GRADE XII

ELECTROCHEMISTRY
It is the branch of chemistry which
deals with the inter-conversion of
chemical energy and electrical
energy
Electrochemical Cell:
An electrochemical cell that converts the chemical energy of a spontaneous redox reaction
into electrical energy. It is also called Galvanic Cell or Voltaic cell.
A typical electrochemical cell consists of two half cells:
- One in which oxidation takes place called the anodic half cell.
- One in which reduction takes place called the cathodic half cell.
Each half cell usually consist of a electrode dipped into a solution of its own ions.

The half cells are connected together using a salt bridge which is rich in a strong electrolyte
KCl, KNO3,NH4NO3,K2SO4 etc.

The main functions of the salt bridge are:

- To maintain electrical neutrality of the two solutions in the half cells.
- To complete the electrical circuit.
DANIEL CELL
The two half cells in the Daniel
cell are:
Zinc rod dipped in ZnSO4 solution
as the anode and Copper rod
dipped in CuSO4 solution as the
cathode.

The two half cells are connected

using a salt bridge which is a
saturated solution of a salt like KCl
which is filled in glass tube in jelly Overall cell reaction:
form using agar-agar or gelatin. Zn(s) + Cu2+ (aq) ⟶ Zn2+(aq) + Cu(s)
Representation of an electrochemical cell
An electrochemical cell can be symbolically represented as given below:
Anode / Anodic solution (Concentration) // Cathodic solution ( Concentration) / Cathode

For example, Daniel cell can be represented as given below:

Zn(s) / Zn2+(aq) (1M) // Cu2+(aq) (1M) / Cu(s)

If the reaction involves a gaseous reactant then it is usually adsorbed on a metal like
platinum to act like an electrode. For example in order to make a hydrogen electrode we
bubble hydrogen gas through platinum wire. In such cases the electrode is represented
as given below. When hydrogen electrode is acting as anode it is represented as:
Pt(s) / H2(g) (1 bar) / H+ (aq) ( 1 M) //
( The pressure of the gas involved is also shown because the pressure is a measure of the
amount of gas present like the concentration of the solution)
EMF of an electrochemical cell

The EMF ( Electromotive force) of a galvanic cell is the maximum potential

difference that exists between the two electrodes in a cell. It is represented as
Ecell. It is also called the cell potential.

Under standard conditions (ie., 1 bar pressure, 298 K temperature and

concentration ions equal to 1M) the EMF is referred to as standard emf Eocell.

The standard emf of Daniel cell is 1.1 V.

Effect of an external potential applied on a galvanic cell:
When an external opposite potential is applied to a galvanic cell
there are three possibilities:

1) When Eext = Ecell (1.1 V for Daniel cell)

(i) No flow of electrons or current.
(ii) No chemical reaction.

2) When Eext < Ecell

(i) Electrons flow from Zn rod to Cu rod hence current flows from
Cu to Zn.
(ii) Zn dissolves at anode and copper deposits at cathode.

3) When Eext > Ecell

(i) Electrons flow from Cu to Zn and current flows from Zn to Cu.
(ii) Zinc is deposited at the zinc electrode and copper dissolves
at copper electrode.
Effect of an external potential applied on a galvanic cell:
ELECTRODE POTENTIAL:
When a metal is dipped in a solution of its own ions
there are two possible processes that may take
place: M
a) The metal gets oxidized liberating ions into the
solution.
M ⇌ Mn+ + n e-
b) The metal ion is solution gets reduced to metal.
Mn+ + n e- ⇌ M

In either case a potential difference is created at the

metal solution interface.
This potential is called electrode potential which is n+
represented as EMn+/ M M
Under standard conditions it is called standard
electrode potential EoMn+/ M
ELECTRODE POTENTIAL:
Since a metal electrode dipped into a solution can have a tendency to undergo oxidation
or reduction in the system, Electrode potential is always taken as reduction potential.
The standard electrode potential is standardized by taking Standard Hydrogen Electrode
(SHE) as the standard. The value of standard electrode potential for SHE is arbitrarily
assigned as ‘ 0 ’.

Any electrode reaction which has a higher tendency for oxidation than hydrogen will have
a negative value for standard electrode potential.
For eg. E0Zn2+/Zn = - 0.76 V which means that Zinc has a higher tendency to get oxidized
than hydrogen.

