).
50.0 cm3 of a 0.100-normal solution of perchloric acid were
added to a sample of glycine in glacial acetic acid. The excess of
Redox Reaction
the perchloric acid was determined after the reaction by titration
with 0.150-normal volumetric solution of sodium acetate. The
consumption was 16.0 cm3.
6. What would be the volume (in dm3) of the nitrogen
released at a pressure of 102.658 kPa and a temperature
of 20°C when assumed that the same quantity of sample
were analysed by the Van Slyke’s method?
PASSAGE V
Chromium exists as FeCr2O4 in the nature and it contains
Fe0.95O & other impurity. To obtain pure chromium from
FeCr2O4, the ore is fused with KOH and oxygen is passed
through the mixture when K2CrO4 and Fe2O3 are produced.
FeCr2O4 + KOH + O2 → K2CrO4 + Fe2O3
Fe0.95O + O2 → Fe2O3
2 g of ore required 280 mL of O2 at 273 K and 1 atm for
complete oxidation of ore. K2CrO4 is precipitated as BaCrO4
when Barium salt is added. To remaining solution 10 mL of
1 M K4Fe(CN)6 is added when Fe3+ ions react with it to form
KFe[Fe(CN)6], often called ‘Prussian Blue’. To determine excess
of K4Fe(CN)6 in solution, 6mL of 0.4 N of Fe2+ is added when
all the K4Fe(CN)6 is precipitated as K2Fe[Fe(CN)6].
7. What % of total iron present in the ore is in +2 state?
(a) 99.64 (b) 85.29 (c) 65.82 (d) 97.73
8. % by mass of Fe0.95O in the ore is ____
(a) 9.6% (b) 6.92% (c) 8.55% (d) 20.2%
9. n factor for Fe0.95O is ____
2
(a) 0.9 (b) 0.85 (c) (d) 1.8
0.95
10. How many moles of Prussian Blue are formed?
(a) 8.8 × 10–3 (b) 12 × 10–3
(c) 5.5 × 10 –4 (d) 6.5 × 10–5
53
 Answer Key

CONCEPT APPLICATION
1. (a) 2. (d) 3. (a) 4. (c) 5. (c) 6. (c) 7. (a) 8. (a) 9. (c)

PRARAMBH (TOPICWISE)
1. (b) 2. (c) 3. (b) 4. (a) 5. (b) 6. (a) 7. (b) 8. (a) 9. (d) 10. (a)
11. (b) 12. (c) 13. (a) 14. (c) 15. (c) 16. (a) 17. (a) 18. (d) 19. (a) 20. (d)
21. (d) 22. (c) 23. (a) 24. (c) 25. (d) 26. (b) 27. (a) 28. (b) 29. (a) 30. (a)
31. (c) 32. (c) 33. (c) 34. (c) 35. (d) 36. (a) 37. (d) 38. (b) 39. (c) 40. (a)
PRABAL (JEE MAIN LEVEL)
1. (c) 2. (d) 3. (c) 4. (a) 5. (c) 6. (c) 7. (b) 8. (b) 9. (c) 10. (c)
11. (b) 12. (a) 13. (b) 14. (c) 15. (c) 16. (a) 17. (a) 18. (a) 19. (a) 20. (a)
21. (d) 22. (d) 23. (a) 24. (a) 25. (c) 26. (b) 27. (c) 28. (a) 29. (a) 30. (a)
31. (a) 32. (c) 33. (d) 34. (c) 35. (c) 36. (c) 37. [2] 38. [6] 39. [1] 40. [3]
41. [66] 42. [6]

PARIKSHIT (JEE ADVANCED LEVEL)

1. (b) 2. (d) 3. (b) 4. (a) 5. (c) 6. (c) 7. (a) 8. (c) 9. (c) 10. (b)
11. (c) 12. (b,c) 13. (a,b,c) 14. (a,b) 15. (a,c) 16. (a,b,c,d) 17. (a,c) 18. (a,c,d) 19. (a,b,d) 20. (c)
21. (a) 22. (b) 23. (a) 24. [50] 25. [80] 26. [27] 27. [3] 28. [7] 29. [24.8] 30. [5.08]

PYQ’s (PAST YEAR QUESTIONS)

1. [6] 2. [59] 3. [6] 4. (d) 5. [0] 6. [1] 7. (c) 8. (b) 9. (c) 10. (b)
11. [6] 12. (d) 13. (a) 14. (a) 15. (c) 16. (d) 17. (d) 18. [12] 19. (c) 20. [19]
21. (c) 22. (d) 23. [1] 24. (a) 25. (a) 26. (c) 27. [24] 28. (c) 29. [173] 30. [4]
31. [50] 32. [18] 33. [1575] 34. [525] 35. [24] 36. (b) 37. (d) 38. (a) 39. (b) 40. (a)

PW CHALLENGERS
1. [68] 2. [0.448] 3. [CoCl2.6H2O] 4. [YCl3.9H2O]
5. [0.316] 6. [0.617]
7. (d) 8. (b) 9. (b) 10. (a)

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