2015-2016

REDOX REACTIONS

(Lecture Notes)

SYLLABUS
1.

Concept of oxidation, reduction and redox reactions.

2.

Oxidation number.

3.

Balancing of redox reactions.

4.

Calculation of n-factor.

5.

Law of Chemical Equivalents.

6.

Titrations.
(i) Simple Titrations.
(ii) Double Titrations.
(iii) Back Titrations.

7.

Types of redox reactions.

8.

Electrode Potential
(i) Types of electrode Potential.
(ii) Measurement of Electrode- Standard Hydrogen Electrode.
(iii) Electrochemical Series & Application of Electrochemical series.
(iv) Galvanic cell: Representation of Galvanic cell, Calculation of Standard EMF & Work done in a cell

Page 2 of 39

INTRODUCTION
Several chemical reactions involve transfer of electrons from one chemical substance to another.
These electron-transfer reactions are termed oxidation-reduction or redox reactions.
Generation of electricity in batteries, production of heat energy by burning chemical substances, extraction of
metals such so sodium, aluminium, iron, etc., manufacture of a number of useful products such as caustic soda,
potassium permanganate, etc., electro deposition or electroplating are common examples of redox reactions.

OXIDATION AND REDUCTION

The term oxidation was first used to describe chemical reactions in which oxygen was added to an element or a
compound. The phenomenon of combustion was the earliest example of oxidation.
Later on the term oxidation was extended to describe many more reactions which occurred even without the use
of oxygen.
Oxidation is a process which involves:
Addition of oxygen:
2Mg + O2
2MgO
SO2
S + O2

(Oxidation of magnesium)
(Oxidation of sulphur)

Removal of hydrogen:
2HCl + S
H2S + Cl2
2H2O + 2I2
4HI + O2
Addition of an electronegative element:
FeS
Fe + S
SnCl4
SnCl2 + Cl2

(Oxidation of hydrogen sulphide)

(Oxidation of hydrogen iodide)

(Oxidation of iron)
(Oxidation of stannous chloride)

Removal of an electropositive element:

2KOH + I2
2KI + H2O2
2KCl + 2KMnO4
2K2MnO4 + Cl2

(Oxidation of potassium iodide)

(Oxidation of potassium manganate)

Reduction is just the reverse of oxidation. Reduction is a process which involves:

Removal of oxygen:
Cu + CO
CuO + C
CO +H2
H2O + C

(Reduction of cupric oxide)

(Reduction of water)

Addition of hydrogen:
2HCl
Cl2 + H2
H2S
S + H2

Removal of an electronegative element:

Hg2Cl2 + SnCl4
2HgCl2 + SnCl2
2FeCl2 + 2HCl
2FeCl3 + H2

Page 3 of 39

(Reduction of chlorine)
(Reduction of sulphur)

(Reduction of mercuric chloride)

(Reduction of ferric chloride)

Addition of an electropositive element:

HgCl2 + Hg
Hg2Cl2
CuCl2 + Cu
Cu2Cl2

(Reduction of mercuric chloride)

(Reduction of cupric chloride)

Note:
The substance which brings oxidation is known as oxidizing agent and the substance which brings reduction
is known as a reducing agent.
The substance, which undergoes oxidation, acts as a reducing agent while a substance, which undergoes
reduction, acts as an oxidizing agent.

COMPLEMENTARY NATURE OF OXIDATION AND REDUCTION

All oxidation and reduction reactions are complementary of one another and occur simultaneously.
Oxidation-reduction reaction is generally termed as a redox reaction. The word redox includes red + ox, red
means reduction and ox means oxidation.
For example, in the following reaction:
2FeCl2 + SnCl4
2FeCl3 + SnCl2
Ferric chloride is an oxidizing agent because it undergoes reduction while stannous chloride is a reducing agent
as it undergoes oxidation.
In this reaction, valency state of iron decreases from 3 to 2 while the valency state of tin increases from 2 to 4.

Note:
Thus, the process in which the valency of electropositive element increases is termed as oxidation and the
process in which the valency of electropositive element decreases is termed as reduction.

MODERN CONCEPTS OF OXIDATION AND REDUCTION

ELECTRON CONCEPT
According to electron concept, Oxidation is defined as a process in which an atom, ion or molecule loses one
or more electrons i.e., oxidation is the process of de-electronation.
For example,
Na+ + e
Na
Zn2+ + 2e
Zn
O2 + 2H+ + 2e
H2O2
MnO2-4
MnO-4 + e
In the above examples, an atomic or ionic species losses electron/electrons and as a result of which there is an
increase in positive charge or decrease in negative charge on the atom or ion undergoing oxidation.
Reduction is defined as a process in which an atom, ion or molecule gains one or more electrons i.e.,
reduction is the process of electronation.
For example,
2ClCl2 + 2e
Fe2+
Fe3+ + e
MnO4 + 8H+ + 5e
Mn2+ + 4H2O

Cr2O72- + 14H+ + 6e
2Cr3+ + 7H2O
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In the above examples, an atomic or ionic species gains electron/electrons and as a result of which there is a
decrease in positive charge or increase in negative charge on the atom or ion undergoing oxidation.
Thus, a Redox reaction may be represented as,
Oxidation

Oxidizing agent + Electrons

Reducing agent
Reduction

Note:
As oxidation and reduction always go hand in hand, a redox equation consists of two half reactions.
One half of the reaction represents the oxidation (loss of electron or electrons) and the other half of the
reaction represents the reduction (gain of one or more electrons).
The number of electrons involved should be the same in both the half reactions as free electrons are not
obtained in a system.
For example,
The reaction between sodium and fluorine to form sodium fluoride can be represented in the following way:
Oxidation half reaction: Sodium loses an electron.
Na+ + e.(i)
Na
Reduction half reaction: Fluorine molecule gains 2 electrons.
2F- .(ii)
F2 + 2e
Eq. (i) must be multiplied by 2 as to make the number of electrons same in both the half reactions.

2Na+ + 2e . (iii)
2Na

Adding eqs. (ii) and (iii), we get

2Na+ + 2F2Na + F2
2NaF
2Na + F2

The material which gains one or more electrons is termed as an oxidizing agent while the material which
loses one or more electrons is termed as a reducing agent.
In the above example, sodium acts as a reducing agent and fluorine acts as an oxidizing agent.
The valency of an element which undergoes oxidation increases and the valency of an element which
undergoes reduction decreases, i.e., the valency of a reducing agent increases while the valency of an
oxidizing agent decreases in a redox reaction.
Increase in valency

Oxidation

4, 3, 2, 1, 0, 1, 2, 3, 4

Reduction
Decrease in valency

Note:
Oxidation is a process in which one or more electrons are lost or valency of the element increases.
Reduction is a process in which one or more electrons are gained or valency of the element decreases.
Oxidising agent is a material which can gain one or more electrons, i.e., valency decreases.
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Reducing agent is a material which can lose one or more electrons, i.e., valency increases.
Redox reaction involves two half reactions, one involving loss of electron or electrons (oxidation) and the
other involving gain of electron or electrons (reduction).
Substances undergoing oxidation an increase in the oxidation number, while substances undergoing
reduction shows a decrease in the oxidation number.
For example:
4+
Hg 2+
2Hg2+ + Sn2+
2 + Sn
This equation can be split into two half reactions.
Hg 2+
2Hg2+ + 2e
(Reduction)
2

Sn4+ + 2e
Sn2+

(Oxidation)

Mercuric ion is reduced to mercurous ion and stannous ion is oxidized to stannic ion, i.e., mercuric ion acts as an
oxidizing agent while stannous ion acts as a reducing agent.
Oxidation (+2e)
4+
Hg 2+
2Hg2+ + Sn2+
2 + Sn

Reduction (-2e)

S4 O62- + 2IS2 O32- + I2

The equation can be split into two half reactions:
S4 O62- + 2e
2 S2 O32-
(Oxidation)
2II2 + 2e

(Reduction)

Thiosulphate ion is oxidized to tetrathionate ion by loss of electrons while iodine is reduced to iodide ion by gain
of electrons. Thiosulphate ion acts as a reducing agent and iodine acts as an oxidizing agent.
Oxidation (+2e)

2S2O32- + I2
S4 O62- + 2IReduction (-2e)

SOLVED EXAMPLES
Example 1. Identify the substance oxidized and the substance reduced as well as the oxidizing and reducing
agents in the following reaction:
K2SO4 + MnSO4 + Cl2 + 2H2O
2KCl + MnO2 + 2H2SO4
Solution: The given reaction is:
Oxidation
1 1

1 6 2

1 6 2

2 6 2

1 2

2 K Cl Mn O 2 2 H 2 S O 4
K 2 S O 4 Mn S O 4 Cl 2 2 H 2 O
Reduction
Cl- ion is oxidized to Cl2 while MnO2 is reduced to Mn2+ ion. Thus, it is a redox reaction.
MnO2 (Undergoes reduction)
Oxidizing agent
KCl (Undergoes oxidation)
Reducing agent
Page 6 of 39

Example 2. Chlorine dioxide ClO2, is used to kill bacteria in the dairy, meat and soft drinks. It is unstable but can
2ClO2 + 2NaCl. Identify the substances oxidized
be synthesized by the following reaction: Cl2 + 2NaClO2
and reduced.
Solution: The given reaction is:
Reduction
1

3 2

4 2

Cl2 2 Na Cl O 2
2 Cl O 2 2 Na Cl
Oxidation
In this reaction Cl2 acts as oxidizing and itself it is reduced while NaClO2 acts as reducing agent and itself it is
oxidized.
Example 3. Photosynthesis involves following overall reaction:
6CO2 + 6H2O

Chlorophyll

Light

C6 H12 O6 + 6O2
Glucose

Identify the species oxidized and the species reduced.

