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06 Redox Reactions

Introduction:
Redox reactions show vital role in non renewable energy sources. In cell reactions where oxidation and
reduction both occurs simultaneously will have redox reaction for interconversion of energy.

Redox Reactions (Oxidation-Reduction):

Many chemical reactions involve transfer of electrons from one chemical substance to another. These
electron-transfer reactions are termed as oxidation-reduction or redox reactions.
Or
Those reactions which involve oxidation and reduction both simultaneously are known as oxidation
reduction or redox reactions.
Or
Those reactions in which increase and decrease in oxidation number of same or different atoms occurs are
known as redox reactions.

Oxidation and Reduction:

There are two concepts of oxidation and reduction.

(A) Classical/old concept :

OXIDATION REDUCTION

Addition of O2 Addition of H2
(1) 2Mg + O2 → 2MgO N2 + 3H2 → 2NH3
C + O2 → CO2 H2 + Cl2 → 2HCl
Removal of H2 Removal of O2
(2) H2S + Cl2 → 2HCl + S (oxidation of H2S) CuO + C → Cu + CO (reduction of CuO)
4HI + O2 → 2I2 + 2H2O (oxidation of HI) H2O +C → CO + H2 (reduction of H2O)
Addition of electronegative element Addition of electropositive element
(3) Fe + S → FeS (oxidation of Fe) CuCl2 + Cu → Cu2Cl2 (reduction of CuCl2)
SnCl2 + Cl2 → SnCl4 (oxidation of SnCl2) HgCl2 + Hg → Hg2Cl2 (reduction of HgCl2)
Removal of electronegative element
Removal of electropositive element 2FeCl3 + H2 → 2FeCl2 + 2HCl
(4) 2NaI + H2O2 → 2NaOH + I2 (reduction of FeCl3)
(oxidation of NaI)

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NEET : Chemistry
(B) Electronic/Modern Concept :
OXIDATION REDUCTION
(1) De-electronation Electronation
Oxidation process is that process in Reduction process is that process in which one
(2) which one or more electrons are lost by or more electrons are gained by an atom, ion or
an atom, ion or molecule. molecule.
Example –
(a) Zn → Zn+2 + 2e– (a) Cu+2 + 2e– → Cu
n+ – n+ –
M → M + ne M + ne → M
+2 +4 – +3 – +2
(b) Sn → Sn + (4 –2)e (b) Fe + (3 – 2)e → Fe
(3) M+n1 → M+n2 + (n2 − n1 )e− M+ x1 + (x1 − x2 )e− → M+ x2
(c) Cl– → Cl + e– (c) O + 2e– → O2–
A–n → A + ne– A + xe– → A–x
(d) MnO4–2 → MnO4– + (2 – 1)e– (d) [Fe(CN)4]3– + (4 – 3)e– → [Fe(CN)4]4–
A−n1 → A−n2 + (n1 − n2 )e− A−n1 + (n2 − n1 )e− → A−n2

Oxidation State:
Oxidation state of an atom in a molecule or ion is the hypothetical or real charge present on an atom due
to electronegativity difference.
Or
Oxidation state of an element in a compound represents the number of electrons lost or gained during its
change from free state into that compound.
Some important points about oxidation number :
(1) Electronegativity values of no two elements are same –
P>H C>H S>C Cl > N
(2) Oxidation number of an element may be positive or negative.
(3) Oxidation number can be zero, whole number or a fractional value.
Ex. Ni(CO)4  O.S of Ni = 0
N3H  O.S of N = –1/3
HCl  O.S of Cl = –1
(4) Oxidation state of same element can be different in same or different compounds.
Ex. H2S  O.S of S = –2
H2SO3  O.S of S = +4
H2SO4  O.S of S = +6
Some Helping Rules for Calculating Oxidation Number:
(A) In case of covalent bond :
(i) For homoatomic molecule
A −A A=A A  A
     
O.N. : 0 0 0 0 0 0
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Redox Reactions
(ii) For heteroatomic molecule (EN of B > A)
A–B A=B AB
     
O.N.: +1 –1 +2 –2 +3 –3
(iii) The oxidation state of an element in its free state is zero.
Ex. Oxidation state of Na, Cu, I, Cl, O etc. are zero.
(iv) Oxidation state of atoms present in homoatomic molecules is zero.
Ex. H2 , O2 , N2 , P4 , S8
(v) Oxidation state of an element in any of its allotropic form is zero.
Ex. CDiamond , CGraphite , SMonoclinic , SRhombic
(vi) Oxidation state of all the components of an alloy are zero.
Ex. (Na - Hg)
 