Any electrode reaction which has a lower tendency for oxidation or higher tendency for
reduction than hydrogen will have a positive value for standard electrode potential.
For eg. E0Cu2+/Cu = + 0.34 V which means that Copper has a higher tendency to get reduced
than hydrogen.
FINDING EMF OF A GALVANIC CELL:
The emf of a cell can be determined by knowing the electrode potentials of the two
electrodes forming the cell.
Ecell = E (cathode) – E (anode)
Under standard conditions the standard emf of the cell Eocell is given as:

Eocell = Eo (cathode) – Eo (anode)

For eg. The standard emf of Daniel cell is calculated as given below
Eocell = Eo (cathode) – Eo (anode)
Eocell = EoCu2+/Cu – EoZn2+/Zn
= 0.34 V – (-0.76V) = 1.1 V
STANDARD HYDROGEN ELECTRODE:
The standard hydrogen electrode consists of
a platinum electrode coated with platinum
black. The electrode is dipped in an acidic
solution and pure hydrogen gas is bubbled
through it. The concentration of both the
reduced and oxidized forms of hydrogen is
maintained at unity. This implies that the
pressure of hydrogen gas is one bar and the
concentration of hydrogen ion in the solution
is one molar.

Electrode reaction of SHE as anode: Representation of SHE as anode:

1
/2 H 2 ⟶ H + + e- Pt(s) / H2(g) (1 bar) / H+ (aq) ( 1 M) //

Representation of SHE as cathode:

Electrode reaction of SHE as cathode:
// H+ (aq) ( 1 M) / H2(g) (1 bar) / Pt(s)
H + + e- ⟶ 1/ 2 H 2
ELECTROCHEMICAL SERIES:
The arrangement of electrodes in increasing order of their electrode potential is called
electrochemical series.
More positive the
electrode potential,
greater is its tendency to
undergo reduction
making it a better
oxidizing agent.

More negative the

electrode potential,
greater is its tendency to
undergo oxidation
making it a better
reducing agent.
NERNST EQUATION: The Nernst equation relates the variation of electrode potential with
respect to change in concentration of electrolytes and temperature.
Consider the electrode reaction given below:
Mn+ + n e- ⇌ M
Nernst equation for the electrode with the above electrode reaction can be written as:
EMn+/M = EoMn+/M - 2.303RT log [M] Where:
nF [Mn+] R = Universal Gas Constant
It can also be represented generally as: T = Temperature
o 2.303RT [Reduced state]
EMn+/M = E Mn+/M - log n = No. of electrons exchanged
nF [Oxidised State] in the process.
Since the terms R and F are universal constants, F = 1 Faraday = 96500 C
assuming the temperature is the standard temperature (Charge on one mole of
of 298K we can simplify the equation as: electrons)

o 0.059 [M]
EMn+/M = E n+
M /M
- log ( Since 2.303RT/F = 0.059 at 298 K)
n [Mn+]
 NERNST EQUATION FOR DANIEL CELL:
We know that the overall cell reaction for Daniel cell is : Zn(s) + Cu2+ (aq) ⟶ Zn2+(aq) + Cu(s)
Ecell = E(cathode) - E(anode)
= ECu2+/Cu – EZn2+/Zn
2.303RT [Zn]
= E Cu2+/Cu - 2.303RT log [Cu]
o
- E o
2+ - log
[Cu2+]
Zn
nF
/Zn [Zn2+]
nF
= EoCu2+/Cu - EoZn2+/Zn - 2.303RT log[Cu] - log[Zn]
nF [Cu2+] 2+ [Zn2+]
= EoCu2+/Cu - EoZn2+/Zn - 2.303RT log [Cu] [Zn ]
nF [Cu2+][Zn]
But the concentration terms of pure metals or liquids can be assumed to be equal to unity.
Therefore the equation (at 298K) becomes
2+
= o
E (Daniel Cell) - 2.303RT log [Zn ] = Eo(Daniel Cell) - 0.059 log[Zn2+]
2+
nF [Cu ] n [Cu2+]
 NERNST EQUATION FOR A GENERAL CELL:
If we consider a hypothetical cell with cell reaction:
aA + bB ⟶ cC + dD
The Nernst equation for this cell can be written as:
c d
Ecell = E o
- 2.303RT log [C] [D]
Cell a b
nF [A] [B]

The value of ‘n’ will depend upon the number of electrons involved in the anodic and
cathodic reactions. It is usually the LCM of the number electrons involved in the reaction at
the two electrodes.

