OXIDATION AND REDUCTION

1. CLASSICAL CONCEPT OF OXIDATION REDUCTION

A. Oxidation : According to this concept, oxidation is considered as the addition of oxygen or removal of
hydrogen in an ion, in a compound or in a species. Or the addition of an electronegative element or
removal of electropositive element in a group, in a ion, in a species or in a compound is called oxidation.
For example :
(a) 2Mg + O2  2MgO Addition of Oxygen.
(b) C + O2  CO2
(c) H 2S + Cl2  2HCl + S Removal of Hydrogen
(d) MnO2 + 4HCl  MnCl2 + Cl2 + 2H2O
B. Reduction : According to this concept, reduction is considered as addition of hydrogen or removal of
oxygen in an atom, in a group, in an ion, in a species or in a compound. Or addition of an electropositive
element or removal of an electronegative element in a group, in an ion, in a species or in a compound
is called reduction.
For example :
(a) H2S + Cl2  2HCl + S Addition of Hydrogen

(b) H2 + Cl2  2HCl

(C) ZnO + C  Zn + CO Removal of Oxygen
(d) Fe2O3 + 3CO  2Fe + 3CO2

2. VALENCY CONCEPT OF OXIDATION REDUCTION

A. Oxidation: According to this concept, increase in (+)ve valency or decrease in (–)ve valency in a
reaction is called oxidation.
For example :
2Mg + O2  2MgO
(0) (+2)
B. Reduction : According to this concept, It is the process in which (+) ve valency decreases whereas
(–)ve valency increases in a reaction is called reduction.
For example :
2HgCl2 + SnCl2  Hg2Cl2 + SnCl4
(+2) (+1)
3. OXIDATION NUMBER CONCEPT OF OXIDATION-REDUCTION
A. Oxidation : According to this concept, increase in oxidation no. in an element in a reaction is called
oxidation.
B. Reduction : According to this concept, decrease in oxidation no. in an element in a reaction is called
reduction.
For example :
KMnO4 + FeSO4  MnO + Fe2(SO4)3
+ 7 + 2 + 2 + 3

4. MODERN OR ELECTRONIC CONCEPT OF OXIDATION REDUCTION

A. Oxidation : According to this concept, the process in which involves the loss of e– in an element or
species is called oxidation. It is also called deelectronation.
For example :
Fe  Fe2+ + 2e– (O.N. of Fe, 0  2)
Fe2+  Fe3+ + e– (O.N. of Fe, 2  3)
2Cl–  Cl2 + 2e– (O.N. of Cl, –1  0)
B. Reduction : According to this concept, the process which involves the gain of electrons by an element
or an atom or an ion is called reduction. It is also called electronation.
For example :
I2 + 2e–  2I – (O.N. of I,0  –1)
Fe3+ + e–  Fe+2 (O.N. of Fe, + 3  + 2)
Sn+4 + 2e–  Sn+2 (O.N. of Sn, + 4  + 2)

5. OXIDANT OR OXIDISING AGENT

Species, which oxidise other species, which is present in a reaction and reduce it self. This type of
species is called oxidant or oxidising agent. Or species, which accepts electron in a reaction by another
species and show decreases in its oxidation no. in the reaction is called oxidant or oxidising agent.
5.1 Some Important oxidising agent or oxidant
1. All elements with high electronegative character like N, O, F, Cl, etc.
2. All metallic oxides like Li2O, Na2O, Na2O2, CO2, CaO, MgO, BaO2 etc.
3. Some nonmetallic oxides like CO2, SO2, H2O2, O3.
4. All neutral compound or ion in which element shows their higher oxidation no. or state are act as
oxidant or oxidising agent like KMnO4, H2SO4, SnCl4, H3PO4, K2Cr2O7, HClO4, CuCl2, HNO3,
H2SO5, FeCl3, HgCl2, etc.

6. REDUCTANT OR REDUCTION AGENT

Species which reduce other element in a reaction and oxidise itself to donate electrons and show
increase in its oxidation no. is called reductant or reducing agent.