0 0
(vii) In complex compounds, oxidation state of metal in metal carbonyl is zero.
(viii) Oxidation state of fluorine in all its compounds is –1.
(ix) Oxidation state of IA & II A group elements are +1 and +2 respectively.
(x) Oxidation state of hydrogen in most of its compounds is +1 except in metal hydrides (-1)
Ex. NaH LiH CaH2 MgH2
       
O.S. : +1 –1 +1 –1 +2 –1 +2 –1
(xi) Oxidation state of oxygen in most of its compounds is -2 except in -
(a) Peroxides ( O2−2 ) → Oxidation state (O) = –1
Ex. H2O2, BaO2
(b) Super Oxides ( O2−1 ) → Oxidation state (O) = –1/2
Ex. KO2

–1/2
(c) Ozonide ( O3−1 ) → Oxidation state (O) = –1/3
Ex. KO3

–1/3
(d) OF2 (Oxygen difluoride)
F–O–F

Oxidation state (O) = + 2
(e) O2F2 (dioxygen difluoride)

Oxidation state (O) = + 1
(xii) Oxidation state of monoatomic ions is equal to the charge present on the ion.
Ex. Mg+2 → Oxidation state = +2

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NEET : Chemistry
(xiii) The algebric sum of oxidation states of all the atoms present in a polyatomic neutral
molecule is 0.
Ex. H2SO4
If O.S of S is x then
2 (+1) + x + 4 (–2) = 0
x–6=0
x = +6
Ex. H2SO3
If O.S of S is x then
2 (+1) +x + 3 (–2) = 0
x–4=0
x = +4
(xiv) The algebric sum of oxidation state of all the atoms in a polyatomic ion is equal to the
charge present on the ion.
Ex. SO4–2
If O.S of S is x then
x + 4 (–2) = –2
x–6=0
x = +6
–
Ex. HCO3
If O.S of C is x then
+1 +x + 3 (–2) = –1
x–4=0
x = +4
(B) In case of co-ordinate bond (EN of B > A) :
A→A B → B A →B B→A
       
O.S.: +2 –2 +2 –2 +2 –2 0 0
(C) In case of Ionic bond :
Charge on cation = O.S of cation
Charge on anion = O.S of anion
+ –
Ex. NaCl → Na + Cl
 
+1 –1
+2
MgCl2 → Mg + 2Cl–
 
+2 –1
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Redox Reactions
Illustration 1:
Oxidation number of cobalt in [Co(NH3)6] Cl2Br is –
(1) +6 (2) Zero (3) +3 (4) +2
Solution :
Let the oxidation number of Co be x
NH3 is a neutral ligand
Oxidation number of Cl is –1
Oxidation number of Br is –1
Hence, x + 6 (0) – (1 × 2) – 1 = 0
 x = +3
So, the oxidation number of cobalt in the given complex compound is +3.
Illustration 2:
The order of increasing oxidation numbers of S in S8, S2O8–2, S2O3–2, S4O6–2 is given below –
(1) S8 < S2O8−2 < S2O3−2 < S4O6−2 (2) S2O8−2 < S2O3−2 < S4O6−2 < S8
(3) S2O8−2 < S8 < S4O6−2 < S2O3−2 (4) S8 < S2O3−2 < S4O6−2 < S2O8−2
Solution :
The oxidation number of S are shown below along with the compounds
S8 S2O8−2 S2O3−2 S4O6−2
0 +6 +2 +2.5
Hence the order of increasing oxidation state of S is –
S8 < S2O3−2 < S4O6−2 < S2O8−2

Illustration 3:
The oxidation number of Cl in NOClO4 is –
(1) +11 (2) +9 (3) +7 (4) +5
Solution :
The compound may be written as NO+ ClO4− .
For ClO4− , Let oxidation number of Cl = a
a + 4 × (–2) = –1
a = +7
Hence, the oxidation number of Cl in NOClO4 is + 7
Illustration 4:
The two possible oxidation states of N atoms in NH4NO3 are respectively –
(1) +3, +5 (2) +3, –5 (3) –3, +5 (4) –3, –5
Solution :
There are two N atoms in NH4NO3, but one N atom has negative oxidation states (attached to H) and the
other has positive oxidation states (attached to O). Therefore evaluation should be made separately as –
Oxidation states of N is NO4+ Oxidation states of N in NO3−
a + 4 × (+1) = +1 and a + 3 (–2) = –1
 a = –3  a=+5
Here the two oxidation states are –3 and +5 respectively.
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NEET : Chemistry
Illustration 5:
The oxidation states of S in H2S2O8 is –
(1) +8 (2) –8 (3) +6 (4) +4
Solution :
In H2S2O8, two O atoms form peroxide linkage i.e.
O O
 
H–O–S–O–O–S–O–H
 
O O
2 × 1 + 2a + 6 (–2) + 2 (–1) = 0
 a = +6
Thus the oxidation states of S in H2S2O8 is +6
Illustration 6:
The oxidation number of S in (CH3)2 SO is –
(1) 1 (2) 2 (3) 0 (4) 3
Solution :
Let the oxidation number of S is 'a'
Oxidation number of CH3 = +1
Oxidation number of O = –2
2 (+1) + a + (–2) = 0
a=0
Hence the oxidation no. of S in dimethyl sulphoxide is zero.

