CH 4

Concept of Electrochemistry

By
Dr.Vaishali Agme
 Electrochemistry
 Study of generation of electricity from the
energy released during chemical
reaction.
Use of electrical energy to carry out chemical
reaction that do not proceed spontaneously.
It helps to use or generate ecofriendly
technology.

Slide 2
What is electrochemistry in
chemistry?
Electrochemistry is the branch of
chemistry concerned with the
What is the principle of
electrochemistry?
Electrochemical cells are systems which
transfer energy of chemical reactions into
electrical energy.
Both half-cells can be immersed in the
same or in different
electrolytes.
Two half-cells in different electrolytes
must be connected ionic via an electrolyte
bridge or a salt bridge.
Compounds like
• Sodium
• Magnesium
• Many of chemical substances like NaOH
• Gasses like Cl2 and F2.
• Can be produced by electrochemical
methods.

Slide 5
Devices converts chemical energy
to electrical energy

Slide 7
 Electrolysis
• Electrolysis: is the process in which electrical
energy is used to drive a non spontaneous
chemical reaction.

• An electrolytic cell is an apparatus for carrying

out electrolysis.

• Processes in an electrolytic cell are the reverse

of those in a galvanic cell.
Slide 8
Extraction of Sodium from NaCl
 Electrolysis
• Electrolysis of Water: Requires an electrolyte
species, that is less easily oxidized and reduced
than water, to carry the current.

• Anode: Water is oxidized to oxygen gas.

2 H2O(l)  O2(g) + 4 H+(aq) + 4 e–

• Cathode: Water is reduced to hydrogen gas.

4 H2O(l) + 4 e–  2 H2(g) + 4 OH–(aq)
Slide 11
 Redox Reactions
Redox reactions are those involving the oxidation
and reduction of species.

OIL – Oxidation Is Loss of electrons.

RIG – Reduction Is Gain of electrons.

Oxidation and reduction must occur together.

They cannot exist alone.
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 Redox Reactions
• Oxidation Half-Reaction: Zn(s)  Zn2+(aq) + 2 e–.
• The Zn loses two electrons to form Zn2+.

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 Redox Reactions
• Reduction Half-Reaction: Cu2+(aq) + 2 e–  Cu(s)
• The Cu2+ gains two electrons to form copper.

Slide 15
 Redox Reactions
• Overall: Zn(s) + Cu2+(aq)  Zn2+(aq) + Cu(s)

Slide 16
Slide 21
 Electrochemical Cells
• Electrodes: are usually metal strips/wires connected
by an electrically conducting wire.
• Salt Bridge: is a U-shaped tube that contains a gel
permeated with a solution of an inert electrolyte.

• Anode: is the electrode where oxidation takes

place.

• Cathode: is the electrode where reduction takes

place.

Slide 22
 Cell notaion / Electrochemical Cells
• Convention for expressing the cell:
Anode Half-Cell || Cathode Half-Cell
Electrode | Anode Soln. || Cathode Soln. | Electrode
Zn(s) | Zn2+ (1 M) || Cu2+ (1 M) | Cu(s)
Pt(s) | H2 (1 atm) | H+ (1 M) || Fe3+(aq), Fe2+(aq) | Pt(s)

• Electrons flow from anode to cathode. Anode is

placed on left by convention.

Slide 23
 Electrochemical Cells
• The standard potential of any galvanic cell is
the sum of the standard half-cell potentials for
the oxidation and reduction half-cells.

E°cell = E°oxidation + E°reduction

• Standard half-cell potentials are always
quoted as a reduction process. The sign must
be changed for the oxidation process.
Slide 26
 Electrochemical Cells
• The standard half-cell potentials are
determined from the difference between two
electrodes.

• The reference point is called the standard

hydrogen electrode (S.H.E.) and consists of a
platinum electrode in contact with H2 gas (1
atm) and aqueous H+ ions (1 M).

• The standard hydrogen electrode is assigned an

arbitrary value of exactly 0.00 V.
Slide 27
 Types of Electrochemical Cells
1. Voltaic / Galvanic Cell
2. Electrolytic Cell

Slide 28
Slide 30
A Galvanic cell converts chemical energy into An electrolytic cell converts electrical energy
electrical energy. into chemical energy.
Here, the redox reaction is spontaneous and is The redox reaction is not spontaneous and
responsible for the production of electrical electrical energy has to be supplied to initiate
energy. the reaction.

The two half-cells are set up in different Both the electrodes are placed in a same
containers, being connected through the salt container in the solution of molten electrolyte.
bridge or porous partition.

Here the anode is negative and cathode is the Here, the anode is positive and cathode is the
positive electrode. The reaction at the anode is negative electrode. The reaction at the anode is
oxidation and that at the cathode is reduction. oxidation and that at the cathode is reduction.