For eg. For the reaction : 2Fe(s) + 3Cu2+ (aq) ⟶ 2Fe3+(aq) + 3Cu(s)
Here 3 electrons are released when Fe is oxidised at the anode to Fe3+ and 2 electrons are
required for reduction for Cu2+ to Cu at the cathode. Hence the value of ‘n’ here will be the
LCM of ‘2’ and ‘3’ which is equal to ‘6’.
Problems related to Nernst equation:
Question: Calculate the emf of the cell
Mg / Mg2+(0.130M) // Ag+(0.0001M) / Ag.
Given that standard emf of the cell is equal to 3.17 V at 298K
Question: Calculate the emf of the cell at 298K
Cr / Cr3+(0.001M) // Cu2+(0.0001M) / Cu.
Given EoCu2+/Cu = + 0.34 V and EoCr3+/Cr = - 0.74 V
Question: Calculate the electrode potential of the electrode with following electrode reaction
Cr2O72− + 14 H+ + 6 e-⟶ 2 Cr3++ 7 H2O
if the concentration of [H+] = 10-7M, [Cr2O72− ] = 0.02M and [Cr3+] = 0.01M if the standard
electrode potential for the reaction is 1.33 V

E = Eo + 0.059/6 log [Cr2O72-][H+]14/ [ Cr3+]2 = 1.33 + 0.01 log 2 x 10-96 = 0.373 V

Equilibrium constant of a cell reaction.
An electrochemical cell will not be delivering a potential indefinitely. The cell potential
becomes equal to zero once the reaction attains equilibrium. Or in other words at
equilibrium Ecell = 0. We know that according to Nernst equation.
a b
Ecell = E o
Cell
+ 2.303RT log [A] [B]
nF [C]c [D]d
o 2.303RT [C]c [D]d
Ecell = E Cell
- log
nF [A]a [B]b
[C]c [D]d
At equilibrium, Ecell = 0 and = K (Equilibrium constant)
[A]a [B]b
2.303RT
Hence , 0 = EoCell - log K
nF
nFEoCell
Therefore, Log K = E 0 cell = 2.303RT log K = 0.059 log k
2.303RT nF n
Gibbs Free energy for a cell reaction.
Gibbs Free energy ΔrG is also the measure of the maximum useful work that can be
done using a cell reaction. The value of ΔrG can be determined from the expression

ΔrG = - nFEcell
Under standard conditions, the standard free energy change ΔrGo is expressed as

ΔrGo = - nFEocell ΔrG = -nF 2.303RT log k = - 2.303 RT log k

nF
We can also determine the equilibrium constant of the reaction from the knowledge of
Gibbs Free Energy.

ΔrGo = - RTlnK = - 2.303RTlogK

Problems related to Gibbs Free Energy and Equilibrium Constant:
Assignment (DOS - 9.9.20)

Question: The cell in which the following reaction occurs:

2Fe3+(aq) + 2 I-(aq) ⟶ 2 Fe2+(aq) + I2 (s)
has Eocell= + 0.236 V at 298 K. Calculate the standard Gibbs energy and the equilibrium
constant of the cell reaction.
ELECTROLYTIC CONDUCTANCE
An electrolyte is a substance which can conduct electricity in aqueous or molten
state. They conduct electricity through movement of ions, hence the ions must
be free in order to make and electrolyte conducting.
Depending upon the ionization of an electrolyte, they can be classified into two
types:
a) Strong electrolyte which completely ionizes in water like NaCl or HCl.
b) Weak electrolytes which only partially ionize in water like CH3COOH or NH4OH

The main factors which decide the conductance of an electrolyte are:

a) Concentration
b) Temperature
c) Nature of the electrolyte.
ELECTROLYTIC CONDUCTANCE
Conductance is the inverse of resistance, It represents the ability of a conductor to conduct
electricity. If G is the conductance and R, the resistance.
1
Conductance, G =
R
The unit of conductance is Ω-1 , mho or Siemens (which is represented as ‘S’)
Since conductance is directly proportional to area of cross section of the conductor ‘A’ and
inversely proportional to the length of the conductor ‘l’

Hence Gα A or G = 1 = κ A
l R l
The term ‘κ’ is the specific conductance of conductivity of the conductor which can be defined
as the conductance offered by a conductor with unit length and unit area of cross section. The
unit of conductivity is Sm-1 or Scm-1.
The magnitude of conductivity varies a great deal and depends on the nature of the material. It
also depends on the temperature and pressure at which the measurements are made.

Materials are classified into conductors, insulators and semiconductors depending on the
magnitude of their conductivity.
Metals and their alloys have very large conductivity and are known as conductors. Certain
non-metals like carbon-black, graphite and some organic polymers* are also electronically
conducting.

Substances like glass, ceramics, etc., having very low conductivity are known as insulators.

Substances like silicon, doped silicon and gallium arsenide having conductivity between conductors
and insulators are called semiconductors and are important electronic materials.