BEGINNER’S BOX-1
1. In which of the following compounds, the oxidation state of I-atom is highest ?
(1) KI3 (2) KIO4 (3) KIO3 (4) IF5
2. The oxidation number of phosphorus in Ba(H2PO2)2 is –
(1) +3 (2) +2 (3) +1 (4) –1
3. Oxidation number of Ni in Ni(CO)4 is –
(1) 0 (2) 4 (3) 8 (4) 2
4. Positive oxidation state of an element indicates that it is –
(1) Elementary form (2) Oxidised (3) Reduced (4) Only reductant
5. Predict the highest and lowest oxidation state of (a) Ti and (b) Tl in combined state.
(1) a[0, +3] b[0, +2] (2) a[+3, 0] b[+4, 0]
(3) a[+4, 0] b[+4, 0] (4) a[+4. +2] b[+3, +1]
6. The oxidation state of oxygen atom in potassium superoxide is –
(1) Zero (2) –1/2 (3) –1 (4) –2

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Redox Reactions
Oxidising and Reducing Nature of the Substances:
Oxidising agents are the substances which accept electrons in a chemical reaction i.e., electron acceptors
are oxidising agent.
Reducing agents are the substances which donate electrons in a chemical reaction i.e., electron donors
are reducing agent.
Highest O.S. +4 +5 +5 +6 +7 +6 +7 +8 +8 +2 +1
Elements C N P S Cl Cr Mn Os Ru O H
Lowest O.S. –4 –3 –3 –2 –1 0 0 0 0 –2 –1

(a) If effective element in a compound is present in maximum oxidation state then the compound
acts as oxidising agent.

Ex. KMnO4 K2Cr2O7 H2SO4 SO3 H3PO4 HNO3 HClO4

      
+7 +6 +6 +6 +5 +5 +7

(b) If effective element in a compound is present in minimum oxidation state then the compound
acts as reducing agent.
PH3 NH3 CH4
  
–3 –3 –4

(c) If effective element in a compound is present in intermediate oxidation state then the
compound can act as oxidising agent as well as reducing agent.
HNO2 H3PO3 SO2 H2O2
   
+3 +3 +4 –1

Types of Redox Reactions:

Types of Redox Reactions

(A) (B) (C) (D)

Intermolecular Intramolecular Disproportionation Comproportionation
redox reaction redox reaction reaction reaction
(A) Intermolecular redox reaction :- When oxidation and reduction takes place separately in different
compounds, then the reaction is called intermolecular redox reaction.
SnCl2 + 2FeCl3 ⎯→ SnCl4 + 2FeCl2
+2 +4
Sn ⎯→ Sn (Oxidation)
+3 +2
Fe ⎯→ Fe (Reduction)
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NEET : Chemistry
(B) Intramolecular redox reaction :- During the chemical reaction, if oxidation and reduction takes
place in single compound then the reaction is called intramolecular redox reaction.

(C) Disproportionation reaction :- When reduction and oxidation takes place in the same element of
the same compound in a reaction then the reaction is called disproportionation reaction.

(D) Comproportionation reaction: Reverse of disproportionation reaction known as comproportionation

reaction.
Ex.
HClO + Cl– → Cl2 + OH–
Cl+1 Cl–1 Cl0
Oxidation
Reduction

BEGINNER’S BOX-2
1. Oxidation is defined as –
(1) Gain of electrons (2) Decrease in positive valency
(3) Loss of electrons (4) Addition of electropositive element
2. Reduction is defined as –
(1) Increase in positive valency (2) Gain of electrons
(3) Loss of protons (4) Decrease in negative valency
3. In the reaction MnO4− + SO3−2 + H+ ⎯⎯→ SO4−2 + Mn2+ + H2O
+ +
(1) MnO4− and H both are reduced (2) MnO4− is reduced and H is oxidised
(3) MnO4− is reduced and SO32− is oxidised (4) MnO4− is oxidised and SO32− is reduced

