SHOBHIT NIRWAN's

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REDOX REACTIONS
NEW NOTES FOR CLASS 11 2022 EXAMS
 OVERVIEW OF THE CHAPTER
1. Uses of redox reaction.

2. Classical idea of redox reactions – oxidation and reduction reaction.

3. Redox reactions in terms of electron transfer reactions.

4. Competitive electron transfer reactions.

5. Oxidation number.

6. Types of Redox Reactions:

(i) Combination reactions
(ii) Decomposition reactions
(iii) Displacement reactions:
Metal displacement and non – metal displacement

7. Balancing of redox reactions:

(i) Oxidation number method
(ii) Half reaction method

8. Redox reactions as the basis for titrations.

9. Limitations of concept of oxidation number.

10. Redox Reactions & electrode process.

1. Uses of Redox Reaction:
a. Extensive use in pharmaceutical, biological, industrial, metallurgical and
agricultural areas.
b. Burning of different types of fuels for obtaining energy.
c. In electrochemical process for extraction of highly reactive metals and non-
metals.
d. Manufacturing of chemical compounds like caustic soda.
e. In dry & wet batteries.
f. Corrosion of metals.
g. Environment issues like use of hydrogen economy (use of liquid hydrogen as
fuel) & development of ‘ozone hole’ are under redox phenomenon)

2.Classical Idea of Redox Reactions – Oxidation &

Reduction Reaction:
(i)Oxidation: Oxygen का जुड़ना
Atmosphere म" dioxygen present है , तो काफ़* elements oxygen के साथ combine हो जाते
है l इसी वजह से 2यादातर elements atmosphere म" oxides के form म" पाए जाते ह8 l

Eg: 2Mg(s) +O2(g) 2MgO (s)

S(s) + O2(s) SO2 (s)

CH4(g) + 2O2(g) CO2(g) + 2H2O(l) → (i)

ऊपर के example से हम यह भी कह सकते ह8 ;क oxidation- removal of hydrogen भी होता है l

Eg: 2H2S (g) + O2(g) → 2S (s) + H2O (l) → (ii)

→ Removal of electropositive elements is also called as oxidation.

2K4 [Fe(CN)6] (aq) + H2O2 (aq) → 2K3 [Fe(CN)6] (aq) + 2KOH (aq)

→ Addition of electronegative element.

Mg (s) + F2 (g) → MgF2 (s)
Mg (s) + Cl2(g) → MgCl2 (s)
Mg (s) + S (g) → MgS (s)
 Oxidation Reduction
Addition of oxygen Removal of oxygen
Addition of electronegative element Removal of electronegative element
Removal of hydrogen Addition of hydrogen
Removal of electropositive element Addition of electropositive element

SOME EXAMPLES:
Δ
2HgO2(s) 2Hg(l) + O2(g)
↓
Removal of oxygen from mercuric oxide

2FeCl3 (aq) + H2(g) ------------------→ 2FeCl2 (aq) + 2HCl (aq)

↓
Removal of electronegative element chlorine from ferric chloride

CH2= CH2 + H2 ------------------→ H3C – CH3 → addition of hydrogen

2HgCl2 (aq) + SnCl2 (aq) ------------------→ Hg2 Cl2 (s) + SnCl4 (aq)
↓
Addition of mercury to mercuric chloride

ऊपर के examples से हम" ये समझ रहा है क* jab oxidation और reduction एक साथ होते ह8 इस
type के reactions को हम Redox Reactions कहते ह8|

Q1) In the reactions given below, identify the species undergoing oxidation and
reduction:
(i) H2S (g) + Cl2 (g) → 2 HCl (g) + S (s)
(ii) 3Fe3O4 (s) + 8 Al (s) → 9 Fe (s) + 4Al2O3 (s)
(iii) 2 Na (s) + H2 (g) → 2 NaH (s)

Solution
(i) H2S is oxidised because a more electronegative element, chlorine is added to
hydrogen (or a more electropositive element, hydrogen has been removed from S).
Chlorine is reduced due to addition of hydrogen to it.

(ii) Aluminium is oxidised because oxygen is added to it. Ferrous ferric oxide (Fe3O4)
is reduced because oxygen has been removed from it.

(iii) With the careful application of the concept of electronegativity only we may infer
that sodium is oxidised and hydrogen is reduced.
Reaction (iii) chosen here prompts us to think in terms of another way to define redox
reactions.
3.Redox Reactions in terms of electron Transfer of
Electrons:

इन Reactions म" दो चीजे हो रह@ है :

(i) gain of e-
(ii) loss of e-
इन steps को हम separate करके भी Aलख सकते ह8 l
From 1st Reaction
(a) 2Na (s) → 2Na+ (g) + 2e-
(b) Cl2 (g) + 2e- → 2Cl- (g)
(a) & (b) step को हम half step कहते ह8, जो clearly electrons को द@खाते है l
→ Half reactions that involve loss of electrons are called oxidation reactions and the
half reactions that involve gain of electrons are called reduction reactions.