Solution: Photosynthesis is a complex series of coordinated redox reactions but the overall effect is to reduce
gaseous CO2 to carbohydrate and the oxidise H2O to O2
Reduction
4

-2

Chlorophyll
6 C O 2 + 6H 2 O
C6 H12O6 + 6 O 2
Light
Glucose

Oxidation

PROBLEMS FOR PRACTICE

1. State whether the following changes involve oxidation or reduction:
(i) Ferrous sulphate into ferric sulphate
(ii) Conversion of Cl2 to NaCl
(iii) Conversion of H2S to S
Fe3+), (ii) Reduction (Cl2
Cl-), (iii) Oxidation (S2-
S)
Ans. (i) Oxidation (Fe2+
2. Which of the following reactions do not involve oxidation reduction?
K4[Fe(CN)6]
(i) 4KCN + Fe(CN)2
NaCl + NH3 + H2O
(ii) NH4Cl + NaOH
2Cul + I2
(iii) 2Cul2
2RbOH + H2
(iv) 2Rb + 2H2O
Ans. (i), (ii)
3. Identify the oxidizing and reducing agents in the following reactions:
4Zn2+ (aq) + NH 4 (aq) + 3H2O(l)
(i) 10H+ (aq) + 4Zn(s) + NO3 (aq)

2HI(g) + S(s)
(ii) I2(g) + H2S(g)

AsO43 (aq) + NO(g) + S(s)

(iii) As2S5(s) + NO3 (aq)
Mn2+ (aq) + CH3COOH(aq)
(iv) MnO4 + C2H5OH(aq)
MgCl2(s)
(v) Mg(s) + Cl2(g)
Page 7 of 39

 BrO4 (aq) + 2F- (aq) + H2O(l)

(vi) BrO3 (aq) + F2(g) + 2OH- (aq)
reducing agent, NO3
oxidizing agent (ii) H2S
reducing agent,
Ans. (i) Zn
oxidizing agent (iii)As2S5
reducing agent, NO3
oxidizing agent;
I2
oxidizing agent, C2H5OH
reducing agent (v) Mg
reducing agent,
(iv) MnO4
oxidizing agent (vi) BrO3
reducing agent, F2
oxidizing agent.
Cl2
4. Split the following redox reactions in the oxidation and reduction half reactions:
2Al3+(aq) + 3Cu(s)
(i) 2Al(s) + 3Cu2+(aq)
2Fe2+ (aq) + I2 (aq)
(ii) 2Fe3+ (aq) + 2I- (aq)
2KCl(s)
(iii) 2K(s) + Cl2(g)
Al3+(aq) + 3e- (Oxidation), Cu2+(aq) + 2e
Cu(s) (Reduction)
Ans. (i) Al(s)
3+
2+
Fe (aq) (Reduction), 2I (aq)
I2(s) + 2e-(Oxidation)
(ii) Fe (aq) + e
K+ + e- (Oxidation), Cl2 + 2e-
2Cl- (Reduction)
(iii) K(s)

OXIDATION NUMBER (OXIDATION STATE)

Oxidation number is defined as the charge (real or imaginary) which an atom appears to have when it is in a
combination.
In the case of electrovalent compounds, the oxidation number of an element is the same as the charge on the
ion. This is the real charge and is developed by the loss and gain of electron or electrons.
For example, in the electrovalent compound sodium chloride (NaCl), the charge on sodium and chlorine is +1
and -1, respectively.
The charges have been developed by the transfer of one electron from Na-atom to Cl-atom. Thus, in NaCl
(Na+ Cl-), the oxidation number of sodium is +1 and that of chlorine is -1.
The oxidation numbers of atoms in covalent compounds can be derived by assigning the electrons of each
bond to the more electronegative atom of the bonded atoms.
For a molecule of HCl both the electrons of the covalent bond are assigned to the chlorine atom since it is
more electronegative than hydrogen.
Thus, chlorine atom has one more electron than the neutral chlorine atom which brings one unit negative
charge on chlorine. The oxidation number of chlorine in this compound is -1.
The hydrogen atom has lost the only electron possessed by it, thus acquiring one unit positive charge. The
oxidation number of hydrogen is, therefore, +1 in this compound.
Note:
In the case of a covalent bond between two identical atoms, i.e., when electronegativity difference is zero, the
bonding electrons are shared equally between the bonded atoms, i.e., no charge is developed on any of the
atoms. Thus, the oxidation numbers of both chlorine atoms are zero in the molecule of chlorine.

RULES FOR CALCULATING OXIDATION NUMBER

Zero group elements have zero oxidation numbers (states) as they do not show chemical activity.
Elements other than noble group elements have at least two oxidation states, zero when they exist in free
Page 8 of 39

state and positive or negative when they exist in compounds.

Alkali metals (IA) show uniformly +1 oxidation state, as they have ns1 configuration and have only a tendency
to lose this electron.
Alkaline earth metals (IIA) show a common oxidation state of +2 as they have ns2 configuration.
Elements of group (IIIA) have ns2 np1 outer shell configuration, suggesting +1 and +3 oxidation states
corresponding to use of np or ns np electrons.
Elements of group (IVA) have ns2 np2 outer shell configuration. They show oxidation states +4 (maximum)
and -4 (minimum). However, Sn and Pb show either +2 or +4 oxidation states being metallic in nature.
Elements of (VA) have outer shell configuration ns2np3.They show oxidation states between +5 and -3.
Elements of (VIA) (with the exception of oxygen) show maximum oxidation state +6 and minimum oxidation
state -2.
Elements of (VIIA) (with the exception of fluorine) show maximum +7 and minimum -1 oxidation state.
Transition metals exhibit a large number of oxidation states due to involvement of (n 1)d electrons besides
ns electrons.
The oxidation number (Ox. no.) of an atom in homo atomic molecules is always zero, no matter how
complicated the molecule is.
For example, Hydrogen in H2, sulphur in S8, phosphorus in P4, oxygen in O2 or O3, all have a zero value of
oxidation numbers.
Fluorine, which is the most electronegative element, has -1 oxidation number in all of its compounds.
Oxidation number of oxygen is -2 in all compounds except in peroxides, superoxides, ozonides and oxygen
fluorides.
In peroxides ( O22 ), oxygen has -1 oxidation number.
1
In superoxides ( O2 ), oxygen has oxidation number - .
2
1
In ozonides ( O3 ), oxygen has oxidation number - .
3
In OF2 and O2F2, oxygen has oxidation number +2 and +1 respectively.
The oxidation number of hydrogen is +1 in all of its compounds except in metallic hydrides like NaH, BaH2,
etc. where the oxidation state of Hydrogen is -1.
In the case of neutral molecules, the algebraic sum of the oxidation numbers of all the atoms present in the
molecule is zero.
The oxidation number of an ion is equal to the electrical charge present on it.
For complex ions, the algebraic sum of oxidation numbers of all the atoms is equal to the net charge on the ion.
Oxidation numbers can be fractional values.
For example,
Na2S4O6
2 x 1 + 4x + 6(-2) = 0
2 + 4x 12 = 0
Page 9 of 39