4. The charge on cobalt in [Co(CN)6]–3 is –

(1) –6 (2) –3 (3) +3 (4) +6
5. Which of the following halogen always show only one oxidating state in its compounds?
(1) Cl (2) F (3) Br (4) I
6. Which of the following reactions do not involve oxidation-reduction ?
(1) 2Rb + 2H2O ⎯⎯→ 2RbOH + H2 (2) 2CuI2 ⎯⎯→ 2CuI + I2
(3) NH4Cl + NaOH ⎯⎯→ NaCl + NH3 + H2O (4) 3Mg + N2 ⎯⎯→ Mg3N2
7. The fast reaction between water and sodium is the example of –
(1) Oxidation (2) Reduction
(3) Intermolecular redo (4) Intramolecular redox
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Redox Reactions
8. Choose the redox reaction from the following–
(1) Cu + 2H2SO4 ⎯⎯→ CuSO4 + SO2 + 2H2O
(2) BaCl2 + H2SO4 ⎯⎯→ BaSO4 + 2HCl
(3) 2NaOH + H2SO4 ⎯⎯→ Na2SO4 + 2H2O
(4) KNO3 + H2SO4 ⎯⎯→ 2HNO3 + K2SO4
9. Which of the following is not a redox reaction ?
(1) MnO4− ⎯⎯→ MnO2 + O2
(2) Cl2 + H2O ⎯⎯→ HCl + HClO
+
(3) 2 CrO24− + 2H ⎯⎯→ Cr2O72− + H2O

(4) MnO4− + 8H+ + 5Ag ⎯⎯→ Mn+2 + 4H2O + 5Ag+

10. In the reaction 6Li + N2 ⎯⎯→ 2Li3N
(1) Li undergoes reduction (2) Li undergoes oxidation
(3) N undergoes oxidation (4) Li is oxidant
11. H2O2 + H2O2 ⎯⎯→ 2H2O + O2 is an example of dispropotionation because –
(1) Oxidation number of oxygen only decreases
(2) Oxidation number of oxygen only increases
(3) Oxidation number of oxygen decreases as well as increase
(4) Oxidation number of oxygen neither decreases nor increases

Balancing of Redox Reactions:

A Ion electron method

Balancing
of Redox
reaction

B Oxidation number change method

(A) Ion-Electron method :-

This method was given by Jette and La Mev in 1972.
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.
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NEET : Chemistry
(iii) Balance these half reactions separately and then add by multiplying with suitable coefficients
so that the electrons are cancelled. Balancing is done using following substeps.
(a) Balance all other atoms except H and O in both half reactions.
(b) Then balance oxygen atoms by adding H2O molecules to the side deficient in oxygen. The
number of H2O molecules added is equal to the deficiency of oxygen atoms.
(c) Balance hydrogen atoms by adding H+ ions equal to the deficiency in the side which is
deficient in hydrogen atoms.
(d) Balance the charge by adding electrons to the side which is rich in +ve charge. i.e. deficient
in electrons. Number of electrons added is equal to the deficiency.
(e) Multiply the half equations with suitable coefficients to equalize the number of electrons.
(iv) Add these half equations to get an equation which is balanced with respect to charge and atoms.
(v) If the medium of reaction is basic, OH– ions are added to both sides of balanced equation, which
is equal to number of H+ ions in Balanced Equation.

Illustration 7:
Balance the following reaction by ion-electron method in acidic medium :
Cr2O72− + C2O24− ⎯⎯→ Cr3+ + CO2
Solution :
3+
Cr2O72− + C2O24− ⎯⎯→ Cr + CO2
(a) Write both the half reaction.
3+
Cr2O72− ⎯⎯→ Cr (Reduction half reaction)

C2O24− ⎯⎯→ CO2 (Oxidation half reaction)

(b) Atoms other than H and O are balanced.
3+
Cr2O72− ⎯⎯→ 2Cr

C2O24− ⎯⎯→ 2CO2

(c) Balance O-atoms by the addition of H2O to another side
3+
Cr2O72− ⎯⎯→ 2Cr + 7H2O

C2O24− ⎯⎯→ 2CO2

+
(d) Balance H-atoms by the addition of H to another side
+ 3+
Cr2O72− + 14 H ⎯⎯→ 2Cr + 7H2O

C2O24− ⎯⎯→ 2CO2

(e) Now, balance the charge by the addition of electron (e–).