Similarly, In 2nd reactions Na oxidise हो रहा यानी e- donate कर रहा है इसीAलए हम Na को

reducing agent कह" गे EयF;क Na e- donate कताG है हर उस element जो उसके साथ interact
करता है l

Summary
Oxidation : loss of electron(s) by any species.
Reduction : gain of electron(s) by any species. Ncert definations
Oxidising agent : Acceptor of electron(s).
Reducing agent : donor of electron(s).
 Q2) Justify that the reaction : 2 Na(s) + H2(g) → 2 NaH (s) is a redox change.
Solution
Since in the above reaction the compound formed is an ionic compound, which may
also be represented as Na+ H- (s), this suggests that one half reaction in this process
is :
2Na (s) → 2 Na+ (g) + 2e-

and the other half reaction is:

H2 (g) + 2e- → 2 H- (g)

This splitting of the reaction under examination into two half reactions automatically
reveals that here sodium is oxidised and hydrogen is reduced, therefore, the complete
reaction is a redox change.

4.Competitive Electron Transfer Reactions:

Take strip of metallic zinc in aqueous solution of copper nitrate (जोक* blue colour का
होता है )
अब थोड़ी दे र बाद तम
ु ये दे खोगे क* strip के ऊपर reddish metallic क* coating आ जाएगी और जो
blue colour solution का था वो गयाब हो जाएगा l

Q. Blue colour disappear EयF हुआ ??

Eयक
ु * strip के Zn2+ ions का solution म" formation हुआ है िजसके कारण से Cu2+ ions disappear
हो गए (Cu2+ blue colour दे रहा था solution म" )

Zn (s) + Cu+2 (aq) → Zn2+ (aq) + Cu (s) → (1)

Zn → lost electrons ∴ zinc is oxidised.

Cu → gained electrons that zinc lost ∴ copper ion is reduced

Q3)अगर hydrogen sulphide (H2S) gas हम colourless solution िजसमे Zn2+ ions से पार कर" गे तो Eया होगा
??
Answer:- Appearance of white zinc sulphide ZnS can be seen on making the solution alkaline with
ammonia.
→ चलो अब ऊपर वाले experiment को उPटा करते ह8 l
Strip हमने लेल@ copper क* zinc sulphate के solution म" But हमे कोई reaction होता हुए नह@ं
Tदखी और H2S gas[hydrogen sulphide] solution के through pass करने पर cupric sulphide
का black colour नह@ं बना; indication होता है Cu2+ ions के pressure का l

→ Thus we conclude that state of equilibrium for reaction 1 greatly favour the products
over the reactant

→ अब हम reaction कर" गे Cu rod और silver nitrate solution क*- solution develops blue
colour due to the formation of Cu2+ ion on account of the reaction.

(i) Cu(s) oxidised to Cu2+ (aq) कौनसा element (s) to (aq) और कौनसा (aq)
(ii) Ag+ (aq) reduced to Ag(s) to (s) हो रहा है observe करो l
(iii) Equilibrium greatly favours the products Cu2+ (aq) and Ag(s)

→ चलो अब metallic cobalt और nickel sulphate solution क* reaction करवाते ह8 l

→अब chemical test से हम ये पता चला क* Ni2+ (aq) and Co2+(aq) are present at moderate
concentrations. In this case neither reactants [Co(s) & Ni+2(aq)] nor the products [Co2+
(aq) and Ni(s)] are greatly favoured.

→ कोVसे metal क* ;कतनी tendency है electron release करने क* ये हम compare करके पता
कर सकते ह8 और इसक* list बना सकते ह8 l

Metal Activity or electrochemical series: List of metals in increasing or decreasing

order of their tendency to release electron. (table for this is given on last page)

5.Oxidation Number:
→Let us take an example 2H2 (g) + O2(g) → 2H2O (l)

→यहा H2 और O2 neutral state से positive state जा रहे ह8 पहले ये assume ;कया जाता था क*
H से 0 electron transfer हो रहा है मतलब H2 is oxidised & O2 is reduced.
बाद म" ये पता चल क* इस reaction म" charge transfer is only partial इिWलये यह electron shift
हो रहा है rather than a complete loss of electron.