6.1 Some Important reducing agent or reductant

1. All metals like, K, Mg, Ca, etc.
2. All metallic hydrides like NaH, CaH2, LiAlH4, NaBH4, AlH3, etc.
3. All hydroacids like HF, HCl, HBr, H2S etc.
4. Some organic compounds like Aldehyde, formic acid, oxalic acid, tartaric acid.
5. All neutral compounds or ions, which show their lower oxidation state.
MnO, HClO, HClO2, H3PO2, HNO2, H2SO3, FeCl2, SnCl2, Hg2Cl2, CH2Cl2 etc.
Some Important compound which can act as oxidant and reductant both
HNO2, SO2, H2O2, O3, Al2O3, CrO2, MnO2, ZnO, CuO,

NOTE : Al2O3, CrO2, MnO2, ZnO, CuO are called as amphoteric oxide.

7. OXIDATION NUMBER
A. Definition : It represents the number of electron gained or lost by atom when it changes in compound
from a free state.
(a) If electron are lose by an atom in the formation of compound, oxidation number is given (+)ve sign.
(b) If electrons are gain by an atom in the formation of compound oxidation number given is (–)ve sign.
(c) It represents the real charge in case of ionic compounds and represents the imaginary charge in
case of covalent compounds.
(d) Maximum oxidation no. of an element is equal to group no. in the periodic table
(e) Minimum oxidation no. of an element is equal to group no. – 8.
I group elements always shows +1 oxidation no.
II group elements always shows +2 oxidation no.
III group elements show +3 oxidation no. but +1 becomes more stable going down the
group (due to inert pair effect)
IV group shows –4 to +4 oxidation no.
V group shows –3 to +5 oxidation no.
VI group shows –2 to +6 oxidation no.
VII group shows –1 to +7 oxidation no.
Inert gases show zero oxidation no.
7.1 Oxidation no. for Coordinate bond
(a) When coordinate bond is formed from low electronegative element to high electronegative element
then the e– donor element shows +2 oxidation number whereas e– acceptor element shows –2,
oxidation no. in this type of bonded compounds. For example in H2SO4.
Here 'S' is low electronegative element than O. therefore, number of S = +2 and O. N. of O = –2
(b) When coordinate bond is formed between the two same electronegative elements then the e– donor
element shows +2 oxidation number where e– acceptor element shows –2 oxidation number in this
type of bonded compound.
For example :– In Na2S2O3
Here O.N. of 'S' is +2, Because it is e– donor and the other 'S' is –2, Because it is e– acceptor.
(c) When coordinate bond is formed from high electronegative element to low electronegative element
then no change will be shown by both the elements, which is bonded by coordinate bond. eg.
CH3NC
8. OXIDATION STATE
Oxidation state of an atom is defined as oxidation number per atom for all practical purposes. Oxidation
state is often expressed as oxidation number.
8.1 The rules to derive oxidation number or oxidation state
(a) The O.S. of an element in its free state is zero. Example O.S.’ s of Na, Cu, I2, Cl2, O2 etc. are zero
(b) Sum of O.S.’ s of all the atoms in neutral molecule is zero.
(c) Sum of O.S.’ s of all the atoms in a complex ion is equal number of charge present on it.
(d) In complex compounds, O.S. of some neutral molecules (ligands) is zero. Example CO, NO, NH3,
H2O.
(e) Generally O.S. of oxygen is –2 but in H2O2 it is –1 and in OF2 it is +2.
(f) Generally O.S. of Hydrogen is +1 but in metallic hydrides it is –1.
(g) Generally O.S. of halogen atoms is –1 but in interhalogen compounds it changes.
NOTE : Some times same atom in a compound has different O.S. For example, structure of Na2S2O3
is
Here S1 and S2 both are sulphur atoms but they have different O.S.
O.S. of S1 = 6
O.S. of S2 = –2 (it is accepting two electrons from S1)