+ – 3+
Cr2O72− + 14 H + 6e ⎯⎯→ 2Cr + 7H2O ...(1)
–
C2O24− ⎯⎯→ 2CO2 + 2e ...(2)
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Redox Reactions
(f) Multiply equations by a constant number to get the same number of electrons on both side. In the
above case second equation is multiplied by 3 and then added to first equation.
+ – 3+
Cr2O72− + 14 H + 6e ⎯⎯→ 2Cr + 7H2O

3 C2O24− ⎯⎯→ 6CO2 + 6e–

+ 3+
Cr2O72− + 3 C2O24− + 14 H ⎯→ 2Cr + 6CO2 + 7H2O

Illustration 8:
Balance the following reaction by ion-electron method in basic medium :
Cr(OH)3 + IO3− → I– + CrO24−
Solution :
Cr(OH)3 + IO3− → I– + CrO24−
(a) Separate the two half reactions.
Cr(OH)3 ⎯⎯→ CrO24− (Oxidation half reaction)

IO3− ⎯⎯→ I– (Reduction half reaction)

(b) Balance O-atoms by adding H2O.
H2O + Cr(OH)3 ⎯⎯→ CrO24−

IO3− ⎯⎯→ I– + 3H2O

+ –
(c) Balance H-atoms by adding H to side having deficiency and add equal no. of OH ions to both side
(medium is known)
H2O + Cr (OH)3 ⎯⎯→ CrO24− + 5H+
– + –
5OH + H2O + Cr(OH)3 ⎯⎯→ CrO24− + 5H + 5OH

or 5OH– + Cr(OH)3 ⎯⎯→ CrO24− + 4H2O

IO3− + 6H+ ⎯⎯→ I– + 3H2O

I + 6H+ + 6OH– ⎯⎯→ I– + 3H2O + 6OH–

or IO3− + 3H2O ⎯⎯→ I– + 6OH–
(d) Balance the charges by adding electrons
5OH– + Cr(OH)3 ⎯⎯→ CrO24− + 4H2O + 3e– ….(1)

IO3− + 3H2O + 6e– ⎯⎯→ I– + 6OH– ….(2)

(e) Multiply first equation by 2 and add to second to give
– –
10OH + 2Cr(OH)3 ⎯⎯→ 2 CrO24− + 8H2O + 6e

IO3− + 3H2O + 6e– ⎯⎯→ I– + 6OH–

4OH– + 2Cr(OH)3 + IO3− ⎯⎯→ 5H2O + 2 CrO24− + I–

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NEET : Chemistry
(B) Oxidation number change method :
This method was given by Johnson. In a balanced redox reaction, total increase in oxidation number
must be equal to total decreases 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 gain of
electrons.
(ii) Select the atom in reducing agent whose oxidation number increases and indicate the loss of
electrons.
(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 H2O molecules to the side deficient in oxygen.
(vi) Then balance the number of H atoms by adding H+ ions to the side deficient in hydrogen.
Illustration 9:
Balance the following reaction by the oxidation number method –
Cu + HNO3 ⎯→ Cu(NO3)2 + NO2 + H2O
Solution :
Write the oxidation number of all the atoms.
+1 +5 −2 +2 +5 −2 +4 −2 +1 −2
Cu + HNO3 ⎯⎯
→ Cu(NO3 )2 + NO2 + H2 O
There is change in oxidation number of Cu and N.
0 +2
Cu ⎯⎯
→ Cu(NO3 )2 ...(1) (Oxidation no. is increased by 2)
+5 +4
HNO3 ⎯⎯
→ NO2 ...(2) (Oxidation no. is decreased by 1)
To make increase and decrease equal, eq. (2) is multiplied by 2.
Cu + 2HNO3 ⎯→ Cu(NO3)2 + 2NO2 + H2O
Balancing nitrates ions, hydrogen and oxygen, the following equation is obtained.
Cu + 4HNO3 ⎯→ Cu(NO3)2 + 2NO2 + 2H2O
This is the balanced equation.
Illustration 10:
Balance the following reaction by the oxidation number method –
MnO4− + Fe+2 ⎯→ Mn+2 + Fe+3
Solution :
Write the oxidation number of all the atoms.
+7 −2
MnO4− + Fe+2 ⎯⎯⎯⎯⎯→ Mn+2 + Fe+3
change in oxidation number has occured in Mn and Fe.
+7
MnO4− ⎯→ Mn+2 ...(1) (Decrement in oxidation no. by 5)

Fe+2 TG:
⎯→ Fe+3
@Chalnaayaaar
...(2) (Increment in oxidation no. by 1)
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Redox Reactions
To make increase and decrease equal, eq. (2) is multiplied by 5.
+2 +2 +3
MnO4− + 5Fe ⎯→ Mn + 5Fe
To balance oxygen, 4H2O are added to R.H.S. and to balance hydrogen, 8H+ are added to L.H.S.
+2 + +2 +3
MnO4− + 5Fe + 8H ⎯→ Mn + 5Fe + 4H2O
This is the balanced equation.