In order to keep track of electron shifts in chemical reactions involving formation of

covalent compounds, a more practical method of using oxidation number has been
developed.
In this method, it is always assumed that there is a complete transfer of electron from
a less electronegative atom to a more electronegative atom

Rules for Oxidation Number:

1. Elements which are in free or uncombine state bear an oxidation number of zero
eg: H2, O2, Cl2, O3, P4, S8, Na, Mg, Al.

2. For ions having only one atom, oxidation number is equal to the change on ion.
Eg: Na+ ion → +1 Cl- ion → -1 Fe+3 ion → +3

Mg+2 ion → +2 O- ion → -2

All alkali metals (grp 1) have +1 oxidation number.
All alkanline earth metals (grp 2) have +2 oxidation number.
K3B:- aluminum has +3 oxidation state in all its compounds.

3. Oxidation number of hydrogen in most of the elements compounds is -2.

Exceptions →
(a) in peroxide oxygen atom are linked to each other ∴ oxidation number = 0

(b) In peroxide oxygen का oxidation number – 1

Eg: H2O2, Na2O2

(c) In superoxide oxygen का oxidation has -1/2 as oxidation number

Eg: KO2 , RbO2

(d) When O is bonded to F

OF2 : O has +2 oxidation number.
O2F2 : O has +1 oxidation number.

4. Oxidation number of hydrogen is +1 except when it is bonded to metals in binary

compounds. (compounds containing 2 elements)
Eg: LiH, NaH, CaH2 → oxidation number number is -1
Halogens (F,Cl, Br & I)

5. (a) Halogens (F,Cl, Br & I) have oxidation number of -1 when they occur as halide
ions in their compounds.
(b) Cl, Br, I when combine with oxygen have +1 oxidation number.

6. (i) The sum of all the oxidation number in a compound must be zero.
 (ii) In polyatomic ion, sum of all the oxidation number must be equal the charge on
the ion.
Eg: (CO3)2- → sum of C & 3O must be equal to -2

→ Metallic elements: +ve oxidation number.

Non-metallic elements: -ve or +ve oxidation number.
Transition elements: generally +ve oxidation number.

→ 1st, 2nd groups के elements oxidation number उनका group number है और बाक* groups
के elements का group number minus 10.

Conclusion: oxidation number generally increases across the period in 3rd period
highest value of oxidation number charges from 1 to 7.

K3B:- oxidation number को oxidation state भी कहते ह8 l

→ If 2 or more than 2 atoms of an element are present in the molecule or ion such as
Na2, S2O3 or Cr2O3, the oxidation number of the atom of that element will then be the
average of the oxidation number of all the atoms of that element.

Group 1 2 13 14 15 16 17
Element Na Mg Al Si P S Cl
Compound NaCl MgSO4 AlF3 SiCl4 P4O10 SF6 HClO4
Highest oxidation +1 +2 +3 +4 +5 +6 +7
number of state of
the group element

→ Stock Notation: ये german chemist Alfred Stock ने $दया था िजसमे हम oxidation

number roman numerical के form म# /लखते ह3 l
Eg: Au(III) Cl3, Au(I)Cl , Sn(II)Cl2

Q4)Using Stock notation, represent the following compounds :HAuCl4, Tl2O,

FeO, Fe2O3, CuI, CuO, MnO and MnO2.
Solution:
By applying various rules of calculating the oxidation number of the desired element
in a compound, the oxidation number of each metallic element in its compound is as
follows:
HAuCl4 → Au has 3
Tl2 O → Tl has 1
FeO → Fe has 2
Fe2O3 → Fe has 3
CuI → Cu has 1
CuO → Cu has 2
MnO → Mn has 2
MnO2 → Mn has 4
Therefore, these compounds may be represented as:
HAu(III)Cl4, Tl2(I)O, Fe(II)O, Fe2(III)O3, Cu(I)I, Cu(II)O, Mn(II)O, Mn(IV)O2.

NCERT: Definitions

Oxidation: An increase in the oxidation number of the element in the given substance.

Reduction: A decrease in the oxidation number of the element in the given substance.

Oxidising agent: A reagent which can increase the oxidation number of an element
in a given substance. These reagents are called as oxidants also.

Reducing agent: A reagent which lowers the oxidation number of an element in a

given substance. These reagents are also called as reductants.

Redox reactions: Reactions which involve change in oxidation number of the

interacting species.

Q5) Justify that the reaction:

2Cu2O(s) + Cu2S(s) → 6Cu(s) + SO2 (g)
is a redox reaction. Identify the species oxidised/reduced, which acts as an
oxidant and which acts as a reductant.