62
Average O.S. of S = =2
2
(h) Generally, O.S. of alkali metals is +1 and that of alkaline earth metals is +2.
(i) O.S. of transition elements very high from compound to compound. Mn has O.S. from +1 to +7.
Mn2O  +1, MnO  +2, Mn3O4  8/3, MnO2  +4, Mn2O5  +5, MnO42–  +6, MnO4–  +7
(j) O.S. of an atom may be fractional, negative, zero as well as Positive.
8.2 Oxidation State As A periodic Property
Oxidation state of an atom depends upon the electronic configuration of atom it is periodic properties.
(a) I A group or alkali metals shows +1 oxidation state.
(b) II A group or alkaline earth metals show +2 O.S.
(c) The maximum normal oxidation state, show by III A group elements is +3. These elements also
show +2 to +1 oxidation states also.
(d) Elements of IVA group show their max & min. oxidation states +4 & - 4 respectively.
(e) Non metals shows number of oxidation states, the relation between max & min. oxidation states for
non metals is equal to maximum O.S. –minimum O.S. = 8
For example sulphur has maximum oxidation number +6 as being in VI A group element.
8.3 Fractional Oxidation States
Lot of elements shows fractional oxidation states. For example oxidation state of oxygen in superoxides of alkali
metals (KO2, SO2, RbO2) is -1/2.
eg. In Fe3O4, Fe shows its oxidation state as 8/3 as it is a mixed oxide and can be written as
FeII Fe2IIIO4.

Example Based on Oxidation number and oxidation state

Ex.1 What is the oxidation state of nitrogen in NaN3 ?
(A) – 3/1 (B) 3
(C) – 3 (D) – 1/3 Ans. [D]
Sol. In NaN3
Na N3
1 + 3x = 0, x = – 1/3
So, oxidation number of nitrogen in NaN3 is – 1/3.
Ex.2 What is the oxidation number of oxygen in OF2 ?
(A) +2 (B) +4 (D) +3 (D) None Ans. [A]
Sol. In OF2
x + 2(– 1) = 0, x = + 2
Hence oxidation number of oxygen in OF2 = + 2.
9. REDOX REACTIONS
(a) The reactions in which oxidation and reduction both occur simultaneously are called redox reac-
tions.
(b) Most of the chemical reactions are redox because if one element is there to lose electrons, other
element has to be there to accept them.

S.No. Reaction Oxidant Reductant

(Getting Reduced) (Getting Oxidised)

1. C + O2  CO2 O [0   – 2] C [0  + 4]
2. PbS + 4O3  PbSO4 + 4O2 O [+ 2  0] S [ – 2  + 6]
3. PbS + 4H2O2  PbSO4 + 4H2O O [–1  –2] S [– 2  + 6]
4. Sn + 2F2  SnF4 F [0  –1] Sn [0 + 4]
5. SO2 + 2H2O +Cl2  2HCl + H2SO 4 Cl [0  –1] S [+ 4  + 6]
6. I2 + 10HNO3  2HIO3 + 10NO2 + 4H2O N [+ 5  + 4] I [0  + 5]
7. CuO + H2  Cu + H2O Cu [+ 2  0] H [ 0  + 1]
8. 2KMnO4 + 3H2SO4 + 5H2S  Mn [+ 7  + 2] S [–2  0]
K2SO4 + 2MnSO4 + 8H2O + 5S
9. H2O2 + Ag2O  2Ag + H2O + O2 Ag [+ 1  0] O [–1  0]
(Oxygen of H2O2)
10. H2SO4 + 2HI  SO2 + I2 + 2H2O S [+6  +4] I [–1  0]
NOTE : In reaction 2 oxygens of ozone have different OS.
Structure of ozone is
O3  O 1=O 2
OS of O1 = + 2
OS of O2 = 0
Here O1 is getting reduced in reaction 2
OS of O3 = – 2
(d) Redox reactions may be intramolecular or disproportionation reactions. It depends upon whether
the migration of electron takes place in the atoms of the same compound or different compounds
.
(i) Intermolecular redox reaction
+6 +2 +4
2H2SO4(conc.) + Cu  CuSO4 + SO2 + 2H2O
(ii) Intramolecular redox reaction
+5–2 –1 0
2KClO3  2KCl + 3O2
(iii) Disproportions Redox Reaction : In this type of redox reactions same element acts as both oxidsing
& reducing agent.
0 +1 –
Cl2 + H2O  HClO + HCl
10. BALANCING OF REDOX EQUATIONS BY ION ELECTRON METHOD