BEGINNER’S BOX-3
1. In the half reaction : 2 ClO3− ⎯⎯→ Cl2
(1) 5 electrons are gained (2) 5 electrons are liberated
(3) 10 electrons are gained (4) 10 electrons are liberated
2. The number of electrons required to balance the following equation –
NO3− + 4H+ + e– ⎯⎯→ 2H2O + NO are –
(1) 5 (2) 4 (3) 3 (4) 2
3. Which of the following equations is a balanced one –
+ 2+ 3+
(1) 5 BiO3− + 22H + Mn ⎯⎯→ 5Bi + 7H2O + MnO4−
+ 2+ 3+
(2) 5 BiO3− + 14H + 2Mn ⎯⎯→ 5Bi + 7H2O + 2 MnO4−
(3) 2 BiO3− + 4H+ + Mn2+ ⎯⎯→ 2Bi3+ + 2H2O + MnO4−

(4) 6 BiO3− + 12H+ + 3Mn2+ ⎯⎯→ 6Bi3+ + 6H2O + 3 MnO4−

Equivalent Weight of Compounds:

The equivalent weight of an oxidising agent or reducing agent is that weight which accepts or loses one
mole electrons in a chemical reaction.
Molecular weight
(a) Equivalent weight of oxidant =
No. of electrons gained by one mole of oxidant
Example :
In acidic medium
6e– + Cr2O72− + 14H+ ⎯⎯→ 2Cr3+ + 7H2O
Here atoms which undergoes reduction is Cr. Its O. S. is decreasing from +6 to +3
Molecular weight of K 2Cr2O7 M
Equivalent weight of K2Cr2O7 = =
3× 2 6
Note : [6 in denominator indicates that 6 electrons were gained by Cr2O72− as it is clear from the
given balanced equation]
Molecular weight
(b) Equivalent weight of a reductant =
No. of electrons lost by one mole of reductant
In acidic medium, C2O24− ⎯⎯→ 2CO2 + 2e–
Here, atoms which undergoes oxidation is C. Its oxidation state is increasing from +3 to +4.
M
Here, Total electrons lost in C2O24− = 2 So, equivalent weight of C2O24− =
2
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(c) In different conditions a compound may have different equivalent weight because, it depends
upon the number of electrons gained or lost by that compound in that reaction.
Example :
+2
(i) MnO4− ⎯⎯→ Mn (acidic medium)
(+7) (+2)
M 158
Here 5 electrons are taken by MnO4− so its equivalent weight = = = 31.6
5 5
(ii) MnO4− ⎯⎯→ MnO2 (neutral medium) or (Weak alkaline medium)
(+7) (+4)
M 158
Here, only 3 electrons are gained by MnO4− so its equivalent weight = = = 52.7
3 3
Note : When only alkaline medium is given consider it as weak alkaline medium.
(iii) MnO4− ⎯⎯→ MnO4−2 (strong alkaline medium)
(+7) (+6)
M
Here, only one electron is gained by MnO4− so its equivalent weight == 158
1
Note : KMnO4 acts as an oxidant in every medium although with different strength which
follows the order –
acidic medium > neutral medium > alkaline medium
while, K2Cr2O7 acts as an oxidant only in acidic medium as follows
Cr2O72– ⎯⎯→ 2Cr3+
(2 × 6) ⎯⎯→ (2 × 3)
M 294
Here, 6 electrons are gained by K2Cr2O7 equivalent weight = = = 49
6 6
Molecular Formula of Compound:
Since the sum of oxidation number of all the atoms present in a compound is zero, so the validity of the
formula can be confirmed.

Some Oxidizing Agents/Reducing Agents with Equivalent Weight:

Electrons
exchanged or
Species Changed to Reaction Eq. wt.
change in
O.N.
Mn +2 M
MnO4− (O.A.) in acidic medium
MnO4− + H+ + 5e– → Mn2+ + 4H2O 5 E=
5
MnO M
MnO4− (O.A.) 2
in neutral medium or MnO4− + 3e– + 2H2O → MnO2 + 4OH– 3 E=
in weak alkaline medium 3

MnO 2− M
MnO4− (O.A.) 4 MnO4− + e– → MnO42– 1 E=
in strong alkaline medium 1
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Redox Reactions

Cr3+ M
Cr2O72− (O.A.) in acidic medium
Cr2O72− + 14H+ + 6e– → 2Cr3+ + 7H2O 6 E=
6