Solution:
Let us assign oxidation number to each of the species in the reaction under
examination. This results into:
+1 -2 +1 -2 0 +4 -2
2Cu2O(s) + Cu2S(s) → 6Cu(s) + SO2
We therefore, conclude that in this reaction copper is reduced from +1 state to zero
oxidation state and sulphur is oxidised from –2 state to +4 state. The above reaction
is thus a redox reaction.
Further, Cu2O helps sulphur in Cu2S to increase its oxidation number, therefore, Cu(I)
is an oxidant; and sulphur of Cu2S helps copper both in Cu2S itself and Cu2O to
decrease its oxidation number; therefore, sulphur of Cu2S is reductant.

6.Types of Redox Reactions:

(i)Combination Reactions:
A+B →C
• Either A & B or both A & B must be in the elemental from.
• All combustion reaction (which use elemental dioxygen) and other reactions
involving elements other than dioxygen are redox reactions.

0 0 Δ +4 -2
C(s) + O2 (g) → CO2 (g)
 0 Δ +2 -3
3Mg(s) + N2 (g) → Mg3 N2 (s)

-4 +1 0 Δ +4 -2 +1 -2
CH4 + 2O2 (g) → CO2 (g) + 2H2O (l)

(ii)Decomposition Reactions:
• Are opposite of combination reactions.
• Breakdown of a compound in 2 or more components and at least one of which
must be in thee elemental state.
+1 -2 Δ 0 0
2H2O (l) ------------------→ 2H2(g) + O2 (g)

+1 -1 Δ 0 0
2NaH (s) ------------------→ 2Na (s) + H2 (g)

+1 +5 -2 Δ +1 -1 0
2KClO3(s) ------------------→ 2KCl (s) + 3O2 (g)
• All decomposition reactions are not redox reactions.

+2 +4 -2 Δ +2 -2 +4 -2
Eg: Ca CO3 (s) ------------------→ Ca O (s) + CO2 (g)
As oxidation number is not changing.

(iii)Displacement Reactions:
An ion or atom in a compound is replaced by an ion or atom of other element.
X + YZ ------------------→ XZ + Y
(a) Metal Displacement:
• Metal can be displaced by another metal in the uncombine state.
• These reaction have many applications in metallurgical process in which pure
metals are obtained from their ores.

+2 +4 -2 0 Δ 0 +2 +4 -2
Eg: Cu SO4 (aq) + Zn (s) ------------------→ Cu (s) + Zn SO4 (aq)

+5 -2 0 Δ 0 +2 -2
V2 O2 (s) + 5Ca (s) ------------------→ 2V (s) + 5Ca O (s)

+4 -1 0 Δ 0 +2 -1
Ti Cl4 (l) + 2Mg (s) ------------------→ Ti (s) + 2MgCl2 (s)

+3 -2 0 Δ +3 -2 0
Cr2 O3 (s) + 2 Al (s) ------------------→ Al2O3 (s) + 2Cr (s)
(b) Non – Metal Displacement:
• Include hydrogen displacement & a rarely occurring reaction involving oxygen
displacement.
• All alkali metals & some alkaline earth metals (Ca, Sr & Ba) which are very good
reductants, will displace hydrogen from cold water.
0 +1 -2 +1 -2 +1 0
2 Na (s) + 2 H2O (l) ------------------→ 2Na OH (aq) + H2 (g)

0 +1 -2 +2 -2 +1 0
Ca (s) + 2 H2O (l) ------------------→ Ca (OH)2 (aq) + H2 (g)

• Less active metals such as magnesium & iron react with steam to produce
dihydrogen gas:
0 +1 -2 Δ +2 -2 +1 0
Mg (s) + 2 H2 O (l) ------------------→ Mg (OH)2 (s) + H2 (g)

0 +1 -2 +3 -2 0
2 Fe (s) + 3 H2 O (l) ------------------→ Fe2 O3 + 3 H2 (g)

• Metals which do not react with cold water are capable of displacing hydrogen
from acids.
Dihydrogen from acids may be produced by such metals which do not react
with steam like cadmium & tin. A few examples for the displacement of
hydrogen from acids are:

0 +1 –1 +2 –1 0
Zn(s) + 2HCl(aq) ---> ZnCl2 (aq) + H2 (g)

0 +1 –1 +2 –1 0
Mg (s) + 2HCl (aq) ---> MgCl2 (aq) + H2 (g)

0 +1 –1 +2 –1 0
Fe(s) + 2HCl(aq) ---> FeCl2(aq) + H2(g)

These reactions are used to prepare dihydrogen gas in the laboratory. Here,
the reactivity of metals is reflected in the rate of hydrogen gas evolution;
• Least reactive Fe
• Most reactive Mg
• Silver (Ag) & Gold (Au) → do not react with HCl.
• Reactivity decreases down the group
Eg: F > Cl > Br > I
Reactivity of metals α rate of hydrogen gas evolution

This implies that fluorine is so reactive that it can replace chloride, bromide
and iodide ions in solution. In fact, fluorine is so reactive that it attacks water
and displaces the oxygen of water :
 +1 -2 0 +1 -1 0
2H2 O (l) + 2F2 (g) ------------------→ 4HF(aq) + O2 (g)

∴ reactions of Cl, Br, I are using F are not carried out in aqueous solution.