10.1 Acidic Medium

(a) consider the example,


H
Cr2O72– + C2O42–  Cr3+ + CO2
(b) Write both the half reactions.
Cr2O72–  Cr3+ (Reduction half reaction)
C2O42–  CO2 (Oxidation half reaction)
(c) Atoms other than H and O are balanced
Cr2O72–  2Cr3+
C2O42–  2CO2
(d) Balance O–atoms by the addition of H2O to another side
Cr2O72–  2Cr3+ + 7H2O
C2O42–  2CO2
(e) Balance H–atoms by the addition of H+ ions to another side
Cr2O72– + 14H+  2Cr3+ + 7H2O
C2O42–  2CO2

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

Cr2O72– +14H+ +6e–  2Cr3+ +7H2O
C2O42–  2CO2 + 2e–
(g) Multiply equations by a constant to get number of electrons same in both side. In the above case
second equation is multiplied by 3 and then added to first equation.
Cr2O72– + 14H+ + 6e–  2Cr3+ + 7H2O

Cr2O72– + 3C2O42– + 14 H+  2Cr3+ + 6CO2 + 7H2O

10.2 Alkaline Medium
(a) Consider the reaction

OH
Cr(OH)3 + IO3–  I– + CrO42–
(b) Separate the two half reactions.
Cr(OH)3  CrO42– (Oxidation half reaction)
IO3–  I– (Reduction half reaction)
(c) Balance O– atoms by adding H2O.
H2O + Cr(OH)3  CrO42–
IO 3–  I– + 3H2O
(d) Balance H–atoms by adding H2O to side having deficiency and OH– to side having deficiency of
H–atoms.
5OH– + H2O + Cr(OH)3  CrO42– + 5H2O or 5OH– + Cr(OH)3  CrO42– + 4H2O
– –
IO3 + 6H2O  I + 3H2O + 6OH –

or IO3– + 3H2O  I– + 6OH–

(e) Balance the charges by electrons
5OH– + Cr(OH)3  CrO42– + 4H2O + 3e–
IO3– + 6H2O + 6e–  I– + 3H2O + 6OH–
(f) Multiply first equation by 2 and add to second to give
10OH– + 2Cr(OH)3  2CrO42– + 8H2O + 6e–
IO 3– + 6H2O + 6e–  I– + 3H2O +6OH–
___________________________________________________

4OH– + 2Cr(OH)3 + IO3–  5H2O + 2CrO42– + I–

Example Based on Balancing of equations

Ex.3 What will be the value of x, y and z in the following equation –
H2C2O4 + xH2O2  yCO2 + zH2O
(A) 2, 1, 2 (B) 1, 2, 2 (C) 2, 2, 1 (D) None
Ans. [B]
Sol. (i) The half reaction for oxidation is,
H2C2O4  CO2
Balancing carbon atoms on both sides,
H2C2O4  2CO2
Balancing hydrogen atoms on both sides,
H2C2O4  2CO2 + 2H+
Balancing the charge on both sides,
H2C2O4  2CO2 + 2H+ + 2e– (balanced)
(ii) The half reaction for reduction is –
H2O2  H2O
Balancing oxygen atoms on both sides,
H2O2  2H2O
Balancing hydrogen atoms,
H2O2 + 2H+  2H2O
Balancing the charge,
H2O2 + 2H+ + 2e–  2H2O
Now, adding both equation,
H2C2O4 + H2O2  2CO2 + 2H2O
This is balanced equation.
Ex.4 What will be the value of x, y and z in the following equation –
x2 + yOH–  O3– + z– + 3H2O
(A) 3, 5, 6 (B) 5, 6, 3 (C) 3, 6, 5 (D) 6, 3, 5 Ans. [C]
Sol. 0 +5
2  O 3 ..... (i) Oxidation
0 –1
  – ..... (ii) Reduction
Balancing atoms of Iodine on two sides,
we get,
2  2O3–
or, 2 + 12OH  2O3– + 6H2O
Balancing change,
2 + 12OH–  2O3– + 6H2O + 10e–
2  2–
and (2 + 2e–  2–) × 5
————————————————————–
Adding, 62 + 12OH–  2O3 + 10– + 6H2O
or, 32 + 6OH–  O3– + 5– + 3H2O
It is balanced equation.
Ex.5 What will be the value of a, b, c, d, e and f in the following equation –
aMnO4– + bC2O4– – + cH+ 
dMn++ + eCO2 + f H2O
(A) 2, 2, 10, 8, 5, 16 (B) 2, 5, 16, 2, 10, 8
(C) 2, 5, 10, 2, 8, 16 (D) 2, 8, 16, 2, 5, 10 Ans. [B]