Certain materials called superconductors by definition have zero resistivity or infinite conductivity.
Earlier, only metals and their alloys at very low temperatures (0 to 15 K) were known to behave as
superconductors, but nowadays a number of ceramic materials and mixed oxides are also known to
show superconductivity at temperatures as high as 150 K
Electrical conductance through metals is called metallic or electronic conductance and is
due to the movement of electrons. The electronic conductance depends on
(i) the nature and structure of the metal
(ii) the number of valence electrons per atom
(iii) temperature
It decreases with increase of temperature.

The conductance of electricity by ions present in the solutions is called electrolytic or ionic
conductance. The conductivity of electrolytic (ionic) solutions depends on:
(i) the nature of the electrolyte added
(ii) size of the ions produced and their solvation
(iii) the nature of the solvent and its viscosity
(iv) concentration of the electrolyte
(v) temperature
It increases with the increase of temperature.
MEASUREMENT OF ELECTROLYTIC CONDUCTANCE
It Is not possible to measure the conductance or resistance of
an electrolyte by directly attaching it to any apparatus
because they conduct only in molten or aqueous state. Hence
the electrolytic solution whose resistance is to be measured is CONDUCTIVITY CELL
taken in a conductivity cell which is glass vessel fitted with
two electrodes having fixed area of cross section kept fixed
distance apart i.e whose l/A value is known.
The conductivity cell filled with the electrolyte is fitted to a
Wheatstone's bridge arrangement which uses an AC source
for power and a suitable detector to find the null point.
Since the area of cross section ‘A’ and distance between the
electrode ‘l’ are a constant. They can be together expressed as
cell constant G* where,
G* = l or GG* = κ or G* = κ R
A
MOLAR CONDUCTIVITY
The comparative study of electrolytic conductivity becomes meaningful only when the
concentration of the electrolyte is also taken into account. Hence a new term molar
conductivity is defined.
Molar conductivity Λm is defined as the conductivity of exactly one mole of an electrolyte kept
between two electrodes with unit area of cross section kept unit distance apart. If ‘C’ is the
concentration of the electrolyte in mol m-3 and κ , the conductivity in Sm-1, Then
Λm = κ (The unit of Λm will be Sm2mol-1 )
C
If concentration is expressed as molarity, M in molL-1 (moldm-3) and if κ is expressed in Scm-1.
Then,
Λm = κ x 1000 (The unit of Λm will be Scm2mol-1 )
M

It may be noted that 1 S m2 mol–1 = 104 S cm2 mol–1

or 1 S cm2 mol–1 = 10–4 S m2 mol–1.
It may be noted that 1 S m2 mol–1 = 104 S cm2 mol–1
or 1 S cm2 mol–1 = 10–4 S m2 mol–1.
Variation of Conductivity and Molar Conductivity with Concentration

Both conductivity and molar conductivity change with the concentration of the
electrolyte. Conductivity always decreases with decrease in concentration both, for
weak and strong electrolytes. This can be explained by the fact that the number of
ions per unit volume that carry the current in a solution decreases on dilution. The
conductivity of a solution at any given concentration is the conductance of one unit
volume of solution kept between two platinum electrodes with unit area of cross
section and at a distance of unit length. This is clear from the equation:
Molar conductivity of a solution at a given concentration is the conductance of the
volume V of solution containing one mole of electrolyte kept between two electrodes
with area of cross section A and distance of unit length. Therefore,