Fe3O4
3x + 4(-2) = 0
3x 8 = 0

N3H
3x + 1 = 0
3x = -1

4x = +10

10
= + 2.5
4
Oxidation number
x=+

of sulphur is +2.5

1
3

3x = 8

x=

8
2
or + 2
3
3
Oxidation number
2
of iron is +2
3

Oxidation number
1
of nitrogen is
3

x=+

Note:
When an element has a fractional oxidation number in a particular compound, this often means that the
compound contains two or more atoms of the element that are not equivalent.
In an organic compound containing carbon, hydrogen and oxygen, the oxidation number of carbon can be
calculated as,
Oxidation number of carbon =

n O 2-n H
nC

where,
n O = Number of oxygen atoms

n H = Number of hydrogen atoms

n C = Number of carbon atoms

SOLVED EXAMPLES
Example 4. What is the oxidation number of Mn in KMnO4 and of S in Na2S2O3?
Solution:
Let the Ox. no. of Mn in KMnO4 be x. Ox. no. of K = +1, Ox. no. of O = -2
+1+ x + 4(-2) =0
x = +8 1 = +7
Ox. no. of Mn in KMnO4 is + 7.
Let the Ox. no. of S in Na2S2O3 be x.
2 x (+1) + 2x + 3(-2) = 0
x = +2
Ox. no. of S in Na2S2O3 = +2.
Example 5. What is the oxidation number of Cr in K2Cr2O7?
Solution:
Let the Ox. no. of Cr in K2Cr2O7 be x. Ox. no. of K = +1, Ox. no. of O = -2
2(+1) + 2(x) + 7(-2) = 0
2x = +14 -2 = +12
12
x = + = +6
2
Hence, oxidation number in Cr in K2Cr2O7 is +6.
Example 6. What is the oxidation number of Fe in K4[Fe(CN)6]?
Solution:
Let the oxidation number of Fe be x. Ox. no. of K = +1, Ox. no. of (CN)- = -1
4(+1) + x + 6(-1) = 0
Page 10 of 39

 x = +6 4 = +2
The oxidation number of iron in K4[Fe(CN)6] is +2.
Example 7. Find the oxidation number of:
(i) S in SO 2-4 ion
(ii) S in HSO3- ion
(iii) Pt in PtCl62- ion
Solution:
(i) Let the oxidation number of. S be x. Ox. no. of O = -2
x + 4(-2) = -2
x 8 = -2
x = +8 2 = +6
The oxidation number of S in SO 2-4 ion is +6.
(ii) Let the oxidation number of S be x in HSO3- ion.
+1+ x + 3(-2) = -1
+1+ x 6 = -1
x 5= -1
x = +5 -1 = +4
The oxidation numbers of S in HSO3- ion is +4.

(iv) Mn in MnO-4 ion

Ox. no. of H = +1 and Ox. no. of O = -2

(iii) Let oxidation number of Pt be x. Ox. no. of Cl = -1

x + 6(-1) = -2
x 6 = -2
x = +6 2 = +4
The oxidation number of Pt in PtCl62- ion is +4.
(iv) Let oxidation number of Mn be x. Ox. no. of O = -2.
x+ 4(-2) = -1
x- 8 = -1
x = +8 1 = +7
The oxidation number of Mn in MnO-4 ion is +7.
Example 8. Which compound amongst the following: KMnO4, K2MnO4, MnO2 and Mn2O3 has the maximum
oxidation number.
Solution:
KMnO4
+1 + x 8 = 0
Ox. no. of Mn
x = +7
+7
K2MnO4
+2+x -8 = 0
x = +6
+6
MnO2
x4=0
x = +4
+4
Mn2O3
2x 6 = 0
x = +3
+3
Thus, the highest oxidation number for Mn is in KMnO4.
Example 9. Assign oxidation number to the underlined elements in each of the following species:
(i) KI3
(ii) CaO2
(iii) NaH2PO4
(iv) H4P2O7
(v) NaBH4
(vi) H2S2O7 (vii) H2S4O6
(viii) CH3CH2OH
(ix) CH3COOH
Solution:
(i) KI3
Page 11 of 39

 + 1 + 3x = 0
1
x = 3
(ii) CaO2
+2 + 2x = 0
x = -1
(iii) NaH2PO4
+ 1 + 2 + x -8 = 0
x = +5
(iv) H4P2O7
+4 + 2x -14 =0
x = +5
(v) NaBH4
+1 + x + (-4) = 0
x = +3
(vi) H2S2O7
O

O
HO

OH

+2 + 2x -14 = 0
x = +6
(vii) H2S4O6
O
HO

OH

+2+4x 12 = 0
x = + 2.5
The two donor sulphur atoms have +5 state, while non-donor atoms have zero oxidation state.
(viii) CH3 CH 2 OH or C2H5OH
2

2n O -n H
2 1-6
=
= -2
nC
2
Carbon labelled 1 has (-3) oxidation state and carbon labelled 2 has (-1) oxidation state.
Oxidation number of carbon =

(ix) C H 3 C OOH or C2H4O2

1

2n O -n H 2 2-4
=
=0
nC
2
Carbon labelled 1 has (-3) oxidation state and carbon labelled 2 has (+3) oxidation state.
Oxidation number of carbon =

Page 12 of 39

BALANCING OF REDOX REACTIONS

A balanced equation must satisfy two conditions.
(i) Atom Balance (Mass Balance): There should be same number of atoms of each kind both in the
reactant and product side.
(ii) Charge Balance: The sum of the actual charges on both the reactant and product side must be equal.
Two methods are used to balance chemical equations:
OXIDATION NUMBER METHOD
Step 1: Write the correct formula for each reactant and 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 the increase or decrease in the oxidation number per atom for the entire molecule/ion in which
it occurs. If these are not equal then multiply by suitable co-efficient so that these become equal.
Step 4: Add H or OH to the expression on the appropriate side so that the total ionic charges are equal.
If the reaction is carried out in acidic medium use H ions in the equation and if it is basic solution use OH .
Step 5: Make the number of hydrogen atoms in the expression on the two sides equal by adding H 2O molecules
either on the reactant or the product side.
Now also check for the number of oxygen atoms, if there are same number of oxygen atoms in the reactants and
products, the equation then represents the balanced redox reaction.
Example 10: Write the net ionic equation for the reaction of potassium dichromate (VI), K 2Cr2O7 , with sodium
sulphite ( Na 2SO3 ) in an acid solution to give chromium(III) ion and the sulphate ion.

Page 13 of 39

Example 11: Permanganate ion reacts with bromide ion in basic medium to give manganese dioxide and bromate
ion. Write the balanced ionic equation for the reaction.

HALF REACTION METHOD (or) ION ELECTRON METHOD

In this method, the two half equations are balanced separately and then added together to give balanced equation.
Step 1: Write down the redox reaction in ionic form.
Step 2: Split the redox reaction into two half reactions, one for oxidation and the other for reduction.
Step 3: Balance each half reaction for the number of atoms of each element.
For this purpose:
(i) Balance the atoms other than H and O for each half reaction using simple multiples.
(ii) Add water molecules to the side deficient in oxygen and H+ to the side deficient in hydrogen.
This is done in acidic or neutral solutions.
(iii) In alkaline solution, for each excess of oxygen, add one water molecule to the same side and 2
OH- ions to the other side. If hydrogen is still unbalanced, add one OH- ion for each excess
hydrogen on the same side and one water molecule to the other side.
Step 4: Add electrons to the side deficient in electrons as to equalize the charge on both sides.
Step 5: Multiply one or both the half reactions by a suitable number so that the numbers of electrons become
equal in both the equations.
Step 6: Add the two balanced half reactions and cancel any term common to both sides.
Example 12: Permanganate (VII) ion, MnO-4 in basic solution oxidizes iodide ion, I - to form molecular iodine
(I2) and manganese (IV) oxide, MnO2. Write a balanced ionic equation to represent this redox reaction.

Page 14 of 39

CALCULATION OF n-factor
For calculating the n-factor of any reactant in any reaction, knowledge regarding the kind of reaction is
necessary. The reactions may be classified into the following three types.
1. Acid-Base Reactions/Neutralization reactions
2. Redox Reactions
3. Precipitation Reactions/Double decomposition reactions

Page 15 of 39

Case 1: ACID-BASE REACTION

According, to the Arrhenius concept, an acid is a substance that furnishes H+ ion(s) in solution, a base is a
substance that furnishes OH- ion(s) in solution and neutralization is a reaction in which H+ ion furnished by acid
combines with OH- ions furnished by base.
The number of H+ ion(s) furnished per molecule of the acid is its n-factor also called basicity.
The number of OH- ion(s) furnished by the base per molecule is its n-factor, also called acidity.
For example,

HCl
H Cl

(n 1)

H2SO4
H HSO4
(n 1)

H2SO4
2H SO24
(n 2)

H3PO4
H H2PO4
(n 1)

H3PO4
3H PO34
(n 3)

H3PO3
H H2PO3
(n 1)

H3PO3
2H HPO3
(n 2)

The n-factor of H3PO3 cannot be 3 as it has only two dissociable H+ ions. So, its n-factor or dissociable protons
is 1 or 2 as one of the H-atoms is linked with P atom directly.
O
HO

OH

Similarly, the n-factor of H3PO2 cannot be 3 or 2 as it has only one dissociable H+ ions. So, its n-factor or
dissociable protons is 1 as only one of the H-atoms is linked with P atom directly.