Sol. (i) The half reaction for reduction is,

MnO4–  Mn++
Balancing with respect to oxygen by adding 4H2O on R.H.S.,
MnO4–  Mn++ + 4H2O
Balancing with respect to hydrogen by adding 8H+ on L.H.S.,
MnO4– + 8H+  Mn++ + 4H2O
Balancing charge by adding electrons,
MnO4– + 8H+ + 5e–  Mn++ + 4H2O
(ii) The half reaction for oxidation is,
C2O4– –  2CO2
Balancing with respect to electrical charge by adding electrons on R.H.S.
C2O4– –  2CO2 + 2e–
Now, to equalise the number of electrons, the reduction half reaction is multiplied by 2 and oxidation
half reaction by 5, so on adding, we get
(C2O42 –  2CO2 + 2e–) × 5
(MnO4– + 8H+ + 5e– 
Mn++ + 4H2O) × 2
————————————————
2MnO4– + 5C2O4– – + 16H+ 2Mn++ + 10CO2 + 8H2O
This is the balanced equation.
11. EQUIVALENT WEIGHT
(a) Equivalent wt. of an oxidant (get reduced)

Mol. wt.
=
No. of electrons gained by one mole

Mol. wt.
=
Decrease in O. S.  No. of atom undergoing reduction
Example :
In acidic medium
6e– + Cr2O72– + 14H+  2Cr3+ + 7H2O
Here atoms undergoing reduction is Cr its O.S. is decreasing from 6 to 3
Mol. wt. of K 2Cr2O7 Mol. wt.
Eq. wt. 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]
(b) Similarly equivalent wt. of a reductant (gets oxidised)
Mol. wt.
=
No. of electrons lost by one mole
Mol. wt.
=
increase in O.S.  No. of atom undergoing oxidation
Example :
In acidic medium, C2O42–  2CO2 + 2e–
Here, O.S. of carbon is changing from +1 to +2 i.e. each carbon atom is losing one electron and there
Mol.wt
are 2 atoms of carbon so total electrons lost = 2 so, eq. wt =
2
(c) In different condition a compound may have different equivalent wts. Because, it depends upon the
number of electrons gained or lost by that compound in that reaction.
Example :
(i) MnO4–    Mn2+ (acidic medium)
(+7) (+2)
So, Here 5 electrons are taken so eq. wt
Mol. wt. of KMn O 4 158
= = = 31.6
5 5
(ii) MnO4 –  MnO2 (neutral medium)
(+7) (+4)
Here, only 3 electrons are gained
Mol. wt. of KMnO4
so, eq. wt =
3
158
= = 52.7
3
(iii) MnO4–  MnO 4–2 (alkaline medium)
(+7) (+6)
Here, only one electron is gained
Mol. wt. of KMn O 4
so, eq. wt = = 158
1
NOTE : It is important to note that KMnO4 acts as an oxidant in every medium although with different
strength which follows the order –
acidic medium > neutral med. > Alkaline medium
while, K2Cr2O7 acts as an oxidant only in acidic medium as follows
Cr2O72–  2 Cr3+
(2 x 6)   (2 x 3)
Here, 6 electrons are gained
Mol. wt. of K 2Cr2O7 294.21
so eq. wt = = = 49.03
6 6
(d) It is clear that KMnO4 is better oxidant than K2Cr2O7 .
(e) Try to balance reaction (a) (b) (c) of reduction of KMnO4 by ion electron method as you should get
following –
(i) MnO4– + 8H+ + 5e–  Mn2+ + 4H2O (acidic medium)
(ii) MnO4– + e–  MnO42– (alkaline medium)