0 +1 -1 +1 -1 0
Cl2 (g) + 2KBr (aq) ------------------→ 2 KCl (aq) + Br2 (s)
0 +1 -1 +1 -1 0
Cl2 (g) + 2KI (aq) ------------------→ 2 KCl (aq) + I2 (s)

• Br2 & I2 are coloured & dissolve in CCl4 ∴ can be easily identified.
0 -1 -1 0
Cl2 (g) + 2 Br- (aq) ------------------→ 2 Cl- (aq) + Br2 (l) → (1)

0 -1 -1 0
Cl2 (g) + 2I (aq) ------------------→ 2 Cl- (aq) + I2 (s) → (2)

Layer Test:
• Test for identifying Br- & I- in laboratory
• Reaction 1 & 2 form base for this reaction
Br displace iodide ion:
0 -1 -1 0
- -
Br2 (l) + 2 I (aq) ------------------→ 2Br (aq) + I2 (s)

Industrial Application of Halogen Displacement:

• Recovery of halogens from their halides required an oxidation process.
2 X- ------------------→ X2 + 2e-
X: halogen

Cl-
Br- oxidised chemically F- no chemical way to oxidise, oxidised
I- electrolytically.

(iv)Disproportionation Reaction:
• एक ह@ element का oxidation भी होगा और reduction भी होगा l
• One element should have at least 3 oxidation states.
• Both the higher & lower oxidation states of that element are formed.

+1 -1 +1 -2 0
Eg: 2H2 O2 (aq) ------------------→ 2H2O (l) + O2 (g)

O of H2O2 -1 to 0 in O2 (oxidation)
-1 to -2 in H2O (reduction)

0 -3 +1
P4 (s) + 3OH (aq)+ 3H2O(l) ------------------→ PH3(g) + 3H2 PO2- (aq)
-
 0 -2 +2
S8 (s) + 12 OH (aq) ------------------→ 4S (aq) + 2S2 O32- (aq) + 6H2O (l)
- 2-

0 +1 -1
Cl2 (g) + 2 OH- (aq) ------------------→ ClO- (aq) + Cl- (aq) + H2O (l) -----(a)
This Reaction is used for formation of household bleaching agents.
ClO- oxidises the colour – bearing stains of the substances to colourless
compounds
In this reaction, िजस तरह Cl react कर रहा है वैसे ह@ Br & I react कर" गे l पर F अलग
ताXरके से react करे गा l
2F2 (g) + 2OH- (aq) ------------------→ 2F- (aq) + OF2 (g) + H2 O (l)
यहा flourine water पे attack करके थोडा oxygen भी produce करे गा l

∴ F does not show disproportionation reaction as it is most electronegative

and cannot have positive oxidation state.

Q6) Which of the following species, do not show disproportionation reaction

and why ?
ClO-, ClO-2, ClO-3 and ClO-4
Also write reaction for each of the species that disproportionate.
Solution
Among the oxoanions of chlorine listed above, ClO4 – does not disproportionate
because in this oxoanion chlorine is present in its highest oxidation state that is, +7.
The disproportionation reactions for the other three oxoanions of chlorine are as
follows:

+1 -1 +5
3ClO ------------------→ 2Cl + ClO-3
- -

+3 hv +5 -1
6 ClO-2 ------------------→ 4ClO-3 + 2Cl-

+5 -1 +7
4ClO-3 ------------------→ Cl- + 3ClO-4

Q7) Suggest a scheme of classification of the following redox reactions

(a) N2 (g) + O2 (g) ------------------→ 2NO (g)
(b) 2Pb(NO3)2 (s) ------------------→2PbO (s) + 2NO2 (g) + ½ O2 (g)
(c) NaH (s) + H2O (l) ------------------→ NaOH (aq) + H2 (g)
(d) 2NO2 (g) + 2OH-2 (aq) ------------------→ NO-2 (aq) + NO-3 (aq) + H2O (l)

Solution
In reaction (a), the compound nitric oxide is formed by the combination of the elemental
substances, nitrogen and oxygen; therefore, this is an example of combination redox
reactions.
The reaction (b) involves the breaking down of lead nitrate into three components; therefore,
this is categorised under decomposition redox reaction.