Molar conductivity increases with decrease in concentration. This is because the

total volume, V, of solution containing one mole of electrolyte also increases. It has
been found that decrease in κ on dilution of a solution is more than compensated by
increase in its volume.
VARIATION OF CONDUCTIVITY AND MOLAR CONDUCTIVITY WITH CONCENTRATION:
Conductivity always decreases with decrease in concentration both, for weak and strong
electrolytes. This can be explained by the fact that the number of ions per unit volume that
carry the current in a solution decreases on dilution.
However, the molar conductivity is defined for one mole of an electrolyte. Hence the
number of ions is always one mole. However as the solution is diluted the mobility of the ions
will increase and hence there will be an increase in the molar conductivity with dilution.
The variation of molar conductivity for strong and weak electrolytes are different.
STRONG ELECTROLYTES: Strong electrolytes are completely ionized in water. There will not be
any increase in concentration of ions with dilution. Hence the variation of molar conductivity
Λm with decrease in √C will be a linear increase. This is mathematically expressed as Debye
Huckel Onsager equation.
Λm = Λom - A√C
Where Λom or Λ∞m is the limiting molar conductivity which is a constant and A is a constant
which depends on the nature of the electrolyte. On plotting Λm against √C we get a straight
line with y-intercept equal to Λom and slope equal to A.
The value of the constant ‘A’ for a given solvent and temperature depends on the type of
electrolyte i.e., the charges on the cation and anion produced on the dissociation of the
electrolyte in the solution. Thus, NaCl, CaCl2 , MgSO4 are known as 1-1, 2-1 and 2-2
electrolytes respectively. All electrolytes of a particular type have the same value for ‘A’.
When concentration approaches zero, the molar conductivity is known as limiting molar
conductivity and is represented by the symbol Λ° m .
For a strong electrolyte the Λm increases because the
mobility of the ions increases as inter-ionic
interaction decreases on dilution.
VARIATION OF CONDUCTIVITY AND MOLAR CONDUCTIVITY WITH CONCENTRATION:
WEAK ELECTROLYTES: Strong electrolytes are only
partially ionized in water. As dilution increases, the
degree of dissociation or ionization of the
electrolyte will also increase. Therefore, there is an
exponential increase in molar conductivity of a o
Λm
weak electrolyte with dilution.
The degree of dissociation α for a weak electrolyte Strong electrolyte
at a particular concentration can be determined by (HCl)
knowing the value of Λm at a particular
concentration and Λom or Λ∞m which is a constant. Λ
α= Λ m
o Weak electrolyte
Λ
m m (CH3COOH)
The dissociation constant K also can be determined.
Cα 2 √C
K=
(1 – α)
LIMITING MOLAR CONDUCTIVITY AND KOHLRAUSCH’S LAW:
Limiting Molar Conductivity or Molar conductivity at infinite dilution Λom can be defined as
the molar conductivity of an electrolytic solution as its concentration approaches zero ( or
dilution approaches infinity). Its value is a constant for a particular electrolyte.It cannot be
calculated for weak electrolyte from the graph as towards 0 concentration, the graph runs
almost parallel to the y axis.It is calculated by applying Kohlrausch’s law.

Kohlrausch law (also called Law of independent migration of ions):

The law states that limiting molar conductivity of an electrolyte can be represented as
the sum of the individual contributions of the anion and cation of the electrolyte. The
contribution made by a particular ion towards limiting molar conductivity is a constant
irrespective of the nature of the counter ion. For example the limiting molar conductivity of
NaCl can be expressed according to Kohlrausch’s law as given below:

Λom (NaCl) = λoNa+ + λoCl-

Where λoNa+ and λoCl- are the limiting ionic molar conductivities of Na+ and Cl- ions.
APPLICATION OF KOHLRAUSCH’S LAW:
The most important application of Kohlrausch’s Law is to determine the limiting molar
conductivities of weak electrolytes. The Λom of strong electrolytes can be determined
graphically by plotting Λm against √C. From the knowledge of Λom of strong electrolytes we
can determine the Λom of a weak electrolyte. Let us consider the Λom of acetic acid.
According to Kohlrausch’s Law, the Λom of acetic acid can be expressed as
Λom (CH3COOH) = λoH+ + λoCH3COO-
But we know that according to Kohlrausch’s law:
Λom (CH3COONa) = λoNa+ + λoCH3COO- ⟶ ①
Λom (HCl) = λoH+ + λoCl- ⟶ ②
Λom (NaCl) = λoNa+ + λoCl- ⟶ ③
Equation ① + ② - ③ will give
Λom (CH3COONa) + Λom (HCl) + Λom (NaCl) = λoNa+ + λoCH3COO- + λoH+ + λoCl- - ( λoNa+ + λoCl- )
= λoCH3COO- + λoH+ = Λom (CH3COOH)
Hence the Λom of acetic acid which is a weak electrolyte can be determined from the
knowledge of Λom values of three strong electrolytes HCl. NaCl and CH3COONa.
Tha other applications of Kohlrausch’s law is to calculate 𝝰 and Ka.
 ELECTROLYSIS
Electrolysis is a process in which a
chemical reaction takes place by the
application of an external voltage. A simple
electrolytic cell consists of a vessel containing
the electrolyte in molten or aqueous state
with the electrodes dipped into it. The positive
terminal of the external cell in connected to
the anode while the negative terminal is
connected to the cathode.
The positive ions in the electrolyte
migrate to the cathode where it undergoes
reduction while the negative ions migrate to
the anode where it gets oxidized.
The process is used in extraction of
metals,electroplating,electrolytic
refining,manufacture of Cl2,NaOH etc
FARADAY’S LAWS OF ELECTROLYSIS

The process of electrolysis is governed by Faraday’s Laws.

(i) First Law: The amount of chemical reaction which occurs at any electrode
during electrolysis by a current is proportional to the quantity of electricity
passed through the electrolyte (solution or melt).

