CLASS-XII-CHEMISTRY

CH-3-ELECTROCHEMISTRY

Mrs. Liji Elizabeth

 SYLLABUS
Unit III: Electrochemistry :

Redox reactions, EMF of a cell, standard electrode

potential, Nernst equation and its application to
chemical cells, Relation between Gibbs energy
change and EMF of a cell, conductance in
electrolytic solutions, specific and molar
conductivity, variations of conductivity with
concentration, Kohlrausch's Law, electrolysis and
law of electrolysis (elementary idea), dry cell-
electrolytic cells and Galvanic cells, lead
accumulator, fuel cells, corrosion
 Electrochemistry

It is that branch of chemistry which deals with

the study of production of electricity from energy
released during spontaneous chemical reactions
and the use of electrical energy to bring about
non-spontaneous chemical transformations.

 Importance of Electrochemistry
 Production of metals like Na, Mg. Ca and Al.
 Electroplating.
 Purification of metals.
 Batteries and cells used in various instruments.
 conductors
Conductors:
Substances that allow electric current
to pass through them are known as
conductors.
Metallic Conductors or Electronic
Conductors:
Substances which allow the electric
current to pass through them by the
movement of electrons are called
metallic conductors, e.g.. metals.
 Electrolytic conductors
Electrolytic Conductors or Electrolytes:
Substances which allow the passage
of electricity through their fused state
or aqueous solution and undergo
chemical decomposition are called
electrolytic conductors, e.g., aqueous
solution of acids. bases and salts.

 Types electrolytes
Electrolytes are of two types:
Strong electrolytes :The electrolytes
that completely dissociate or ionise into
ions are called strong electrolytes. e.g.,
HCl, NaOH, K2SO4

 Weak electrolytes :The electrolytes

that dissociate partially (ex < 1) are
called weak electrolytes, e.g., CH3COOH,
H2CO3, NH4OH, H2S, etc.
 Electrochemical cells or Galvanic cells
Or Voltaic cell

The devices in which chemical energy of a spontaneous

redox reaction is converted into electrical energy are
called electro chemical cells or galvanic cells.
These cells are very important because of their many
applications.
An early example of a galvanic cell is a Daniell cell
which was invented by the British chemist John Daniell
in 1836. Daniell cell was constructed on the basis of the
following spontaneous redox reaction:

Zn (s) + Cu 2+ (aq) ------Zn2+ (aq) + Cu (s)

 Electrolytic cell or Electrolysis
These constitute the electrochemical reactions in which
electrical energy is converted into chemical energy. In these
cells electrical energy is used to drive redox reactions which
have positive Gibbs energy & non –spontaneous .

The phenomenon of chemical changes taking place by the

passage of electrical energy from an external source is called
electrolysis. The devices or cells used to carry out electrolysis
are called electrolytic cells.
For ex: when electric current is passed through molten sodium
chloride , sodium is produced at cathode & chlorine is liberated
at anode.
2NaCl ------ 2 Na + Cl2
cathode anode
General Representation of an Electrochemical Cell
 Redox Reactions in Aqueous Solutions

In direct redox reactions, the

transference of electrons from the

reducing agent to the oxidizing agent
takes place in the same container. Hence, no
useful electric work is obtained.
 Daniell Cell

Electrochemical cells are also called

galvanic cells or voltaic cells after the
names of Luigi Galvani & Alessandro Volta
who were the first to perform experiments
on the conversion of chemical energy to
electrical energy .
The first galvanic cell- Daniell cell
Functioning of the Daniell cell
Consider a Daniell cell in which the
Zn electrode is dipped in ZnSO4 & cu
electrode is dipped Cu SO4. The cell
reaction
 The electrical potential (emf) of the cell is 1.1 V when concentration
of Zn 2+ & Cu 2+ ions is 1 M .

1.) Let this arrangement in which an external opposite potential is

applied & increased slowly. It is observed that the reaction continues
to take place till the opposing voltage reaches the value of 1.1V
.
2) External opposite potential is less than1.1 V , the electron continue
to flow from Zn rod to Cu rod & hence current flows from Cu to Zn .
Zinc dissolves in anode & copper deposits at cathode.