In reaction (c), hydrogen of water has been displaced by hydride ion into dihydrogen gas.
Therefore, this may be called as displacement redox reaction.

The reaction (d) involves disproportionation of NO2 (+4 state) into NO-2 (+3 state) and NO-3
(+5 state). Therefore reaction (d) is an example of disproportionation redox reaction.

# Paradox of Fractional Oxidation Number: (NCERT green box)

• कुछ compounds ऐसे होते ह8 िजनमे particular elements का oxidation number fraction म"
होता है l
Eg: C3O2 (oxidation number of carbon is 4/3)
Br3O8( oxidation number of bromine is 16/3) g.m.l
Na2S4O6( oxidation number of sulphur is 2.5)

Actually ये factional oxidation state element का average oxidation state है l

O O O
II II II +2 0 +2
+6 +4
O == Br - Br – Br+6 == O O=C=C=C=O
II II II
O O O

(Br3O8) Tribromoactaoxide Carbon suboxide(C3O2)

O O
II 0 II
O - S – S – S – S+5- O Tetrathinoate ion (S4 O2-6)
+5

II II
O O

More examples – Fe3O4, Mn3O4, Pb3O4

Q8) Why do the following reactions proceed differently ?

Pb3 O4 + 8HCl → 3PbCl2 + Cl2 + 4H2O
and
Pb3O4 + 4HNO3 → 2Pb(NO3)2 + PbO2 + 2H2O

Solution
Pb3O4 is actually a stoichiometric mixture of 2 mol of PbO and 1 mol of PbO2. In PbO2, lead is
present in +4 oxidation state, whereas the stable oxidation state of lead in PbO is +2. PbO2
thus can act as an oxidant (oxidising agent) and, therefore, can oxidise Cl- ion of HCl into
chlorine. We may also keep in mind that PbO is a basic oxide. Therefore, the reaction

Pb3O4 + 8HCl → 3PbCl2 + Cl2 + 4H2O

can be splitted into two reactions namely:

2PbO + 4HCl → 2PbCl2 + 2H2O (acid-base reaction)

+4 -1 +2 0
PbO2 + 4HCl → PbCl2 + Cl2 + 2H2O (redox reaction)

Since HNO3 itself is an oxidising agent therefore, it is unlikely that the reaction may occur
between PbO2 and HNO3. However, the acid-base reaction occurs between PbO and HNO3 as:

2PbO + 4HNO3 → 2Pb(NO3)2 + 2H2O

It is the passive nature of PbO2 against HNO3 that makes the reaction different from the one
that follows with HCl.

7. Balancing of Redox Reactions:

(i) Oxidation Number Method:

• Based of change in the oxidation number of reducing agent and oxidising agent.
Step 1: Write the correct formular for each reactant & product.

Step 2: Identify atoms which undergo change in oxidation number in the reaction
by assigning the oxidation number to all elements in the reaction.

Step 3: Calculate increase or decrease in the oxidation number per atom & for the
entire molecule or ion.
If not equal then multiply by suitable coefficients.

Step 4: If reaction is taking place in water add H+ or OH- ions to the expression on
the appropriate side. So that total ionic charges of reactants & products are equal.
If the reaction is carried out in acidic solution, use H+ ions in equation, if basic
solution is OH- ions.

Step 5: Now make numbers of hydrogen atoms in the expression on the 2 sides
equal by adding water (H2O) molecules to the reactant or products.

• Now also check number of oxygen atom in reactants & products.

• And hence the equation gets balanced.

Q9)Write the net ionic equation for the reaction of potassium dichromate(VI),
K2Cr2O7 with sodium sulphite, Na2SO3, in an acid solution to give chromium(III)
ion and the sulphate ion.
Solution
Step 1: The skeletal ionic equation is:

Cr2O2-7 (aq) + SO2-3 (aq) → Cr3+ (aq) + SO2-4 (aq)

Step 2: Assign oxidation numbers for Cr and S

+6 -2 +4 -2 +3 +6 -2
Cr2O 7 (aq) + SO 3 (aq) → Cr(aq) + SO2-4 (aq)
2- 2-

This indicates that the dichromate ion is the oxidant and the sulphite ion is the
reductant.