Example based on equivalent weight

Ex.6 What will be the equivalent weight of permanganate ion in the following redox reaction
–
MnO4– + 8H+ + 5e–  Mn++ + 4H2O
(A) M/5 (B) M/6 (C) M/8 (D) 5M
Ans.[A]
Sol. Equivalent weight of MnO4–
Molecular weight of MnO4 – M
= 
5 5
Ex.7 What will be the equivalent weight of a reducing agent is that weight which donates one
electron in a chemical reaction–
2S2O3– –   S4O6– – + 2e–
(A) 2M (B) 3M (C) M /2 (D) M
Ans. [D]
2M
Sol. Equivalent weight of S2O3– – = = M.
2
Ex.8 In the following reaction, what is the molecular weight of oxidant and reductant
respectively –
5Zn + V2O5  5ZnO + 2V [V = 50.94, Zn = 65.38 and O = 16]
(A) 18.2, 32.69 (B) 30, 20 (C) 34.10, 20.2 (D) 40, 10
Ans.[A]
Sol. Change in the O.N. of Zn : Zn  ZnO
Zn = 0, Zn in ZnO = + 2
Change = 2
V2O5  2V, [for V2] + 10  0
Change = 10
65 . 38 50 . 94  2  80
eqvt. wt. of reductant = = 32.69 gm eqvt. wt. of oxidant =
2 10
= 18.18 or 18.2
12. EQUIVALENT WEIGHT IN DISPROPORTION REACTION
The equivalent weight of the substance undergoing disproportion can be determined by the following
method.
Consider the substance ‘X’ is undergoing disproportionation reaction.
(i) Find out the equivalent weight of ‘X’ for oxidation reaction, say it is E1.
(ii) Also find out the equivalent weight of ‘X’ for reduction reaction, say it is E2.
(iii) The equivalent weight of ‘X’ = E1 + E2 for example, Cl2 disproportionate in Cl– & ClO3–

The X factor for oxidation = 2

The X factor for reduction = 10

71 71
The equivalent wt of Cl2 = + = 35.5 + 7.1 = 42.6 Ans.
2 10

Solved Example

Ex.1 Which of the following acts as both oxidant and reductant –

(A) HNO3 (B) HNO2

(C) Both HNO3 & HNO2 (D) Neither HNO3 nor HNO2
(Ans. B)
Sol. O.N. of N in HNO2 is + 3
Max. O.N. of N is + 5
Min. O.N. of N is – 3
Thus O.N. of N in HNO2 can show an increase or decrease as the case may be. That is why HNO2
acts as oxidant and reductant both.
O.N. of N in HNO3 is + 5, Hence it can act only as an oxidant.

Ex.2 State which of the following reactions is neither oxidation nor reduction –
(A) Na  NaOH (B) Cl2  Cl + ClO–3
–

(C) P2O5  H4P2O 7 (D) Zn + H2SO4  ZnSO4 + H2

(Ans. C)
Sol. In the reaction P2O5  H4P2O 7
The O.N. of P in P2O5 is
2x + 5 (–2) = 0 or x = +5
The O.N. of P in H4P2O7 is
4 (+1) + 2 (x) +7 (–2) = 0
2x = 10 or x = +5
Since there is no change in O.N. of P, hence the above reaction is neither oxidation nor reduction.

Ex.3 In the reaction

C2O4–2 + MnO–4 + H+  Mn+2 + CO2

the reductants is –

(A) C2O4– 2 (B) H+

(C) MnO¯4 (D) None of the above
Ex.3 In the reaction

C2O4–2 + MnO–4 + H+  Mn+2 + CO2

the reductants is –

(A) C2O4– 2 (B) H+

(C) MnO¯4 (D) None of the above (Ans. A)
Sol. In the above reaction C2O4–2 acts as a reductant because it is oxidised to CO2 as
C2O4–2  2CO2 + 2e(oxidation)
C2O4–2 reduces MnO4¯ to Mn+2 ion in solution.