Mn2+ M
MnO2(O.A.) in acidic medium MnO2 + 4H+ + 2e– → Mn2+ + 2H2O 2 E=
2

Cl (O.A.) M
2 Cl– Cl2 + 2e– → 2Cl– 2 E=
in bleaching powder
2

CuSO (O.A.) M
4 Cu+ Cu2+ + e–→ Cu+ 1 E=
in iodometric titration
1

2 2M
S2O32− (R.A.) S4O26− 2 S2O32− → S4O26− + 2e– (for two moles)
E= =M
2
M
H2O2 (O.A.) H2O H2O2 + 2H+ + 2e– → 2H2O 2 E=
2
H2O2 → O2 + 2H+ + 2e–
M
H2O2 (R.A.) O2 (O.N. of oxygen in H2O2 is –1 per 2 E=
2
atom)
M
Fe2+ (R.A.) Fe3+ Fe2+ → Fe3+ + e– 1 E=
1

I 2 M
I– (R.A.) 2 2I– → I2 + 2e– (for two moles)
E=
(in acidic medium)
1

IO3– M
I– (R.A.) I– + 6OH– → IO3– + 3H2O + 6e– 6 E=
(inbasic medium) 6

Illustration 11:
Find the n-factor of reactant in the following chemical changes.
+
KMnO4 ⎯⎯ → Mn2+
H
(i)
H2O
(ii) KMnO4 ⎯⎯ → Mn4+
-( )
OH concentrated basic medium
(iii) KMnO4 ⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯ → Mn6+
+
(iv) K2Cr2O7 ⎯⎯ → Cr3+
H

(v) CrO24− → CO2

(vi) FeSO4 → Fe2O3
(vii) Fe2O3 → FeSO4
Solution :
2+
(i) In this reaction, KMnO4 which is an oxidizing agent, itself gets reduced to Mn under acidic
conditions.
n = |1 × (+7) – 1 × (+2)| = 5
4+
(ii) In this reaction, KMnO4 gets reduced to Mn under neutral or slightly (weakly) basic conditions.
n = |1 × (+7) – 1 × (+4)| = 3
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(iii) In this reaction, KMnO4 gets reduced to Mn6+ under basic conditions.
n = |1 × (+7) – 1 × (+6)| = 1
(iv) In this reaction, K2Cr2O7 which acts as an oxidizing agent reduced to Cr3+ under acidic conditions.
(It does not react under basic conditions.)
n = |2 × (+6) – 2 × (+3)| = 6
(v) In this reaction, C2O42– (oxalate ion) gets oxidized to CO2 when it is reacted with an oxidizing agent.
n = |2 × (+3) – 2 × (+4)| = 2
(vi) In this reaction, ferrous ions get oxidized to ferric ions.
n = |1 × (+2) – 1 × (+3)| = 1
(vii) In this reaction, ferric ions are getting reduced to ferrous ions.
n = |2 × (+3) – 2 × (+2)| = 2
Illustration 12:
Suppose that there are three atoms A, B, C and their oxidation numbers are 6, –1, –2, respectively.
Then the molecular formula of compound will be.
Solution :
Since, the charge on a free compound is zero. So
+6 = (–1 × 4) + (–2)
+6 = –6
or +6 = (–1 × 2) + (–2 × 2)
= –2 + (–4) = –6
So molecular formula, AB4C or AB2C2.

BEGINNER’S BOX-4

1. Molecular weight of KMnO4 in acidic medium and neutral medium will be respectively –
(1) 7 equivalent weight and 2 equivalent weight
(2) 5 equivalent weight and 3 equivalent weight
(3) 4 equivalent weight and 5 equivalent weight
(4) 2 equivalent weight and 4 equivalent weight
2. In acidic medium, equivalent weight of K2Cr2O7 (Molecular weight = M) is –
(1) M/3 (2) M/4 (3) M/6 (4) M/2

Law of Equivalence
The law states that one equivalent of an element combine with one equivalent of the other and in a chemical
reaction equal number of equivalents or milli equivalents of reactants react to give equal number of
equivalents or milli equivalents of products separately.
According to low of equivalence:
(i) aA + bB → mM + nN
m. eq of A = number of m. eq of B = number of m. eq of M = number of m. eq of N
(ii) In a compound MxNy
Number of m. eq of MxNy = m.eq of M = number of m.eq of N
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Redox Reactions

For Redox Reactions :

Number of m. eq. of oxidant = Number of m. eq. of reductant
N1V1 = N2V2 is always true.
But (M1 × V1) × n1 = (M2 × V2) × n2 (always true where n term represents valency factor).