Step 3: Calculate the increase and decrease of oxidation number, and make
them equal: from step-2 we can notice that there is change in oxidation state of
chromium and sulphur.
Oxidation state of chromium changes form +6 to +3. There is decrease of +3 in
oxidation state of chromium on right hand side of the equation.
Oxidation state of sulphur changes from +4 to +6. There is an increase of +2 in
the oxidation state of sulphur on right hand side.
To make the increase and decrease of oxidation state equal, place numeral 2
before chromium ion on right hand side and numeral 3 before sulphate ion on
right hand side and balance the chromium and sulphur atoms on both the sides
of the equation. Thus we get

+6 -2 +4 -2 +3 +6 -2
Cr2O 7 (aq) + 3SO 3 (aq) → 2Cr (aq) + 3SO2-4 (aq)
2- 2- 3+

Step 5: Finally, count the hydrogen atoms, and add appropriate number of water
molecules (i.e., 4H2O) on the right to achieve balanced redox change.

Cr2O2-7 (aq) + 3SO2-3 (aq)+ 8H+ (aq) → 2Cr3+ (aq) + 3SO2-4 (aq) +4H2O (l)

(ii) Half Reaction Method:

• Based on splitting the redox reaction into 2 half reactions – one involving oxidation
and the other involving reduction.
• 2 half equations are balanced separately and then added together to give balanced
equation.
 • अगर हम" ये equation balance करनी है िजसमे Fe2+ का oxidation हो रहा है Fe3+ ions म" by
dichromate ions (Cr2O7)2- in acidic medium और Cr2O2-7 reduce हो रहा है Cr3+ म" हम" इWके
Aलए कुछ steps follow करने हFगे l

Step 1: पहले तो equation बना लो l

Fe2+ (aq) + Cr2O2-7 (aq) → Fe3+ (aq) + Cr3+ (aq)

Step 2: Separate the equation into half reactions

+2 +3
Oxidation half : Fe (aq) → Fe3+ (aq)
2+

+6 -2 +3
Reduction half: Cr2O 7 (aq) → Cr3+ (aq)
2-

Step 3: Balance the atom other than O & H in each half reaction
यहा oxidation half already balanced है l
Reduction half को balance करने के Aलए Cr3+ को 2 से multiply कर" गे l

Cr2O2-7 (aq) → 2Cr3+ (aq)

Step 4: For reactions occurring in acidic medium, add H2O to balance O atoms & H+ to balance
H atoms, thus we get

Cr2O2-7 (aq) + 14H+ → 2Cr3+ (aq) + 7H2O (l)

Step 5: Add e- to one side of the half reaction to balance the changes. If need be make the
number of e- equal in the 2 half reactions by multiplying one or both half reactions.

Fe2+ (aq) → Fe3+ (aq) + e- } oxidation half

Cr2 O2-7 (aq) + 14H+ (aq) + 6e- → 2Cr3+ (aq) + 7H2O (l) } reduction half

(Net 12 +ve Charges on the left hand side ∴ add six electrons on left side. )

Multiply the oxidation half by 6

6 Fe2+ (aq) → 6 Fe3+ (aq) + 6e-

Step 6: add the 2 half reaction to get a final reaction, cancel the e- on each side.

6 Fe2+ (aq) Cr2O2-7 (aq) + 14H+ (aq) → 6 Fe3+ (aq) + 2Cr3+ (aq) + 7H2O (l)

Step 7: Verify the reaction

 • अगर reaction basic medium म" हो रहा है तो पहले तो atoms balance काल^ ;फर हर H+ ion
के Aलए OH- ion add करो equation के दोनो तरफ जहां H+ और OH- same side हFगे वहा ये
combine होके H2O बन जाएंगे l

Q10)Permanganate(VII) ion, MnO-4 in basic solution oxidises iodide ion, I- to

produce molecular iodine (I2) and manganese (IV) oxide (MnO2). Write a
balanced ionic equation to represent this redox reaction.

Solution:
Step 1: First we write the skeletal ionic equation, which is

MnO-4 (aq) + I- (aq) → MnO2(s) + I2(s)

Step 2: The two half-reactions are:

-1 0
Oxidation half : I- (aq) → I2 (s)

+7 +4
-
Reduction half: MnO 4 (aq) → MnO2 (s)

Step 3: To balance the I atoms in the oxidation half reaction, we rewrite it as:
2I- (aq) → I2 (s)

Step 4: To balance the O atoms in the reduction half reaction, we add two water
molecules on the right:
MnO-4 (aq) → MnO2 (s) + 2 H2O (l)

To balance the H atoms, we add four H+ ions on the left:

MnO-4 (aq) + 4 H+ (aq) → MnO2(s) + 2H2O (l)

As the reaction takes place in a basic solution, therefore, for four H+ ions, we add four
OH- ions to both sides of the equation:
MnO-4 (aq) + 4H+ (aq) + 4OH- (aq) → MnO2 (s) + 2 H2O(l) + 4OH- (aq)

Replacing the H+ and OH- ions with water, the resultant equation is:
MnO-4 (aq) + 2H2O (l) → MnO2 (s) + 4OH- (aq)

Step 5: In this step we balance the charges of the two half – reactions in the manner
depicted as:
2 I- (aq) → I2 (s) + 2e-

MnO-4 (aq) + 2H2O (l) + 3e- → MnO2 (s) + 4OH- (aq)

Now to equalise the number of electrons we multiply the oxidation half – reaction by 3
and the reduction half – reaction by 2.
6 I- (aq) → 3 I2 (s) + 6e-

2 MnO-4 (aq) + 4H2O (l) + 6e- → 2MnO2 (s) + 8OH- (aq)

Step 6: Add to half – reactions to obtain the net reactions after cancelling electrons on
both sides.