3)when the opposing voltage reaches the value 1.1 v, cell reaction
stops altogether & no current flows through the cell. There is no
chemical reaction .

4) Further increase in the external potential again starts the reaction ,but
in the opposite direction. The cell now starts functioning as an
electrolytic cell.
* In this case electrical energy is used to carry out non-
spontaneous chemical reaction. The electrons flow from
Cu to Zn rod & current flows from Zn to Cu.
As a result of electrolysis , zinc is deposited at the zinc
electrode & copper dissolves at copper electrode.
 Representation of this Electrochemical Cell

Practical- find out the emf of Daniell cell.-1.1V

 Representation of some common cells
1) Cu - AgNO3 cell
Cu ---- Cu2+ + 2 e- [oxidation]
2Ag+ + 2e- ------- 2Ag [reduction]
------------------------------------------------------
overall cell reaction :
Cu + 2A g + ---- CU2+ + 2Ag
The cell may be represented as :
 2Ni –AgN03 cell

Ni (s)-- Ni2 +(a q) + 2e-

[oxidation ]
2 Ag2+ (aq) + 2e-  2Ag(s)
[reduction]

over all reaction:

Ni (s) +2Ag (aq) + --Ni2(aq)+ 2Ag
The cell may represented as

Ni Ni2+ (aq) Ag+ (aq) Ag(s)

 Salt-bridge and its
functions
It is an inverted U- tube filled with concentrated solution of inert
electrolyte
[KCl,KNO3 or NH4NO3 are generally preferred because ions have
almost equal mobility - (transport number ] .

Functions :1) The salt bridge connects the two

solutions of the half cells & their electrodes are
connected by means of wire Therefore, the salt
bridge completes the circuit .
 2) Salt bridge maintains neutrality of two cell
solutions.
 Note:The electrons released by the oxidation of Zn to Zn 2+ ions will be
accepted by Cu 2+ ions of CuSO4 , in other half Cell & the & latter will
be reduced to copper. The positively charged Zn 2+ ions pass into the
solution After some time, this results accumulation of extra positive
charge in the solution around the anode. Similarly due to reduction of
some Cu2+ ions to Cu, the solution around the cathode will acquire extra
negative charge due to excess of SO4 2- ions. & this prevents the
further flow of electrons in respective electrodes & the cell will stop working.

It can be prevented by using salt bridge , which provides a passage

for the flow of the charge in the internal circuit. When the concentration of
Zn2+ ions around anode increases, sufficient number of Cl- ions migrate
from the salt bridge to anode half cell& sufficient number of K+ migrate
from the salt bridge to neutralize the excess negative due to the additional
SO4 2- ions in cathode half cell.

 Electrode potential

The electrical potential difference set up between the

metal & its solution is known as electrode potential .
It may be of two types
.
i) oxidation potential : The tendency of an electrode to
lose electrons or to get oxidized is called its oxidation
potential .

ii) Reduction potential : The tendency of an electrode to

gain electrons or to get reduced is called reduction
potential .
 Standard electrode potential

The potential difference developed

between metal electrode and solution
of ions of unit molarity (1M) at 1 atm
pressure and 25°C (298 K) is called
standard electrode potential.
It is denoted by E°.
 The electrode of known potential is called reference
electrode.
Reference Electrode

It may be primary reference electrode like hydrogen electrode

or secondary reference electrode like calomel electrode.

Standard hydrogen electrode (SHE) Standard hydrogen

electrode (SHE). also known as normal hydrogen electrode
(NHE), consists of platinum wire, carrying platinum foil coated
with finely divided platinum black.
The wire is sealed into a glass tube. placed in beaker
containing 1 M HCl. The hydrogen gas at 1 atm pressure is
bubbled through the solution at 298K.