Similarly, n-factor of CH3COOH is 1, because it contains only one dissociable H+ ion.

Now, we will consider the n-factor of some bases.

NaOH
Na OH
(n 1)

Ba(OH)2
[Ba(OH)] OH
(n 1)

Page 16 of 39

Ba(OH)2
Ba 2 2OH
(n 2)

Al(OH)3
Al3 3OH
(n 3)

Similarly, n-factor of Al(OH)3 can also be 1 or 2 or 3, depending upon the number of OH released.
Case 2: REDOX REACTIONS
Case 1: When only one atom undergoing either reduction or oxidation.
In such a case, we consider the change in oxidation state of atom undergoing oxidation or reduction change
per molecule as the n-factor of the species.
7

MnO4
n 5

2
2

Mn

n-factor = |(+2) 1 (+7) 1| = 5

2
2

Fe

n 1

3
3

Fe

n-factor = |(+3) 1 (+2) 1| = 1

32
2
2 4
n 2

42

C O
2CO2
n-factor = |(+4) 2 (+3) 2| = 2
62
Cr2O72
n 6

32
3

2Cr

n-factor = |(+3) 2 (+6) 2| = 6

Case 2: Compounds which reacts in such a way that only one atom undergoes change in oxidation state but
appears in two products with the same oxidation state.
In such a case the method of calculation of n-factor remains the same i.e., we will calculate the change in
oxidation state of the atom per mole of that substance (reactant).
62

Cr2O72
Cr 3 Cr 3
In this example, oxidation state of Cr changes from +6 to +3 in both the products.
n-factor = |(+6) 2 (+3) 2| = 6
Case 3: Salts which react in such a way that only one atom undergoes change in oxidation state but goes in
two products with different oxidation state as a result of either only oxidation or only reduction.
7

3MnO 4
2Mn 2 Mn 6
In such a case, it is impossible to calculate the n-factor until and unless one knows how much of MnO4 is gets
converted to Mn2+ and how much gets converted Mn6+ and if one knows the balanced equation then there is
no need of calculation of n-factor.
Nevertheless in such case the n-factor can be calculated by deducing the total change in oxidation state
divided by total number of atom undergoing reduction/oxidation change.
Page 17 of 39

So, for the calculation of n-factor in the above example, out of three moles of MnO4 , two moles are being
converted to Mn2+ and one mole changes to Mn6+.
Total decrease in oxidation state of Mn = ((2 (+2) 2 (+7))) + ((1 (+6) 1 (+7)))

= (4 14) + (6 7) = 11
n-factor =

11
3

Case 4: Salts which react in such a way that only one atom undergoes change in oxidation state in two
product, in one product with changed oxidation state and in other product with same oxidation state as that of
reactant.
In such case also one cannot calculate the n-factor without knowing the balanced chemical equation because
one must know how much of atom has changed its oxidation state.
For example,
2KCl + 2CrCl3 + 3Cl2 + 7H2O
K2Cr2O7 + 14HCl
Let us calculate the n-factor of HCl. Out of 14 moles of Cl (in HCl) only 6 moles of Cl are changing its
oxidation state from 1 to 0 in the product Cl2 and the oxidation state of remaining 8 Cl ions remains same in
KCl and CrCl3. So, total no. of moles of electrons lost by 14 moles of HCl is 6. So each mole of HCl takes up
6/14 i.e., 3/7 moles of electrons and hence n-factor of HCl is 3/7.

Case 5: Compounds which react in such a way that two or more atoms in the salt undergoes change in
oxidation states as a result of either oxidation or reduction.
In such a case we will calculate the n-factor of the salt as the total increase or decrease in oxidation state per
mole of the salt.
Let us consider the following example,
Fe3+ + 2CO2
FeC2O4
In this case, the oxidation of both Fe2+ and C3+ are changing from + 2 and +3 to +3 and +4 respectively.
As one can see that one mole of FeC2O4 contains one mole of Fe2+ and one mole of C2O42 (i.e. 2 carbon
atoms per mole of C2O42.)
Total change in oxidation state = | 1 (+2) 1 (+3) | + | 2 (+3) 2 (+4) |
=1+2=3
n-factor of FeC2O4 is 3

Case 6: Compounds which react in such a way that two atoms undergoing change in oxidation state but one
undergoing oxidation and other reduction reaction.
Case 1: Number of moles of electrons involved during oxidation and reduction is same.
In such a case one has to calculate the change in oxidation state of either the atom being oxidized or the atom
being reduced.
For example,
N 2 + Cr2O3
NH 4 2 Cr2O7
In this reaction, the oxidation state of N is increasing by 6 units and that of Cr is decreasing by 6 units. So, we
can consider either oxidation or reduction product for the calculation of n-factor and it will be the same.
n-factor of (NH4)2Cr2O7 considering oxidation = |(-3) 2 (0) 2| = 6
Page 18 of 39

n-factor of (NH4)2Cr2O7 considering reduction = |(+6) 2 (+3) 2| = 6

Case 2: Number of moles of electrons involved during oxidation and reduction is not the same.
In such a case, the difference in the number of moles of electrons involved in oxidation and reduction is
reported as the n-factor.
CuS
Cu + SO24
In this reaction, the oxidation state of Cu is decreasing by 2 units and that of S is increasing by 8 units.
So, the n-factor of CuS will be 8-2 = 6.
Case 7: Species which undergoes disproportionation reaction:

Note:
Disproportionation is a specific type of redox reaction in which a species is simultaneously reduced and
oxidized to form two different products.
The reverse of disproportionation, when a compound in an intermediate oxidation state is formed from
compounds in lower and higher oxidation states, is called Comproportionation.
Case 1: When the number of moles of atoms being oxidized is equal to the number of moles of atoms being
reduced.
The n-factor can be calculated by knowing the balanced chemical equation and considering any of the change
taking place.
For example,
2H2O + O2
2H2O2
O2) and
Out of 2 moles of H2O2 consumed in the reaction, one mole of H2O2 is being oxidized (H2O2
2H2O).
one mole of H2O2 is being reduced (H2O2

Considering the oxidation reaction,

n-factor = |2 0 (1) 2| = 2
Considering the reduction reaction,
n-factor = |(-2) 2 (-1) 2| = 2
So, n-factor of H2O2 either considering oxidation or reduction reaction is same i.e. 2.
Case 2: When the number of moles of atoms being oxidized is not equal to the number of moles of atoms being
reduced.
The n-factor is calculated by first knowing the total number of moles of electrons exchanged (lost or gained)
by the number of moles of substance appearing in the balanced equation and then dividing the number of
moles of electrons exchanged by the number of moles of substance, to get the number of moles of electrons
exchanged by one mole of the substance, which is the n-factor of that substance.
For example,
6Br2 +12OH-
10Br - +2BrO3- +6H 2 O
In this reaction, the electrons released by the oxidation of some of the Br2 is the same as used up in the reduction
of rest of the Br2.
Br2
2Br 5+ +10e5Br2 +10e-
10Br 6Br2
10Br - +2Br 5+
In overall reaction, the number of moles of electrons lost or gained by 6 moles of Br2 are 10.
Page 19 of 39

Therefore, by each mole of Br2, the number of moles of electrons exchanged are

10 5
or , which is the n- factor
3
6

of Br2 in this reaction.

Case 3: PRECIPITATION/DOUBLE DECOMPOSITION REACTIONS

In such reaction, there is no change in oxidation state of any atom.
The n-factor of the salt can be calculated by multiplying the oxidation state of the cation /anion by total no. of
atoms per molecule of the salt.
For example,
For BaCl2
n-factor = Oxidation state of Ba atom in BaCl2 number of Ba atoms in 1 molecule of BaCl2
= (+2) 1 = 2
For Na2SO4
n-factor = Oxidation state of Na number of Na-atoms in 1 molecule of Na2SO4
= (+1) 2 = 2

TITRATION
The process of determination of concentration of a solution with the help of a solution of known
concentration (standard solution) is called titration.
Titration is divided into following four categories.