6 I- (aq) + 2MnO-4 (aq) 4H2O (l) → 3 I2 (s) + 2MnO2 (s) + 8OH- (aq)

Step 7: A final verification shows that the equation is balanced in respect of the
number of atoms and charges on both sides.

8. Redox Reaction as basis of Titration:

Redox sensitive indicator से हम redox system म" titration method use कर सकते ह8
reductant या oxidant क* strength determine करने के Aलए l

Paramagnetic ion MnO-4 acts as a self-indicator (reagent खद

ु ह@ coloured है )

When last of the reductant (Fe2+ or C2O2-4) is oxidised and the pink colour appears at
MnO-4 concentration as low as 10-6 mol dm-3 then end point is achieved.
जब MnO-4 Fe2+ और C2O-4 react करते ह8 तो MnO-4 का colour धीरे धीरे disappear होने लगता
है और pink colour appear होता है , ये एक indication है क* Fe2+ या C2O2-4 oxidise हो रहे ह8 l
जब Fe2+ या C2O2-4 परू @ तरह से react हो जाते ह8 तो उसे end point कहते ह8 l

Equivalence Point:
• Point where the reductant and the oxidant are equal in terms of mole
stoichiometry.

• Cr2O2-7 which is not a self-indicator, but oxidises the indicator substance

diphenylamine just after the equivalence point to produce an intense blue
colour, thus signalling the end point.

• Iodine is blue colour with starch

2Cu2+ (aq) + 4I- (aq) → Cu2I2 (s) + I2 (aq)

• Blue colour disappears as soon as iodine is consumed by thiosulphate ions

(S2O2-3), which is the end point.

• This method is used to restrict to these reagents which are able to oxidise I-
ions eg: Cu(II)
9. Limitations of concept of Oxidation Number:
• Concept of redox process has been evolving with time.
• In recent past the oxidation process is visualized a decrease in electron density
& reduction process as an increase in electron density around the atom(s)
involved in the reaction.

10. Redox Reaction & Electrode Process:

• अगर zinc rod को copper sulphate solution म" dip कर" गे तो redox reaction होगा l
Zinc is oxidised to zinc ions & copper to copper ion & heat is allowed is also
involved.
• अब ईसी reaction को हम इस तरह कर" गे िजसमे e- का transfer indirectly हो l इस तार@के
से zinc metal copper sulphate से seperate हो जाएगा l
• Take copper sulphate solution in a beaker & put copper strip or rod in it.
• Take zinc sulphate solution in another beaker & put zinc strip or rod in it.
• अब दोनो ह@ beaker म" reaction होगी और दोनो ह@ beaker म" interface of metal और
उनके salt solution oxidised और reduced form म" present हFगे l ये reduction और
oxidation half reaction को represent करते ह8 l

Redox Couple:

• A redox couple is defined as having together oxidised & reduced forms of a

substance taking part in oxidation or reduction half reaction.

• Representation of couples: Zn2+/Zn and Cu2+/Cu oxidised form is put before

the reduced form.

• Now we connect both the beaker by a salt bridge ( U – tube containing a solution
of potassium chloride or ammonium nitrate usually solidified by boiling with
agar) which provides electric contact between 2 solutions without mixing.

• Zinc & Copper rods are connected by a metallic wire with a provision for an
ammeter & switch this set up is called Daniel Cell

Switch off → no reaction, no current flows.

Switch on → 1. Transfer of e- does not take place directly from Zn to Cu2+, but
through metallic wire.
2. Electricity flows through salt bridge by migration of ions copper & zinc are
electrodes here.

Electrode Potential: Potential associated with each electrode.

Standard Electrode Potenital(E-): Potential of each electrode if Concentration

of species in reaction is unity (pressure = 1atm) temperature is 298 K. E- of hydrogen
is 0.00 volts
• It is a value of each electrode process in a measure of the relative tendency of
the active species in the process to remain in oxidised or reduced form.
• If E- is -ve : redox couple is strong reducing agent
• If E- is -ve : redox couple is weak reducing agent.