Half-cell is pt H2 (1 atm) H+ (1 M)
 Chemical reacions in S.H.E
 When in a cell, this electrode acts as the anode , i.e oxidaion takes
place , the cell reaction must be,
H2  2H+ +2 e-
i.e , some hydrogen gas changes into H+ ions which go into the
solution.
when this electrode acts as cathode ,i.e reduction takes place,
 the cell reaction must be,

2 H+ + 2 e  H2 , i.e some H+ ions from the solution change

into H2 gas . Thus the electrode is reversible with respect to H+
ions. This electrode is usually represented as

Half-cell is pt H2 (1 atm) H+ (1 M)

 ** The electrode potential of the standard hydrogen

electrode is taken as 0.000 at 298 k.
Standard hydrogen electrode
To determine the
electrode potential of any
electrode, a cell is set up
using this electrode as
one of the electrodes &
the second electrode is
the standard hydrogen
electrode . The EMF of the
cell is measured.
Since the std. hydrogen
electrode for which the
electrode potential is
taken as zero, EMF of the
cell will directly give the
elcrode potential of the
electrode under
investigation.
E0 Cell=Eo cathode – Eo
 Measurement of electrode potential of
Zn2+/Zn electrode
An electrode consisting of zinc rod immersed in 1 M solution of ZnSO4 is
combined with S.H.E.
In this case , the electrons flow from zinc electrode to hydrogen electrode &
therefore, the zinc electrode acts as anode & S.H.E acts as a cathode. The
cell may be represented as :
The cell may be represented as :

Zn zn 2+(1M) H+ (1M)H2 (1
atm)Pt
The cell potential has been measured
to be 0.76V. Now , emf of cell,
E0 cell = E0 R – E 0 L
= E 0 (H+ /H2) - E0 (Zn2+/Zn)
0.76 = 0 - E0 (Zn2+/Zn)

E0 (Zn2+/Zn)= - 0.76V
Measurement of electrode potential of Cu2+/Cu
electrode
 To measure electrode potential of cu electrode , a cell
consisting of cu electrode immersed in 1 M CuSO4
solution & S.H.E.
 In the case hydrogen has greater tendency to lose

electrons than cu . Therefore oxidation occurs hydrogen

electrode.& reduction occurs at cu electrode.
Consequently , hydrogen electrode acts as anode & cu
electrode acts as cathode.
The cell may be represented as
Pt,H2(1atm) H+ (1M) Cu2+(1M) Cu
E0 cell = E0 R –E0 L
= E0 (Cu2+/ Cu) - E0 ( H+/ H2)
0.34 = E0 (Cu2+/ Cu)
E0 (Cu2+/ Cu) = 0.34V
 In SHE. at the surface of platinum, either of (the following
reaction can take place
 2H+(ag) + 2e- → H2 (g)Reduction
H2(g) → 2H+(ag) + 2e- Oxidation
 The electrode potential of SHE has been fixed as zero at all
temperatures.

 Its main drawbacks are

 1. It is difficult to maintain 1 atm pressure of H2 gas.
2. It is difficult to maintain H+ ion concentration 1 M.
3. The platinum electrode is easily poisoned by traces of
impurities.
 Hence, calomel electrodes are conveniently used as reference
electrodes, It consists of mercury in contact with
Hg2 Cl2 (calomel) paste in a solution of KCl.
 Emf
Electromotive Force (emf) of a Cell
It is the difference between the
electrode potentials of two half-cells
and cause flow of current from
electrode at higher potential to
electrode at lower potential. It is also
the measure of free energy change.
 Electrochemical Series

It is the arrangement of electrodes in

the increasing order of their standard
reduction potentials.
[ Standard Electrode Potential at 298
K]
Standard Electrode Potentials at
298 K
 Applications of Electrochemical Series (ECS)
1.To compare the relative oxidizing and reducing powers.
As by convention, + ve sign is used to represent the
reduction potential, it indicates that greater is the reduction
potential, more easily is the substance reduced or in other
words stronger oxidizing agent it is .
In the electrochemical series, F2 has the highest reduction
potential& Li + ion has lowest reduction potential-( F2 is
reduced most easily whereas Li+ ions are reduced with
greatest difficulty.
In other words, F2 is the strongest oxidizing agent & Li + is
the weakest oxidizing agent –[ strongest reducing agent ]
 2.To compare the relative activities of metals:

Greater the oxidation potential of a metal, more easily it can lose electrons & hence
greater is its reactivity. As a result, a metal with greater oxidation potential can displace
metals with lower oxidation potential from their salt solutions.
Ex: oxidation potentials of Mg, Zn, Fe, Cu & Ag are in the order
Mg, >Zn,> Fe, > Cu > Ag Hence each metal can displace metals on its right from the salt
solutions. So their reactivity is in the order.