Simple Titration
Double Titration
Back Titration
Iodimetric and Iodometric Titration

SIMPLE TITRATION
A known volume of the solution of unknown concentration is taken in a flask and required reagents are added
to it. The solution of known concentration is added from the burette in the solution of unknown concentration
till the latter reacts completely. This process is called titration. At the end point (equivalence point) the
equivalents or milliequivalents of the two reacting substances are equal.
Volume of solution (A) = VA litres
Normality of solution (A) = NA
Equivalents of substance (A) = NAVA
Similarly, equivalents of substance (B) = NBVB
At the equivalence point (end point) the equivalents (not the moles) of the two substance are equal.
NAVA (litres) = NB VB (litres)
Example 10: 40 ml N/10 HCl and 60 ml N/20 KOH are mixed together. Calculate the normality of the
acid or base left and the normality of the salt formed in the solution.
Page 20 of 39

Solution:

1 40
4
10
1 60
Milli equivalents of KOH = N V (ml) =
3
20
One milli equivalent of an acid neutralizes one milli equivalent of a base
Milli equivalent of HCl left
=43=1
Total volume of the solution
= 40 + 60 = 100 ml
Milli equivalents of HCl
= N V (ml)
1 = N 100
Normality (N) of HCl left in solution = 0.01
Salt formed = Milli equivalent of acid or base neutralized
Milli equivalents of the salt formed = N V (ml)
3= N 100
Normality (N) of salt formed = 0.03N
Milli equivalents of HCl = N V (ml) =

DOUBLE TITRATION
If an aqueous solution contains a mixture of any two of the three NaOH, NaHCO3 and Na2CO3 and it has
to be titrated against an acid HCl or H2SO4, it will require two indicators to determine the strength of the
bases present. The two indicators used are phenolphthalein and methyl orange.
Method: A given volume of the aqueous solution of the bases is taken and phenolphthalein indicator is
added to it. This solution is titrated with an acid of known normality to the end point and the volume of the
acid used is noted. This end point is called first end point. Now in the same solution methyl orange is added
and again titrated with an acid of known strength to the end point. It is called second end point. The volume
of acid, used in the second end point is also noted. The normality of the bases present is then calculated.
The following reactions take place,
NaCl + H2O
NaOH + HCl

(pH= 11-12)

NaHCO3 + NaCl
Na2CO3 + HCl

(pH= 9-10)

NaHCO3 HCl
NaCl H 2O CO 2

(pH= 3.5-4.5)

Weak base

Weak base

1. Titration of the solution containing both NaOH and Na2CO3

Case 1: When Phenolphthalein indicator is used for the first endpoint followed by Methyl Orange for the
second end point.
For Ist endpoint or Phenolphthalein endpoint:
Meq of HCl = Meq of NaOH+

1
Meq of Na2CO3
2

For 2nd endpoint or Methyl orange endpoint:

Meq of HCl =

1
Meq of Na2CO3
2

Case 2: When Methyl Orange indicator is used in the beginning.

Meq of HCl = Meq of NaOH+ Meq of Na2CO3
Page 21 of 39

2. Titration of the solution containing both Na2CO3 and NaHCO3

Case 1: When Phenolphthalein indicator is used for the first endpoint followed by Methyl Orange for the
second end point.
For Ist endpoint or Phenolphthalein endpoint:
Meq of HCl =

1
Meq of Na2CO3
2

For 2nd endpoint or Methyl orange endpoint:

1
Meq of HCl = Meq of Na2CO3 + Meq of NaHCO3
2
Case 2: When Methyl Orange indicator is used in the beginning.
Meq of HCl = Meq of Na2CO3 + Meq of NaHCO3
3. Titration of the solution containing both NaOH and NaHCO3
Case 1: When Phenolphthalein indicator is used for the first endpoint followed by Methyl Orange for the
second end point.
For Ist endpoint or Phenolphthalein endpoint:
Meq of HCl = Meq of NaOH
For 2nd endpoint or Methyl orange endpoint:
Meq of HCl = Meq of NaHCO3
Case 2: When Methyl Orange indicator is used in the beginning.
Meq of HCl = Meq of NaOH+ Meq of NaHCO3
BACK TITRATION
Let us consider that we have an impure solid substance Z weighing w g and we are required to calculate
the percentage purity of Z in the sample. We are also provided with two solutions X and Y. For the
back titration to work, following conditions are to be satisfied
(i) Compounds X, Y and Z should be such that X and Y reacts with each other.
(ii) X and pure Z also reacts with each other but the impurity present in Z does not react with X.
Product 1
Z + X (excess)
Product 2
Remaining (X) + Y

Note:
Product 1 should not react with Y
Initial milli equivalent of X = N1V1
where N1 and V1 (ml) is the normality and volume of X
Milli equivalent of Y = N2V2
where N2 and V2 (ml) is the normality and volume of Y
Reacted milli equivalents of X after reacting with Y = N1V1 N2V2
Page 22 of 39

Reacted milli equivalents of X = milli equivalents of Z

a

N1V1 N2V2
1000
Equivalent weight of Z
where a is the weight of pure Z which is reacted.

Molecular weight of Z N1V1 N 2 V2

Percentage purity of Z

n factor 1000

N1V1 N1V1

Molecular weight of Z
100 Iodimetric
n factor 1000
w

and
IODIMETRIC AND IDOMETRIC TITRATIONS
The redox-titration using iodine directly or indirectly as an oxidizing agent are called Iodine Titrations.
These are of two types.
IODIMETRIC TITRATIONS
Iodimetric titrations are defined as those iodine titrations in which a standard iodine solution is used as an
oxidant and iodine is directly titrated against a reducing agent. Iodimetric procedures are used for the
determination of strength of reducing agent like thiosulphates, sulphites, arsenites and stannous chloride
etc., by titrating them against standard solution of iodine taken in a burette.
Some cases of oxidation-reduction reactions are given as under:
2Na2S2O3 + I2
Na2S4O6 + 2NaI
Na2SO3 + I2 + H2O
Na2SO4 + 2HI
Na3AsO3 + H2O
Na3AsO4 + 2HI
IODOMETRIC TITRATIONS
Iodometric titrations are defined as those iodine titrations in which some oxidizing agent liberates iodine
from an iodine solution and then liberated iodine is titrated with a standard solution of a reducing agent
added from a Burette. In such titrations, a neutral or an acidic solution of oxidizing agent is employed. The
amount of iodine liberated from an iodide, (i.e. KI) is equivalent to the quantity of the oxidizing agent
present. Iodometric titrations are used for the determination of CuSO4, K2Cr2O7, KMnO4, ferric ions,
antimonite ions, H2O2, MnO2, bromine and chlorine etc.
The equations for some of the reactions are as follows:
2CuSO4 +4KI
Cu2I2+ 2K2SO4 + I2
2KMnO4 +10KI + 8H2SO4
6K2SO4 + 2MnSO4 + 8H2O + 5I2
K2Cr2O7 + 6KI + 7H2SO4
4K2SO4 + Cr2(SO4)3 + 7H2O + + 3I2
In the above reactions, the liberated iodine is titrated with a standard sodium thiosulphate.
2Na2S2O3 + I2
Na2S4O6 + 2NaI

Page 23 of 39

CLASSIFICATION OF REDOX REACTIONS

Redox reactions may be classified into two types:
DIRECT REDOX REACTIONS
The reactions in which oxidation and reduction take place in the same vessel are termed direct redox
reactions.
For example,
Reaction between zinc and copper sulphate solution.
Reaction between HgCl2 and SnCl2.
Reaction between acidified K2Cr2O7 and oxalic acid.
Reaction between acidified KMnO4 and ferrous ammonium sulphate.
INDIRECT REDOX REACTIONS
The reactions in which oxidation and reduction take place in different vessels are termed indirect redox
reactions.

Note:
Indirect redox reactions are the basis of electrochemical cells.
DIFFERENCES BETWEEN DIRECT AND INDIRECT REDOX REACTIONS
Direct redox reaction
Indirect redox reaction
Oxidation and reduction reactions occur in Oxidation and reduction reaction occur in different
the same container.
containers called half cells.
Transference of electrons takes place
Transference of electrons takes place through
directly in the solution.
connecting metallic wires.
Heat energy is released.
Electrical energy is liberated.
There is precipitation of one metal at the
The precipitation of one metal occurs in the
bottom of the container.
cathodic half-cell.
Reaction quickly proceeds to completion.
Reaction is not completed.