Ex.4 Oxidation number of cobalt in [Co(NH3)6]Cl2Br is –

(A) + 6 (B) Zero (C) + 3 (D) + 2 (Ans. C)
Sol. Let the O.N.of Co be x
O.N. of NH3 is zero
O.N. of Cl is –1
O.N. of Br is –1
Hence, x + 6 (0) – 1 x 2 –1 = 0
 x=+3
so, the oxidation number of cobalt in the given complex compound is +3.

Ex.5 The order of increasing O.N. of S in S8, S2O8–2 , S2O3–2, S4O6–2 is given below –
(A) S8 < S2O8–2 < S2O3–2 < S4O6–2
(B) S2O8–2 < S2O3–2 < S4O6–2 < S8
(C) S2O 8–2 < S8 < S4O6–2 < S2O3–2
(D) S8 < S2O3–2 < S4O6–2 < S2O8–2 (Ans. D)
Sol. The O.Ns. of S are shown below along with the compounds
S8 , S2O8–2, S2O3–2, S4O 6–2
0 + 6 +2 +2.5
Hence the order of increasing O.N. of S is
S8 < S2O3–2 < S4O6–2 < S2O8–2

Ex.6 The composition of a sample of wustite is Fe0.93O1.00. What percentage of iron is present in the
form of Fe (III)
(A) 13.05 (B) 14.05
(C) 15.05 (D) 16.05 (Ans. C)
200
Sol. O.N. of. Fe in wustite is = = 2.15
93
It is an intermediate value in between Fe (II) & Fe (III)
Let % of Fe (III) be a, then
2 x (100 – a) + 3 x a = 2.15 x100
a = 15.05
 % of Fe (III) = 15.05%
Ex.7 The oxid.no. of Cl in NOClO4 is –
(A) + 11 (B) + 9
(C) + 7 (D) + 5 (Ans. C)
Sol. The compound may be written as NO+ ClO4¯
For ClO4 –, Let Ox. No.of Cl = a
a + 4 x (–2) = –1
a = +7
Hence, the oxidation no. of Cl in NOClO4 is +7.
Ex.8 The two possible oxidation numbers of N atoms in NH4NO3 are respectively –
(A) +3, +5 (B) +3, –5
(C) –3, +5 (D) –3, –5 (Ans. C)
Sol. There are two N atoms in NH4NO3, but one N atom has negative oxidation number (attached to
H) and the other has positive oxid.no. (attached to O). Therefore evaluation should be made
separately as –
O.N. of N is NH4+ O.N. of N in NO3¯
a + 4 x (+1) = +1 and a + 3 (–2) = –1
 a = –3 a=+5
Here the two O.N. are –3 and +5 respectivley.
Ex.9 The oxidation number of S in H2S2O8 is –
(A) +8 (B) –8 (C) +6 (D) +4 (Ans. C)
Sol. In H2S2O8, two O atoms form peroxide linkage i.e
O O
 