3.To calculate the standard EMF of any electrochemical cell [ Eo cell ]

An electrochemical cell is split into two half cells –oxidation half reaction & reduction half
reaction.

Standard EMF of the cell = [standard oxidation potential of the

oxidation half reaction] + [standard
reduction potential of the reduction
half reaction]

As oxidation potential = - reduction potential , Then the above expression can be written
as ,
Standard EMF of the cell = [standard reduction potential of the
reduction half reaction] - [standard
reduction potential of the oxidation
half reaction]
It can be also written as,
Standard EMF of the cell = [ Standard reduction potential of the right-

hand side electrode (cathode)] - [Standard

reduction
the potential of the left-hand side electrode (anode)]

Eo cell = E o cathode - E o anode

4. To predict whether a metal reacts with acid to give hydrogen

gas.
All metals lying above hydrogen in the electrochemical series react with
the acid to give hydrogen gas.

5. To predict the spontaneity of a redox reaction.

For a redox reaction to be spontaneous, the EMF of the cell
must be positive. If the EMF comes out to be negative, the direct
reaction cannot take place, reverse reaction may take place.
 Numericals
• Q1.Write the half cell reaction and the over
all cell reaction for the electrochemical cell:
• Zn Zn 2+(1.0 M) Pb 2+(1.0 M ) Pb .
• Calculate the standard emf for the cell if
standard electrode potentials (reduction) for
Pb2+ Pb and Zn2+ Zn electrodes are
• -0.126Vand -0.763V respectively.
 Solution

Zn electrode acts as anode while Pb

electrode acts as cathode and therefore
oxidation occurs at zinc electrode and
reduction occurs at lead electrode.
The half cell reaction are:
Ox. Reaction : Zn (s) Zn2+ (aq) + 2e-
Red .Reaction :Pb2+(aq) + 2e-  P (s)
-------------------------------------------------------
Overall Reaction :Zn (s)+ Pb2+(aq) Zn2+ (aq)+
pb(s)
E0 cell= E0 R- E0 L
= -0.126 – (- 0.763)
= 0.637 V
 Q2. In a simple electrochemical cell,
which is in the standard state , the
half cell reactions with their
appropriate reduction potentials are :
 Pb 2+ + 2e-  Pb (s) , E0 = -0.13V
 Ag + (aq) + e -  Ag (s) , E0 = +
0.80V
 (a) What is the cell reaction for the
cell ?
 (b) Calculate the emf of the cell?
 Solution
Pb2+ (aq) +2e- Pb (s); E0 = -0.13V
Ag+(aq) +e- Ag (s) ; E0 = +0.80V
Reduction potential of Ag+/Ag electrode is more than that of
Pb2+/Pb .
Therefore , reduction will occur at silver electrode &
oxidation will occur at lead electrode and the cell reaction
will be
Pb (s) + 2 Ag+  2Ag (s)+ Pb2+(aq)
The cell may be represented as :
Pb Pb2+ Ag + Ag
E0 cell = E0 cathode - E0 anode
= 0.80 – (- 0.13)
=0.93 V
 Nernst Equation
The std. electrode potentials means the
concentration of the electrolyte solutions are
fixed as 1M , at 298 k.
But electrochemical cells do not have always
fixed concentration of the electrolyte solutions.
Nernst gave a relationship between electrode
potentials & the concentration of electrolyte
solutions known as Nernst equation .
For ex :
M n+ (aq) + ne-  M (s)------------reduction reaction

the Nernst equation is

E (Mn+ /M) =E0 (Mn+/ M) – RT [ M(s)]

-------- ln ---------
nF [Mn+ (aq)]

E (Mn+ /M) =E0 (Mn+/ M) – 2.303 RT [ M(s)]