ELECTRODE POTENTIAL
When a metal is placed in a solution of its ions, the metal acquires either a positive or negative charge with
respect to the solution.
On account of this, a definite potential difference is developed between the metal and the solution, this
potential difference is called Electrode potential.
For example,
When a plate of zinc is placed in a solution having Zn2+ ions, it becomes negatively charged with respect to
solution and thus, a potential difference is set up between zinc plate and the solution. This potential difference is
termed as the electrode potential of zinc.
Similarly, when copper is placed in a solution having Cu2+ ions, it becomes positively charged with respect to
solution. A potential difference is set up between the copper plate and the solution. The potential difference
thus, developed is termed as electrode potential of copper.
Page 24 of 39

The potential difference is established due to the formation of electrical double layer at the interface of metal
and the solution.
The development of negative charge (as on zinc plate) or positive charge (as on copper plate) can be explained in
the following manner.

When a metal rod is dipped in its solution, two changes occur:

OXIDATION
Metal ions pass from the electrode into solution leaving electrons and thus, a negative charge on the electrode.
Conversion of metal atoms into metal ions is by the attractive force of polar water molecules.
n+
M (s)
M (aq)
+neThe metal ions go into the solution and the electrons remain on the metal making it negatively charged.
This tendency of the metal to change into ions is known as electrolytic solution pressure.
REDUCTION
Metal ions in solution gain electrons from the electrode and start depositing on the metal surface leaving a
positive charge on the electrode.
n+
M (aq)
+ne-

M (s)

This tendency of ions in solution to get deposited on the metal surface is termed osmotic pressure.
In the beginning, both these changes occur with different speeds but soon equilibrium is established and in
practice, one effect is greater than the other.
If electrolytic solution pressure is greater than osmotic pressure, the metal acquires a negative charge with
respect to solution.
Page 25 of 39

If the osmotic pressure is greater than electrolytic solution pressure, the metal acquires positive charge with
respect to solution.
Thus in both the cases a potential difference is set up.

Note:
The magnitude of electrode potential of a metal is a measure of its relative tendency to lose or gain electrons,
i.e. it is a measure of the relative tendency to undergo oxidation (loss of electrons) or reduction (gain of
electrons).
The magnitude of potential depends on the following factors:
Nature of the electrode.
Concentration of the ions in solution.
Temperature.
Depending on the nature of the metal electrode to lose or gain electrons, the electrode potential may be of two
types:
OXIDATION POTENTIAL
When electrode is negatively charged with respect to solution, i.e. it acts as anode and oxidation occurs.
n+
M (s)
M (aq)
+neREDUCTION POTENTIAL
When electrode is positively charged with respect to solution, i.e. it acts as cathode and reduction occurs.
n+
M (aq)
+neM (s)

Note:
It is not possible to measure the absolute value of the single electrode potential directly and only the difference
in potential between two electrodes can be measured experimentally.
It is, therefore, necessary to couple the electrode with another electrode whose potential is known and this
electrode is termed as reference electrode. Knowing the value of electrode potential of the reference electrode,
the electrode potential value of the other electrode can be determined.
STANDARD ELECTRODE POTENTIAL
In order to compare the electrode potentials of various electrodes, it is necessary to specify the concentration of
the ions present in solution in which the electrode is dipped and the temperature of the half cell.
The potential difference developed between metal electrode and the solution of its ions of unit molarity (1M)
at 25oC (298 K) is called standard electrode potential.

Note:
According to the IUPAC convention, the electrode potential is regarded as the reduction potential, i.e. the
given value of electrode potential be regarded as reduction potential unless it is specifically mentioned that it is
oxidation potential.
Page 26 of 39

Reduction potential of an electrode means that reduction reaction is taking place at the electrode, if the
reaction is reversed and written as oxidation reaction, the numerical value of electrode potential will to be
reversed.
i.e,

Standard reduction potential = - (Standard oxidation potential)

or
Standard oxidation potential = - (Standard reduction potential)

REFERENCE ELECTRODE: STANDARD HYDROGEN ELECTRODE (SHE)

Standard Hydrogen Electrode consists of a small platinum strip coated with platinum black as to adsorb
hydrogen gas.
A platinum wire is welded to the platinum strip and sealed in a glass tube as to make contact with the outer
circuit through.
The platinum strip and glass tube is surrounded by an outer glass tube which has an inlet for hydrogen gas at
the top and a number of holes at the base for the escape of excess of hydrogen gas.
The platinum strip is placed in an acid solution which has H+ ion concentration 1M. Pure hydrogen gas is
circulated at one atmospheric pressure.
A part of the gas is adsorbed and the rest escapes through the holes. This gives equilibrium between the
adsorbed hydrogen and hydrogen ions in the solution.
H2

2H + +2e-

The temperature of the cell is maintained at 25oC.

The standard hydrogen electrode is arbitrarily assigned a potential of exactly 0.000 Volt.
The hydrogen electrode thus, obtained forms one of two half cells of a voltaic cell. When this half-cell is
connected with any other half-cell, a voltaic cell is constituted.
Page 27 of 39

The hydrogen electrode can act as cathode or anode with respect to other electrode.
SHE half reaction
H2
2H + +2e2H + +2e-

H2

Electrode potential
0.0 V (Anode)
0.0 V (Cathode)

ELECTROCHEMICAL SERIES
By measuring the potentials of various electrodes versus a standard hydrogen electrode (SHE), a series of
standard electrode potentials has been established.
When the electrodes (metals and non-metals) in contact with their ions are arranged on the basis of the
values of their standard reduction potentials or standard oxidation potentials, the resulting series is called the
electrochemical or activity series of the elements.
By international convention, the standard potentials of electrodes are tabulated for reduction half reactions,
indicating the tendencies of the electrodes to behave as cathodes towards SHE.
The electrodes with positive E0 values for reduction half reaction do in fact act as cathode versus SHE, while
those with negative E0 values of reduction half reactions behave instead as anode versus SHE.
STANDARD AQUEOUS ELECTRODE POTENTIALS AT 25C THE ELECTROCHEMICAL SERIES
Element
Electrode Reaction (Reduction)
Standard Electrode Reduction
potential E, Volts
+
Li
-3.05
Li
Li + e
+
K
-2.925
K + e
K
2+
Ca
-2.87
Ca
Ca + 2e
+
Na
-2.714
Na + e
Na
2+
Mg
-2.37
Mg
Mg + 2e
3+
Al
-1.66
Al
Al + 3e
2+
Zn
-0.7628
Zn
Zn + 2e
3+
Cr
-0.74
Cr
Cr + 3e
2+
Fe
-0.44
Fe
Fe + 2e
2+
Cd
-0.403
Cd
Cd + 2e
2+
Ni
-0.25
Ni
Ni + 2e
Sn
-0.14
Sn
Sn2+ + 2e-
+
H2
0.00
H2
2H + 2e
2+
Cu
+0.337
Cu
Cu + 2e
I2
+0.535
2I
I2 + 2e
+
Ag
+0.799
Ag
Ag + e
2+
Hg
+0.885
Hg
Hg + 2e
Br2
+1.08
2Br
Br2 + 2e
Cl2
+1.36
2ClCl2 + 2e -
Au
+1.50
Au
Au3+ + 3e-
F2
+2.87
2F
F2 + 2e

Page 28 of 39

APPLICATIONS OF ELECTROCHEMICAL SERIES

REACTIVITY OF METALS
The activity of metals depends on its tendency to lose electron or electrons, i.e. tendency to form cation (Mn+)
and this tendency depends on the magnitude of standard reduction potential.
The metal which has high negative value or smaller positive value of standard reduction potential readily loses
the electron or electrons and is converted into cation.
The chemical reactivity of metals decreases from top to bottom in the series. The metal higher in the series is
more active than the metal lower in the series.
For example,
Alkali metals and alkaline earth metals having high negative values of standard reduction potentials are
chemically active. These react with cold water and evolve hydrogen.
Metals like Fe, Pb, Sn, Ni, Co, etc, which lie a little down in the series do not react with cold water but react
with steam to evolve hydrogen.
Metals like Cu, Ag and Au which lie below hydrogen are less reactive and do not evolve hydrogen from water.
ELECTROPOSITIVE CHARACTER OF METALS
The electropositive character also depends on the tendency to lose electron or electrons and like reactivity, the
electropositive character of metals decreases from top to bottom in the electrochemical series.
On the basis of standard reduction potential values, metals are divided into three groups:
Strongly electropositive metals:
Metals having standard reduction potential near about 2.0 volt or more negative like alkali metal, alkaline earth
metals are strongly electropositive in nature.
Moderately electropositive metal:
Metal having values of reduction potentials between 0.0 and about 2.0 volt are moderately electropositive. Al,
Zn, Fe, Ni, Co, etc., belong to this group.
Weakly electropositive metal:
The metals which are below hydrogen and possess positive values of reduction potentials are weakly electropositive
metal. Cu, Hg, Ag, etc., belong to this group.
DISPLACEMENT REACTIONS
Case 1: To predict whether a given metal will displace another, from its salt solution:
A metal higher in the series will displace the metal from its solution which is lower in the series, i.e. the metal
having low standard reduction potential will displace the metal from its salts solution which has higher value
of standard reduction potential.
A metal higher in the series has greater tendency to provide electrons to the cations of the metal to be
precipitated.