(ii) Second Law: The amounts of different substances liberated by the same
quantity of electricity passing through the electrolytic solution are
proportional to their chemical equivalent weights. (Atomic Mass of Metal ÷
Number of electrons required to reduce the cation).
MATHEMATICAL EXPRESSION FOR FARADAY’S LAWS OF ELECTROLYSIS

If ‘m’ is the mass of a metal deposited through electrolysis when ‘Q’ amount of electricity is
passed through it. Then according to Faraday’s Law,
m α Q
If ‘I’ amperes of current is passing through the electrolyte for ‘t’ seconds then.
m α Ixt (∵ Q = I x t)
or m = Z x I x t ( Z is the electrochemical equivalence)
M
Where, Z = n F ( M = Molar mass, F = 1 Faraday and n = no. of electrons involved)
PROBLEMS RELATED TO ELECTROLYSIS
PROBLEMS RELATED TO ELECTROLYSIS
PROBLEMS RELATED TO ELECTROLYSIS
PROBLEMS RELATED TO ELECTROLYSIS
PROBLEMS RELATED TO ELECTROLYSIS
Assignment (DOS - 9.9.20)
Question: How many Faradays of electricity is required to deposit 54 g of Aluminium by
electrolysis of molten Al2O3?
(ii) Second Law: The amounts of different substances liberated by the same
quantity of electricity passing through the electrolytic solution are
proportional to their chemical equivalent weights. (Atomic Mass of Metal ÷
Number of electrons required to reduce the cation)

1F

Mass Cu 63.5/2g Ag 108g

deposited
Cu2+ + 2e Cu
2F deposits 63.5g
Ag+ + e Ag
1F deposits 108g
PREDICTING PRODUCTS OF ELECTROLYSIS
The products obtained on electrolysis of an electrolyte depends upon a variety
of factors like nature of electrodes, whether electrolyte is in molten or aqueous
state, etc….
If there is a competition for two ions to undergo reaction at a particular
electrode, the reaction will generally depend upon the electrode potentials of
the reactions involved.

In general,
The cation with higher tendency to reduce, ie., more positive electrode
potential is preferentially get reduced at the cathode and the anion with higher
tendency to oxidize, ie., more negative electrode potential is preferentially
oxidized at the anode.
Electrolysis of molten NaCl with Pt electrodes.

_
+
Anode (Pt) Cathode (Pt)

Cl- (aq) ⟶ 1/2Cl2 (g) + e- (s) Na+ (aq)+ e- ⟶ Na (s)

Chlorine is released at the Sodium is formed at the

anode. cathode.

Molten NaCl
Electrolysis of aqueous NaCl with Pt electrodes.

_
+
Anode (Pt) Cathode (Pt)

Cl-(aq) ⟶ ½ Cl2 (g) + e –(s) H+ (aq) + e– ⟶ ½ H2 (g)

(Eocell = + 1.36V) (Eocell = 0.00 V)
redn potential
2H2O(l) ⟶ O2(g) + 4H+(aq) + 4e – Na+ (aq)+ e – ⟶ Na (s)
(Eocell = + 1.23V) (Eocell = - 2.71V)
Even though oxidation of
water to oxygen is less Since the reduction of
positive, It does not take place hydrogen ion to hydrogen
due to overpotential of the Aqueous NaCl gas a more positive Eo
reaction. Hence, Chlorine is value, Hydrogen is released
released at the anode. at the cathode.
Electrolysis of aqueous CuSO4 with Pt electrodes.

_
+
Anode (Pt) Cathode (Pt)
Cu2+ (aq)+ 2e – ⟶ Cu (s)
2H2O(l) ⟶ O2(g) + 4H+(aq) + 4e – (Eocell = + 0.34V)
(Eocell = + 1.23V)
H+ (aq) + e– ⟶ ½ H2 (g)
2SO42– (aq) ⟶ S2O82– (aq) + 2e– (Eocell = 0.00 V)
(Eocell = + 1.96V)
Since the oxidation of water Since the reduction of
to oxygen has less positive Eo Cupric ion to copper has
value, Oxygen is liberated at Aqueous CuSO4 more positive Eo value,
the anode. Copper is deposited at the
cathode.
Electrolysis of aqueous CuSO4 with Cu electrodes.

_
+
Anode (Cu) Cathode (Cu)

Cu2+ (aq)+ 2e – ⟶ Cu (s)

Cu (s) ⟶ Cu2+ (aq)+ 2e –
Cupric ion in solution gets
Copper gets oxidized at the reduced to copper and gets
anode.( Anode disintegrates) deposited at the cathode.

Aqueous CuSO4
Electrolysis of aqueous AgNO3 with Pt electrodes.

_
+
Anode (Pt) Cathode (Pt)
Ag+ (aq)+ e – ⟶ Ag (s)
2H2O(l) ⟶ O2(g) + 4H+(aq) + 4e –

Oxygen is liberated at the Silver is deposited at the

anode. cathode.