-------- log ---------
nF [Mn+ (aq)]

where E (Mn+ /M) = electrode potential

R= gas constant ,

T = temperature,

n= no of electrons gained during the electrode reaction

[Mn+ (aq)] = molar concentration of ions,

[M] = molar concentration of metal

 Substituting the values of R (8.314 j/k/mol),T(298 K) & F
(96500 coulombs). Nernst equation at 25 o C becomes

E (Mn+ /M) =E0 (Mn+/ M) – 2.303 8.314 x298 [ M(s)]

----------- log ------------
n x 96500 [Mn+ (aq)]

E (Mn+ /M) =E0 (Mn+/ M) – 0.059 1

---------- log ----------
n [Mn+ (aq)]
We may write this equation as
E = E0 – 0.059 1 [ where [ M(s) ] = 1]

-------- log --------

n [Mn+ (aq)]
Effect of electrolyte concentration & temperature on
EMF of a cell --- NERNST EQUATION :
Let us consider DANIEL CELL,
the cell reacion is

Zn (s) + Cu 2+ (aq) --- Zn2+ (aq) + Cu

Apply the Nernst equation ,
for Zn elecrode ,
RT 1


E Zn2+ /Zn = E0 Zn2+ /Zn - -----------ln --------------

2F [Zn2 +]
similarly , for cu elecrode
RT 1


E Cu2+ / cu = E0Cu2+ / Cu - -------- ln ---------------------

2F [Cu2 +]

Then the emf of cell , Ecell = E cathode - E anode

= E Cu2+ / cu - E Zn2+ /Zn
 RT 1
= [ E0Cu2+ / Cu - -------- ln ------------- ] _ [ E0 Zn2+ /Zn
]
2F [Cu2 +]

RT [Zn 2+ (aq )]
=[E0Cu2+ / Cu _ E0 Zn2+ /Zn] - --------- ln ------------------
2F [Cu2+ (aq)]

2.303 RT [zn2+]
E CELL = E 0 cell - __________ log ----------

2F [C u2 +]

E CELL = E 0 cell - 0.059

--------- log
2
 EXAMPLE -2
consider the cell,

Cu /Cu 2+(aq) Ag+ (aq) / Ag

In Daniel cell , the valencies of zinc &copper are the same i.e n=2.
in the above cell, the valencies of metals are not the same.

Oxidation reaction : Cu (s) ----- Cu 2+(aq) + 2 e-

Reduction reaction : Ag + (aq) + e- ----- Ag (s) x 2
To balance the loss & gain of electrons , the reduction half cell is multiplied by 2 so
that the net reaction are

Cu (s) --------- Cu2+ + 2e-

2 Ag + (aq) + 2e- -----2 Ag

Note : We should use the same no : of electrons for both the electrodes.
hence the Cell reaction must be written as ,
Cu + 2Ag+ (aq) ------ Cu2+ + 2Ag

[NOTE : But E0 values will not change, It does not depend on the coefficient
s in the equation .]
 RT 1
E Cu2+ / cu = E0Cu2+ / Cu - -------- ln -------------------
2F [Cu2 +]

RT 1

E Ag+ / Ag = E0 Ag+ / Ag - -------- ln -------------------
2F [ Ag + (aq) ] 2

E CELL = E 0 cell - 0.059 [Cu2+]

--------- log -----------
2 [Ag+ (aq)]2
 General formula
In general ,for an electrochemical cell
reaction :
aA + bB------ cC + dD

E cell = E0 cel l – RT ln Q
----------
nF

E cell = E0cel l – RT ln [C]c [D]d

---------- --------------------
nF [A]a [B]b
 Equilibrium constant from Nernst equation
 At equilibrium, the electrode potentials of the two
electrodes become equal so that emf of the cell is zero.

 As the reaction progresses the concentration of Zn 2+

ions in the solution increases & consequently its
reduction potential increases .