H – O – S – O –O – S – O – H
 
O O
2 x 1 + 2a + 6( –2) + 2 (–1) = 0
 a = + 6
Thus the O.N. of S in H2S2O8 is + 6.
Ex.10 When K2Cr2O7 is converted into K2CrO4 the change in oxidation number of Cr is –
(A) 0 (B) 3 (C) 4 (D) 6 (Ans. A)
Sol. When Cr2O7–2 is converted into CrO4–2 the change in oxidation number of Cr is zero
Cr2O7–2  CrO4–2
+6 +6
There is no change in oxidation state of Cr, hence it is neither oxidised nor reduced and remains
in the same oxidation state.
Ex.11 The oxidation number of S in (CH3)2 SO is –
(A) 1 (B) 2 (B) 0 (D) 3 (Ans. C)
Sol. Let the oxidation no. of S is 'a'
O.N. of CH3 = +1
O.N. of O = –2
2(+1) + a + (–2) = 0
a = 0
Hence the oxidation no. of S in Dimethyl sulphoxide is zero.
Ex.12 What will be the oxidation number of I in the KI3 –
1 1
(A) – (B) – (C) + 4 (D) + 3 (Ans. A)
3 4
1
Sol. In KI3 1 + 3 × (a) = 0 a = –
3
or KI3 is KI + I2
 I has two oxidation no. –1 and 0 respectively. However factually speaking oxidation number of
I in KI3 is on average of two values – 1 and 0.
1  2  ( 0 ) 1
Average O.N. =  .
3 3
Ex.13 Oxidation number of Fe in [Fe(CN)6]–3, [Fe(CN)6]–4, [Fe(SCN)]+2 and [Fe(H2O)6]+3 respectively
would be–
(A) +3, +2, +3 and +3 (B) +3, +3, +3 and +3
(C) +3, +2, +2 and +2 (D) +2, +2, +2 and +2 (Ans. A)
Sol. Oxidation number of Fe in–
First Second Third Fourth
x–6 = –3 x–6 = –4 x–1 =+2 x+ 6×0 =+3
x = +3 x = +2 x = +3 x = +3
Ex.14 Which of the following is not a redox reaction–
1 1
(A) H2 + I  HI (B) PCl5  PCl3 + Cl2
2 2 2
(C) 2CuSO4 + 4KI  Cu2I2 + 2K2SO4 + I2 (D) CaOCl2 Ca+2 + OCl¯ + Cl¯ (Ans. D)
Sol. In all the above reaction except (D) there is change in oxidation states of reactant and product
atoms, hence they are all redox reactions. In reaction (D) the oxidation states of the atoms of the
reactants and products remain unchanged hence, it is not a redox reaction.
Ex.15 In the reaction Al + Fe3O4  Al2O3 + Fe –
what is the total no. of electrons transferred during the change –
(A) 16 (B) 24 (C) 8 (D) 12 (Ans. B)

Sol. 2Alº  Al2+3  6e¯ ............. (A)

8e + Fe3+8/3 3Feº ............. (B)
Multiplying Eq. (A) by 4 and Eq. (B) by 3, then on addition
8Alº  4Al2+3 + 24e
24e + 3Fe3+8/3  9Feº
—————————————————————
8Alº + 3Fe3+8/3  9Feº + 4Al2+3
————————————————
or 8Al + 3Fe3O4  4Al2O3 + 9Fe
Therefore, it is clear that total no. of electrons transferred during change = 24
Ex.16 In the redox reaction –
10FeC2O4 + x KMnO4 + 24H2SO4 
5Fe2 (SO4)3 + 20CO2 + y MnSO4 + 3 K2SO4 + 24H2O.
The values of x and y are respectively –
(A) 6, 3 (B) 3, 6 (C) 3, 3 (D) 6, 6 (Ans. D)
Sol. The balanced redox reaction given above can be written as :
10FeC2O4 + 6KMnO4 + 24H2SO4 
            5Fe2 (SO4)3 + 20CO2 + 6 MnSO4 + 3 K2SO4 + 24H2O
so the value of x = 6 and y = 6
Ex.17 A solution containing 2.68 x 10–3 mol of A+n ions requires 1.61 x 10–3 mole of MnO–4 for the
oxidation of A+n to AO–3 in acidic medium. What is the value of n –
(A) 1 (B) 2 (C) 3 (D) 4 (Ans. B)
Sol. The reaction are
MnO–4 + 8H+  5e–  Mn+2 + 4H2O
A+n + 3H2O AO3– + 6H+ + (5–n) e–
Amount of electrons involved in the given amount of MnO4– = 5 x 1.61 x 10–3 mol.
Equating these two we get
5 x 1.61 x 10–3 = (5–n) 2.68 x 10–3
 n = 2 (approx.)
Ex.18 Which of the following is correctly balanced half reaction –
(A) AsO3–3+ H2O  AsO4–3 + 2H+ – 2e– (B) H2O 2 + 2e  O 2 + 2H+
(C) Cr2O7–2 + 14H+  2Cr+3 + 7H2O – 6e– (D) IO–3 + 6H+  I2 + 3H2O + 5e–
(Ans. C)
Sol. The correctly balanced half reaction is –
Cr2O7–2 + 14H+  2Cr+3 + 7H2O –6e– It is a reduction half reaction in balancing the
equation by ion–electron method.