Illustration 13:
Calculate the normality of a solution containing 15.8 g of KMnO4 in 50 mL acidic solution.
Solution :
W  1000
Normality (N) =
E  V(mL)
Where, W = 15.8 g, V = 50 mL
molar mass of KMnO4
E= = 158/5 = 31.6
Valence factor
So, Normality = 10 N
Illustration 14:
Calculate the normality of a solution containing 50 mL of 5 M solution K2Cr2O7 in acidic medium.
Solution :
Normality (N) = Molarity × Valency factor= 5 × 6 = 30 N
Illustration 15:
Find the number of moles of KMnO4 needed to oxidise one mole Cu2S in acidic medium. The reaction is
KMnO4 + Cu2S ⎯→ Mn2+ + Cu2+ + SO2
Solution :
From law of equivalence
equivalents of Cu2S = equivalents of KMnO4
moles of Cu2S × v.f = moles of KMnO4 × v.f.
1 × 8 = n2 × 5
8
n2 = = 1.6
5
Illustration 16:
Find the number of moles of oxalate ions oxidized by one mole of MnO4– ion in acidic medium.
5 2 3 5
(1) (2) (3) (4)
2 5 5 3
Solution :
Equivalents of C2O42– = equivalents of MnO4–
5
x (mole) × 2 = 1 × 5 ; x =
2
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Illustration 17:
What volume of 6 M HCl and 2 M HCl should be mixed to get two litre of 3 M HCl?
Solution :
Let, the volume of 6 M HCl required to obtain 2 L of 3M HCl = x L
 Volume of 2 M HCl required = (2 – x) L
M1V1 + M2V2 = M3V3
6M HCl 2M HCl 3M HCl
6 × (x) + 2 × (2 – x) = 3 × 2
 6x + 4 – 2x = 6  4x = 2
 x = 0.5 L
Hence, volume of 6 M HCl required = 0.5 L
Volume of 2M HCl required = 1.5 L
Illustration 18:
In a reaction vessel, 1.184 g of NaOH is required to be added for completing the reaction. How many
millilitre of 0.15 M NaOH should be added for this requirement ?
Solution :
Amount of NaOH present in 1000 mL of 0.15 M NaOH = 0.15 × 40 = 6 g

 1 mL of this solution contain NaOH = 6 × 10–3 g

1
 1.184 g of NaOH will be present in = × 1.184 = 197.33 mL
6  10−3
Illustration 19:
What weight of Na2CO3 of 85% purity would be required to prepare 45.6 mL of 0.235N H2SO4 in any
particular process ?
Solution :
Meq. of Na2CO3 = Meq. of H2SO4 = 45.6 × 0.235
WNa2CO3
 × 1000 = 45.6 × 0.235
ENa2CO3

WNa2CO3
 × 1000 = 45.6 × 0.235
106 / 2

 WNa2CO3 = 0.5679 g

For 85 g of pure Na2CO3, weight of sample = 100 g

100
 For 0.5679 g of pure Na2CO3, weight of sample = = 0.6681 g
85
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Redox Reactions
Illustration 20:
The number of moles of KMnO4 that will be required to react with 2 mol of ferrous oxalate is
6 2 4
(1) (2) (3) (4) 1
5 5 5
Solution :

Mn7+ + 5 e– → Mn2+ ]×3

Fe2+ → Fe3+ + e–
×5
–
CrO24− → 2CO2 + 2e

3 moles of KMnO4 = 5 moles of FeC2O4

6
 2 mol of ferrous oxalate  mole of KMnO4
5
Hence, (A) is the correct answer.
Illustration 21:
What volume of 6 M HNO3 is needed to oxidize 8 g of Fe2+ to Fe3+, HNO3 gets converted to NO?
(1) 8 mL (2) 7.936 mL (3) 32 mL (4) 64 mL
Solution :

Meq. of HNO3 = Meq. of Fe2+

8
or 6 × 3 × V = × 1000
56
V = 7.936 mL
valency factor = 3

+5 2+
(NO3– → NO)

Hence, (B) is the correct answer.

Illustration 22:
Which of the following is / are correct?
(1) g mole weight = molecular weight in g = wt. of 6.02 × 1023 molecules
(2) mole = NA molecule = 6.02 × 1023 molecules
(3) mole = g molecules
(4) none of the above
Solution :
Ans. (1), (2) and (3)

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BEGINNER’S BOX ANSWERS KEY

Que. 1 2 3 4 5 6
BEGINNER'S BOX-1
Ans. 2 3 1 2 4 2

Que. 1 2 3 4 5 6 7 8 9 10
Ans. 3 2 3 3 2 3 3 1 3 2
BEGINNER'S BOX-2
Que. 11
Ans. 3

Que. 1 2 3
BEGINNER'S BOX-3
Ans. 3 3 2

Que. 1 2
BEGINNER'S BOX-4
Ans. 2 3

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