Aqueous AgNO3
Electrolysis of aqueous AgNO3 with Ag electrodes.

_
+
Anode (Ag) Cathode (Ag)

Ag+ (aq)+ e – ⟶ Ag (s)

Ag (s) ⟶ Ag+ (aq)+ e –

Silver gets oxidized at the Silver ions get reduced and

anode.( Anode disintegrates) gets deposited at the
cathode.

Aqueous AgNO3
Electrolysis of dilute Sulphuric acid solution with Pt electrodes.

_
+
Anode (Pt) Cathode (Pt)

H+ (aq) + e– ⟶ ½ H2 (g)
2H2O(l) ⟶ O2(g) + 4H+(aq) + 4e –
Water is oxidized to oxygen Hydrogen ion is reduced to
gas at the anode. hydrogen at the cathode.

Aqueous Dil. H2SO4

Electrolysis of Concentrated Sulphuric acid solution with Pt electrodes.

_
+
Anode (Pt) Cathode (Pt)

H+ (aq) + e– ⟶ ½ H2 (g)
2SO42– (aq) ⟶ S2O82– (aq) + 2e–
Sulphate ion is oxidized to Hydrogen ion is reduced to
peroxodisulphate ion at the hydrogen at the cathode.
anode

Aqueous Conc. H2SO4

COMMERCIAL CELLS
Any commercial cell that we use as a source of electrical energy is basically a
galvanic cell where the chemical energy of the redox reaction is converted into
electrical energy..

There are mainly two types of commercial cells.

1) Primary cells : Here the reaction occurs only once and after use over a
period of time battery becomes dead and cannot be reused again.

2) Secondary cells: This cell can be recharged by passing current through it in

the opposite direction so that it can be used again. The initial reactants in the
cell are restored through electrolysis of the products. A good secondary cell
can undergo a large number of discharging and charging cycles.
EXAMPLES FOR PRIMARY CELLS – LECHLANCHE DRY CELL
The cell consists of a zinc container that also acts as
anode and the cathode is a carbon (graphite) rod
surrounded by powdered manganese dioxide and
carbon. the space between the electrodes is filled by a
moist paste of ammonium chloride (NH4Cl) and zinc
chloride (ZnCl2). The electrode reactions taking place
are:
Anode: Zn(s) ⟶ Zn2+ + 2e–
Cathode: MnO2+ NH4+ + e–⟶ MnO(OH) + NH3
Overall reaction:
Zn(s) + 2 MnO2+ 2 NH4+ ⟶ Zn2+ + 2 MnO(OH) + 2 NH3

Ammonia produced in the reaction forms a complex

with Zn2+. The cell has an approximate potential of
1.5V
 EXAMPLES FOR PRIMARY CELLS – MERCURY CELL OR BUTTON CELL
Mercury cell, suitable for low current
devices like hearing aids, watches, etc.
consists of zinc – mercury amalgam as
anode and a paste of HgO and carbon as the
cathode. The electrolyte is a paste of KOH
and ZnO. The electrode reactions for the cell
are given below:
Anode: Zn(Hg) + 2OH– ⟶ ZnO(s) + H2O + 2e–
Cathode: HgO + H2O + 2e– ⟶ Hg(l) + 2OH–
Overall reaction:
Zn(Hg) + HgO(s) ⟶ ZnO(s) + Hg(l)

The cell potential of a mercury cell is approximately 1.35 V and remains constant during its
life as the overall reaction does not involve any ion in solution whose concentration can
change during its life time.
 EXAMPLES FOR SECONDARY CELLS – LEAD STORAGE BATTERY
It consists of a lead anode and a grid of lead
packed with lead dioxide (PbO2 ) as cathode. A 38%
solution of sulphuric acid is used as an electrolyte.
The cell reactions during the discharge of the cell
are:
Anode: Pb(s) + SO42–(aq) ⟶ PbSO4(s) + 2e–
Cathode:
PbO2(s) +SO42–(aq) +4H+(aq) +2e– ⟶ PbSO4 (s) +2H2O (l)

The overall cell reaction on discharge of the cell is :

Pb(s) + PbO2(s) + 2 SO42–(aq) + 4H+(aq) ⟶ 2 PbSO4 (s) +2 H2O (l)

The overall cell reaction during recharge of the cell is :

2 PbSO4 (s) +2 H2O (l) ⟶ Pb(s) + PbO2(s) + 2 SO42–(aq) + 4H+(aq)
EXAMPLES FOR SECONDARY CELLS – NICKEL - CADMIUM CELL
In this cell the anode is a Cadmium rod and cathode is
Nickel oxyhydroxide NiO(OH). The electrolyte is Aqueous
potassium hydroxide (KOH). The cell reactions during the
discharge of the cell are:

Anode: Cd(s) + 2OH– (aq) ⟶ Cd(OH)2(s) + 2e–

Cathode: 2NiO(OH)(s) + 2H2O(l) +2e– ⟶ 2Ni(OH)2(s) + 2OH– (aq)

The overall cell reaction on discharge of the cell is :

Cd (s) + 2NiO(OH)(s) + 2H2O(l) ⟶ Cd(OH)2(s) + 2Ni(OH)2 (s)

The overall cell reaction on discharge of the cell (as per NCERT TEXT) is :
Cd (s) + 2Ni(OH)3 (s) ⟶ CdO (s) + 2Ni(OH)2 (s) + H2O (l)
FUEL CELL
It is now possible to make cells in which
reactants are fed continuously to the electrodes and
products are removed continuously from the
electrolyte compartment. Galvanic cells that are
designed to convert the energy of combustion of
fuels like hydrogen, methane, methanol, etc.
directly into electrical energy are called fuel cells. A
very popular fuel cell is the H2-O2 fuel cell also called
the Bacon cell. It uses the reaction of hydrogen with
oxygen to form water.
The cell was used for providing electrical power in the Apollo space programme. The water
vapours produced during the reaction were condensed and added to the drinking water supply
for the astronauts. In the cell, hydrogen and oxygen are bubbled through porous carbon
electrodes into concentrated aqueous sodium hydroxide solution. Catalysts like finely divided
Pt or Pd metal are incorporated into the electrodes for increasing the rate of electrode
reactions.
FUEL CELLS
The electrode reactions taking place in
the H2-O2 fuel cell are given below:

Anode: O2 (g) + 2H2O (l) + 4e– ⟶ 4OH–(aq)

Cathode: 2 H2 (g) + 4OH–(aq) ⟶ 4H2O(l) + 4e–

The overall cell reaction is:

2H2 (g) + O2 (g) ⟶ 2H2O (l)

Main advantages of fuel cells are:

• The cell runs continuously as long as the reactants are supplied.
• Fuel cells produce electricity with an efficiency of about 70 % compared to thermal
plants whose efficiency is about 40%.
• Fuel cells are pollution free.
CORROSION
Corrosion can be defined as the eating up or breaking down of metals through
chemical processes. Rusting of iron is classic example for a process involving corrosion of
a metal. The process of rusting takes place in the presence of moist air. However, the
extend of rusting is greatly influenced by the presence of dissolved salts and it can be
also noted that it is more difficult for rusting to occur on polished metal surfaces.
All these factors point out that rusting is not merely a normal chemical oxidation of
iron in the presence of moist air. It is a more complex phenomenon. The most accepted
theory which explains the process of rusting of iron is the electrochemical theory of
rusting.
In this theory, a droplet of water sticking to the metal surface acts like a tiny
electrochemical cell. In the anodic region Fe oxidises to Fe2+ and the electrons produced
travel to the cathodic region where its is used for reduction of dissolved oxygen in the
presence of H+ ions to water. The Fe2+ ions formed combines with more water in the
presence of oxygen to form Fe2O3 which precipitates as brown coloured rust which is
hydrated Ferric oxide. (Fe2O3.xH2O)
ELECTROCHEMICAL THEORY OF RUSTING:

Fe (s) ⟶ Fe2+ (aq)+ 2e –

O2 (g) + 4H+(aq) +4e– ⟶ 2H2O(l)

Overall reaction: 2Fe(s) + O2(g) + 4H+(aq) ⟶ 2Fe2+(aq) + 2 H2O (l)

2Fe2+(aq) + 2H2O (l) + ½O2 (g) ⟶ Fe2O3 (s) + 4H+(aq)
Fe2O3 (s) + xH2O(l) ⟶ Fe2O3. xH2O (rust)
PREVENSION OF RUSTING:
Different methods can be used to prevent rusting. These methods can be grouped
into four types:
1) Barrier Protection: Here a coating of some inert substance is made on the metal to
prevent the contact of the metal surface with the atmosphere. Eg. Painting, greasing, etc.

2) Sacrificial protection: Here the metal is coated a more reactive metal like zinc
(Galvanization). This metal oxidises preferentially at the anode, protecting the iron.

3) Electrical protection: This method is used in protecting long iron pipelines. The iron
pipes are connected to a piece of more reactive metal which oxidises to provide the
electrons required for the reaction in place of iron preventing the iron from
disintegrating.

4) Anti rust chemicals: Chemicals like Bisphenol are coated on the surfaces of the metal
to prevent it from rusting.
End
of
Chapter