Page 29 of 39

Case 2: Displacement of one non-metal from its salt solution by another non-metal:
A non-metal lower in the series (towards bottom side), i.e. having high value of reduction potential will displace
another non-metal with lower reduction potential, i.e. occupying position above it in the series.
The non-metal which possesses high positive reduction potential has the tendency to accept electrons readily
and these electrons are provided by the ions of the non-metal having low value of reduction potential.
For example,
Cl2 can displace bromine and iodine from bromides and iodides.
2KCl + I2
Cl2 + 2KI
I2 + 2e2I

2ClCl2 + 2e

(Oxidation)
(Reduction)

Case 3: Displacement of hydrogen from dilute acids by metals:

The metal which can provide electrons to H+ ions present in dilute acids for reduction, evolve hydrogen from
dilute acids.

Mn+ + neM

(Oxidation)

H2
2H+ + 2e-

(Reduction)

The metal having negative values of reduction potential possess the property of losing electrons or electrons.
Thus, the metals occupying top positions in the electrochemical series readily liberate hydrogen from dilute
acids and on descending in the series tendency to liberate hydrogen gas from dilute acids decreases.
The metals which are below hydrogen in electrochemical series like Cu, Hg, Au, Pt, etc., do not evolve hydrogen
from dilute acids.
REDUCING POWER OF METAL
Reducing nature depends on the tendency of losing electron or electrons.
More the negative reduction potential, more is the tendency to lose electron or electrons, thus, reducing nature
decrease from top to bottom in the electrochemical series.
The power of the reducing agent increases as the standard reduction potential becomes more and more negative.
For example,
Sodium is a stronger reducing agent than zinc and zinc is a stronger reducing agent than iron.
Element
Na
Zn
Fe
Reducing potential
-2.71
-0.76
-0.44

Note:
Alkali and alkaline earth metals are strong reducing agents.
OXIDIZING NATURE OF NON-METALS
Oxidizing nature depends on the tendency to accept electron or electrons, i.e., more the value of reduction
potential, higher is the tendency to accept electron or electrons.
Thus, oxidizing nature increases from top to bottom in the electrochemical series.
Page 30 of 39

The strength of an oxidizing agent increases as the value of reduction potential becomes more and more positive.
For example,
F2 (Fluorine) is a stronger oxidant than Cl2, Br2 and I2.
Cl2 (Chlorine) is a stronger oxidant than Br2 and I2.
Element
Reduction potential

I2
+ 0.53

Br2
+ 1.06

Cl2
+ 1.36

F2
+ 2.85

Oxidising natureincreases

SOLVED EXAMPLES
Example 1: Four metals A, B, C and D have their standard reduction potential value equal to -0.14 volt, +0.34
volt, -1.66 volt and +0.80 volt respectively. Arrange these metals in the decreasing order of reactivity.
Solution:
The metal which has higher negative value of reduction potential is more reactive. Thus, the reactivity of these
metals will decreases in order of
C
> A > B > D
-1.66 -0.14 +0.34 +0.80 Reduction potentials

Decreasing order
Example 2: Iron can displace copper from copper sulphate solution but silver does not displace copper. Why?
Solution:
The position of iron in the electrochemical series is above copper but of silver is below copper. Iron having low
reduction potential is capable of providing electrons to Cu2+ ions for reduction but silver is less active than
copper as its reduction potential is higher than copper.
Fe2+ +2e (Oxidation)
Fe
Cu (Reduction)
Cu2+ + 2e-
2+
Silver does not provide electrons to Cu ions.

GALVANIC (or) VOLTAIC CELL

It is a device in which a redox reaction is used to convert chemical energy into electrical energy, i.e. electricity
can be obtained with the help of oxidation and reduction reaction.
The chemical reaction responsible for production of electricity takes place in two separate compartments. Each
compartment consists of a suitable electrolyte solution and a metallic conductor.
The metallic conductor acts as an electrode. The compartment containing the electrode and the solution of the
electrolyte is called a half cell.
When the two compartments are connected by a salt bridge and electrodes are joined by a wire through
galvanometer, the electricity begins to flow.
DANIEL CELL
It is designed to make use of the spontaneous redox reaction between zinc and cupric ions to produce an
electric current.
It consists of two half cells. The half-cell on the left contains a zinc metal electrode dipped in ZnSO4 solution.
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The half-cell on the right consists of copper metal electrode in a solution of CuSO4.
The half cells are joined by a salt bridge that prevents the mechanical mixing of the solution.

When the zinc and copper electrodes are joined by a wire, the following observations are made:
There is a flow of electric current through the external circuit.
The zinc rod loses its mass while the copper rod gains in mass.
The concentration of ZnSO4 solution increases while the concentration of copper sulphate solution decreases.
The solutions in both the compartments remain electrically neutral.
During the passage of electric current through external circuit, electrons flow from the zinc electrode to the
copper electrode.
At the zinc electrode, the zinc metal is oxidized to zinc ions which go into the solution.
The electrons released at the electrode travel through the external circuit to the copper electrode where, they
are used in the reduction of Cu2+ ions to metallic copper which is deposited on the electrode.
The two half-cell reactions in Daniel cell can be represented as,
Oxidation half reaction: Zn s
Zn 2 aq 2e
Cu s
Reduction half reaction: Cu 2 aq 2e

Cu s Zn 2 aq
Thus, the overall redox reaction is: Zn s Cu 2 aq

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SALT BRIDGE AND ITS SIGNIFICANCE

Salt bridge is usually an inverted U-tube filled with concentrated solution of inert electrolytes.
An inert electrolyte is one whose ions are neither involved in any electrochemical change nor do they react
chemically with the electrolytes in the two half cells. Generally salts like KCl, KNO3, NH4NO3, etc, are used.
For the preparation of salt bridge, gelatin or agar-agar is dissolved in a hot concentrated aqueous solution of
an inert electrolyte and the solution thus, formed is filled in the U-tube. On cooling the solution sets in the
form of a gel in the U-tube.
The ends of the U-tube are plugged with cotton wool as to minimize diffusion effects.
SIGNIFICANCE/FUNCTIONS OF SALT BRIDGE
Salt bridge connects the solutions of two half cells and completes the cell circuit.
Salt bridge prevents transference or diffusion of the solutions from one half cells to the other.
Salt bridge keeps the solutions in two half cells electrically neutral.
For example,
In anodic half-cell, positive ions pass into the solution and there shall be accumulation of extra positive
charge in the solution around the anode which will prevent the flow of electrons from anode. The does not
happen because negative ions are provided by salt bridge.
Similarly, in cathode half-cell negative ions will accumulate around cathode due to deposition of positive ions
by reduction. To neutralize these negative ions, sufficient numbers of positive ions are provided by salt bridge.
Thus, salt bridge maintains electrical neutrality.