 Ultimately a stage is reached when the reduction

potentials of the two electrodes become equal & have
same value . . The emf of the cell becomes zero & the
reaction stops. Under these conditions, the
electrochemical cell is said to have attained
equilibrium .
 Gibbs ‘ free energy & cell potential
 When a cell reaction takes place, electrical energy is
produced. The electrical work thus done by the system
(cell)results in the corresponding decrease in the free
energy of the system,
 So , electrical work done = decrease in free
energy .
 Thus free enegy change , -Δ G of a system comes out
to be negative , this means that the electrical work has
been done by the system on the surroundings( vice
versa).
 In the case of electrochemical cell, the electrical work
done is equal to the electrical energy produced which in
turn is equal to the product of the quantity of electricity
flowing in the circuit & emf of the cell .
 Electrical work done = electrical
energy produced x Quantity of
electricity flowing x EMF.
 NOTE : For every one mole of
electrons transferred in the cell
reaction, the quantity of electricity
that flows through the cell is one
faraday [ 1 F = 96500 Coulombs],
Hence , if n moles of electrons are
transfrerred
 electrical work done = n FECELL
-ΔG = nFEcell ----------(1)
As we know , standard cell potential is represented as , Eo cell.
The corresponding free energy change is called the standard
free energy change of reaction & is represented by Δ Go

RT
Eo CELL = ---------- ln Kc, by substituting this value in the
nF

above equation

- Δ Go = nFEo

-ΔG0 = nF . RT ln kc
 --------------
 nF
-ΔG = RT ln kc
ΔG = -RT ln kc

For comparing different cells, standard cell potentials are used

which are represented by E0 Cell, the corresponding free
energy change is called standard free energy change,
represented by the following equation.

- ΔG0 = RT ln kc
ΔG0 = -2.303 RT log kc,
Knowing Eo cell, ΔG0 can be calculated which
in turn can be used for the calculation of
equilibrium constant K.
 Numericals
 Q1.Calculate the electrode potential of a copper wire
dipped in 0.1M Cu SO4 solution at 25 C . The standard
0

electrode potential of copper is 0.34 V ?

 Solution
The electrode reaction :
Cu2+ + 2e- Cu , n=2
Applying Nernst Equation:
0.0591 1
E = E0 - --------- log ------- [Cu(s)]=1
2 [Cu2+]
0.0591 1
E = 0.34 - --------- log -------
2 0.1
= 0.34 – 0.02955
= 0.31045 V
 NUMERICALS
Q2. Write the Nernst equation & emf of the following
cell at 298 k:
i) Mg(s) / Mg2+(0.001M) Cu2+ (0.0001)/Cu (s)
Given E0 Mg2+ /Mg = -2.37 v ,
E0 Cu2+/ Cu = +0.34 v
Solution:
 Solution
Applying Nernst Equation:
0.0591 [Mg2+]
E = E0 - --------- log ---------------
2 [Cu2+]
0.0591 10 -3
E = 0.34 –(-2.37) --------- log ------- = 2.71-
0.02955 =2.68 V.
2 10 -4
 ii) Fe (s) /Fe2+(0.001) M H+ (1M) /H2 (g)
(1 bar) /Pt (s).
Given E0 Fe2+/Fe = -0.44v
Solution :
The electrode reactions & overall cell reactions are:
Fe(s)  Fe2+(aq) + 2e- (at anode)
2H+ + 2e-  H2 (g) ( at cathode )
-------------------------------------------------
Fe (s) 2H+  Fe2+ (aq)+ H2 (g) [over all reaction]
Applying Nernst Equation:
0.0591 [Fe2+] 0.0591 0.001
E = E0 - --------- log --------------- = 0.44 - ------------log --------
2 [H+]2 2 (1) 2

= 0.44 +0.0885
=0.5285V
 Numericals
iii).Pt (s) Br2 (l) Br- (0.01M) H+ (0.030M ) H2 (g)(1bar)
Pt(s)
Solution :
Since Br2 is liquid , Pt is acting as electrode,
Cell reactions are:
2Br-  Br2 + 2e-
2H+ + 2e-  H2
-------------------------------------------------------
2Br- + 2H+  Br2 + H2
Applying Nernst Equation:
0.0591 1
E = E0 - --------- log -------
2 [Br-]2 [ H+]2
0.0591 1
=(0- 1.08) - --------- log -------------------
2 (0.01)2 (0.030)2
= -1.08- 0.208
= - 1.288V
[NOTE: The given reaction is not feasible. Thus ,oxidation will occur at the hydrogen electrode &
reduction on the Br2 electrode and E cell = 1.288V.]