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REPRESENTATION OF AN ELECTRO-CHEMICAL CELL (GALVANIC CELL)

The following universally accepted conventions are followed in representing an electrochemical cell:
The anode (negative electrode) is written on the left hand side and cathode (positive electrode) on right hand side.
A vertical line or semicolon (;) indicates a contact between two phases.
The anode of the cell is represented by writing metal first and then the metal ion present in the electrolytic
solution.
Both the metal and the metal ion are separated by vertical line or a semicolon.
For example,
Zn | Zn2+ or Zn; Zn2+ or Zn | Zn2+ (1M)
The cathode of the cell is represented by writing the cation of the electrolyte first and then metal.
Both are separated by a vertical line or semicolon.
For example,
Cu2+ | Cu or Cu2+; Cu or Cu2+ (1M) | Cu
The molar concentration of the solution is written in brackets after the formula of the ion.
For example,
Zn | Zn2+ (1M) or Zn | Zn2+ (0.1M)
The salt bridge which separates the two half cells is indicated by two parallel vertical lines.
The Daniel cell can be represented as:
Zn (s) | ZnSO4( aq ) || CuSO4( aq ) | Cu ( s )

Anode Salt bridge Cathode

Oxidation half-cell Reduction half-cell
or

Zn | Zn2+ ||Cu2+ | Cu

or

Zn | Zn2+ (1M) || Cu2+ (1M) | Cu

EMF OF A GALVANIC CELL

Every galvanic or voltaic cell is made up of two half cells, the oxidation half cell (anode) and the reduction
half cell (cathode). The potentials of these half cells are always different.
On account of this difference in electrode potentials, the electric current moves from the electrode at higher
potential to the electrode at lower potential, i.e. from cathode to anode.
The direction of the flow of electrons is from anode to cathode.
i.e

Anode

Flow of electrons
Flow of current

Cathode

The difference in potentials of the two half-cells is known as the electromotive force EMF of the cell or cell
potential.
The EMF of the cell potential can be calculated from the values of electrode potentials of the two half cells
constituting the cell. The following three methods are in use:

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Case 1: When oxidation potential of anode and reduction potential of cathode are taken into account.
E0cell = Standard oxidation potential of anode + Standard reduction potential of cathode
= E0ox (anode) + E0red (cathode)
Case 2: When reduction potentials of both electrodes are taken into account.
E0cell = Standard reduction potential of cathode Standard reduction potential of anode
= E0cathode E0anode
Case 3: When oxidation potentials of both electrodes are taken into account.
E0cell = Standard oxidation potential of anode Standard oxidation potential of cathode
= E0ox (anode) E0ox (cathode)
MEASUREMENT OF ELECTRODE POTENTIAL
The measurement of electrode potential of a given electrode is made by constituting a voltaic cell, i.e. by
connecting it with a standard hydrogen electrode (SHE).
1M solution is used in hydrogen half-cell and the temperature is maintained at 250C.
The reading of the voltmeter gives the electrode potential of the Electrode selected with respect to the hydrogen
electrode.

The standard electrode potential of a metal may be determined as it is the potential difference in volt developed
in a cell consisting of two electrodes.
The pure metal in contact with a molar solution of one of its and the standard hydrogen electrode.
Case 1: Determination of standard electrode potential of Zn/Zn2+ electrode.
A Zinc rod is dipped in 1M Zinc nitrate solution.
This half-cell is combined with a standard hydrogen electrode through a salt bridge.
Both the electrodes are connected with a voltmeter as shown in the figure below.
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The deflection of the voltmeter indicates that current is following from hydrogen electrode to metal electrode or
the electrons are moving from zinc rod to hydrogen electrode.
The zinc electrode acts as an anode and the hydrogen electrode as cathode and the cell can be represented as:

Zn s Zn 2 aq 2H aq H 2 g

The cell reactions are:

At Anode:
Zn

At Cathode:
2H + +2e-

Zn 2+ +2e-

H2

The EMF of the cell is 0.76 volts

E 0cell = E 0 Anode + E0 Cathode

0.76 = E0Anode + 0
E0Anode = + 0.76V
As the reaction on the anode involves the oxidation of Zinc, E0Anode is the standard oxidation potential of Zinc i.e
E 0 Zn / Zn2 0.76 volt

Standard reduction potential of Zn, i.e. E 0 Zn2 / Zn = - E0ox = - (+0.76)

= - 0.76 volts
Case 2: Determination of standard electrode potential of Cu2+/Cu, electrode.
A copper rod is dipped in 1M solution of CuSO4.
It is combined with hydrogen electrode through a salt bridge.
Both the electrodes are joined through a voltmeter.
The deflection of the voltmeter indicates that current is flowing from copper electrode towards hydrogen
electrode, i.e. the electrons are moved from hydrogen electrode to copper electrode.
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The hydrogen electrode acts as an anode and the copper electrode as a cathode.
The cell can be represented as:

H 2 g 2H aq Cu 2 aq Cu (s)
The cell reactions are:
At Anode:
H2

At Cathode
Cu 2+ (aq) +2e-

2H + +2e-

Cu (s)

The EMF of the cell is 0.34 volt.

E 0cell E 0 Anode E 0 Cathode

0.34 0 E 0Cathode

Cu, E0 Cathode is the standard reduction

Since, the reaction on the cathode is reduction, i.e.Cu2+ + 2e-
potential of copper.
E0ox (standard oxidation potential of copper) = -0.34 volt
The standard electrode potential (oxidation or reduction) of various elements can be measured by combining the
electrode in question with a standard hydrogen electrode and measuring the EMF of the cell constituted.

S. No
1.

DIFFERENCES BETWEEN EMF AND POTENTIAL DIFFERENCE

EMF
Potential difference
It is the potential difference between two
It is difference of the electrode potentials of the
electrodes when no current is flowing in the two electrodes when the cell is under operation.
circuit.

2.

It is maximum voltage that the cell can deliver.

It is always less than the maximum value of

voltage which the cell can deliver.

3.

It is responsible for the steady flow of current inIt is not responsible for the steady flow of current
the cell.
in the cell.

PREDICTION FOR OCCURRENCE OF A REDOX REACTION

Any redox reaction would occur spontaneously only if the free energy change (G) is negative.
The free energy is related to cell EMF in the following manner:

G nFE cell
and

G 0 nFE 0cell
where,
n is the number of electrons involved.
F is the value of Faraday.
E 0cell is the standard cell EMF.

Note:
G will be negative if E is positive.
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WORK DONE BY THE CELL

Let n faraday charge be taken out of cell of EMF E then work done by the cell will be calculated as:
Work = Charge Potential
= nFE 0
Work done by the cell is equal to decrease in free energy.
- G = nFE 0
Similarly, maximum obtained work from the cell will be
wmax = nFE 0cell
where,

E 0cell = standard EMF or standard cell potential

- G0 = nFE0

PROBLEMS FOR PRACTICE

1.

2.

3.

4.

5.
6.

Which of the following reaction will be feasible?

CuSO4 + Zn(s)
(i) ZnSO4 + Cu
ZnSO4 + Cu(s)
(ii) CuSO4 + Zn
0 2+
Given: E Zn /Zn = -0.76 V; E0 Cu2+/Cu = +0.34V
Ans. (ii) is feasible. Metal with lesser standard reduction potential will displace other metal from
its salt, thus zinc will displace copper from the solution of copper sulphate.
Construct a galvanic cell using following electrodes:
E0Zn2+/Zn = -0.76V
; E0Cu2+/Cu =+0.34V
Calculate its standard EMF.
Ans. +1.10 volt
Construct the cells in which the given reactions are taking place. Which electrode shall act as anode
(negative electrode) and which one as cathode (positive electrode)?
ZnSO4 + Cu
(i) Zn + CuSO4
Cu(NO3)2 + 2Ag
(ii) Cu + 2AgNO3
ZnSO4 + H2
(iii) Zn + H2SO4
FeCl2 + Sn
(iv) Fe + SnCl2
Consider the cell: Zn | Zn2+ (aq) (1.0 M) | | Cu2 (aq) (1.0M) | Cu
The standard electrode potentials are:
Cu(aq)
Cu2+ + 2e-
; E0 = 0.350 volt
Zn(aq)
Zn2 + 2e-
; E0 = -0.763vilt
(i) Write down the cell reaction.
(ii) Calculate the EMF of the cell.
Ans. 1.113 volt
2+
2+
Will Fe be oxidized to Fe by reaction with 1.0M HCl? E for Fe / Fe = +0.44 volt.
Ans. EMF = 0.44 volt. Since, EMF is positive, the reaction shall occur.
The value of E of some of the reactions are given below:
2II2 + 2e-
; E = +0.54 volt
2Cl- ; E = +1.36 volt
Cl2 + 2e-
Fe2+ ; E = +0.76 volt
Fe3+ + e-

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7.

Ce4+ + e-
Ce3+ ; E = +1.60 volt
Sn4+ + 2e-
Sn2+ ; E = +0.15 volt
On the basis of the above data, answer the following questions.
(i) Whether Fe3+ oxidizes Ce3+ or not?
(ii) Whether I2 displaces chlorine from KCl?
(iii) Whether the reaction between FeCl3 and SnCl2 occurs or not?
Ans. Fe3+ does not oxidise Ce3+, I2 does not displace Cl2 from KCl, Fe3+ will oxidize Sn2+
Can we use a copper vessel to store 1M AgNO3 solution? Given that 2+/ =0.34V and E Ag / Ag = 0.80V
Ans. Since, EMF is positive, copper reacts with AgNO3, hence, AgNO3 solution cannot be stored in a
copper vessel.

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