The electrons are supplied by the species The external battery supplies the electrons. They
getting oxidized. They move from anode to the enter through the cathode and come out through
cathode in the external circuit. the anode.
Slide 31
 Electrolytic Cell
• Electrolytic cells are used for all kinds of things:
electroplating metals, recharging a battery, and
separating pure metals from metallic
compounds.
• When electrolytic cells are used to separate
chemical compounds, the process is known as
electrolysis.

Slide 32
Slide 33
Charging smart phone

Slide 34
 Electrolytic cells are used for
are used for all kinds of
things:
• electroplating metals,
• recharging a battery, and separating pure
metals from metallic compounds.
• When electrolytic cells are used to separate
chemical compounds, the process is known
as .

Slide 35
How are electrolytic cells used in real life?
Electrolytic cells are used for all kinds of things:
electroplating metals, recharging a battery, and
separating pure metals from metallic
compounds.
When electrolytic cells are used to separate
chemical compounds, the process is known as
electrolysis.

Slide 36
• Electrolytic cells can be used to
produce oxygen gas and
hydrogen gas from water by
subjecting it to electrolysis.
• These devices can also be used
to obtain chlorine gas and
metallic sodium from aqueous
solutions of sodium chloride
(common salt).
• Another important application
of electrolytic cells is in
electroplating.
Voltaic Cell
• voltaic cell is an that uses
a chemical reaction to produce electrical
energy.
The important parts of a voltaic cell:
• The anode is an electrode where oxidation
occurs.
• The cathode is an electrode where reduction
occurs.
• A salt bridge is a chamber of electrolytes
necessary to complete the circuit in a voltaic
cell. Slide 39
• The oxidation and reduction reactions are
separated into compartments called half-
cells.
• The external circuit is used to conduct the
flow of electrons between the electrodes of
the voltaic cell and usually includes a load.
• The load is the part of the circuit which
utilizes the flow of electrons to perform
some function.

Slide 40
Slide 41
 Uses of voltaic Cell
• Voltaic cells are typically used as a source of
electrical power.
• By their nature, they produce direct current. A
battery is a set of voltaic cells that are
connected in parallel.
• For instance, a lead–acid battery has cells with
the anodes composed of lead and cathodes
composed of lead dioxide.

Slide 42
Electrochemical Series
The electrochemical series helps to pick out substances that are
good oxidizing agents and those which are good reducing agents.
In this, species which are placed above hydrogen are more
difficult to be reduced and their standard reduction potential
values are negative.
 is actually table that lists up the electrode potentials( reduction
potential or oxidation potential) of different chemical species.
Usually, we use reduction potentials for the chemical species.
This list help us compare different chemical substances based on
their reduction potential.
Predicting Liberation of H2 gas from acids by metals: All metals
having negative electrode potential show greater tendency of
losing electrons as compared to hydrogen.

Slide 44
The electrochemical series is built up by
arranging various redox equilibria in
order of their standard electrode
potentials (redox potentials).
The most negative E° values are placed
at the top of the electrochemical series,
and the most positive at the bottom.
Electrochemical series also sometimes referred
to as activity series is a list that describes the
arrangement of elements in order of their
increasing electrode potential values.
The series has been established by measuring
the potential of various electrodes versus
standard hydrogen electrode (SHE).
The electrochemical series helps to pick out
substances that are good oxidizing agents and
those which are good reducing agents.
Electrochemical Cells

Slide 48
Slide 49
Standard Electrode Potential
In electrochemistry,
standard electrode potential is defined as “the measure the
individual potential of reversible electrode at standard state with
ions at an effective concentration of 1mol dm-3 at the pressure of 1
atm”.

Electricity is generated due to electric potential difference

between two electrodes.
The convention is to designate the cell so that the oxidised form is
written first.
For example,

Pt(s)|H2(g)H+(aq)|Zn2+(aq)|Zn(s)
The e.m.f. of this cell is -0.76 V and the standard electrode
potential of the Zn2+|Zn half cell is -0.76 V.
Slide 50
Slide 51
Slide 52
What is Nernst Equation?
• The Nernst equation provides a relation between the cell
potential of an electrochemical cell, the standard cell
potential, temperature, and the reaction quotient.
• Even under non-standard conditions, the cell potentials of
electrochemical cells can be determined with the help of the
Nernst equation.

• The Nernst equation is often used to calculate the cell

potential of an electrochemical cell at any given
temperature, pressure, and reactant concentration.
• The equation was introduced by a German chemist named
Walther Hermann Nernst.
1. This equation was named after a German physicist
Walther Nernst.
2. The Nernst Equation empowers the assurance of cell
potential under non-standard conditions and relates the
measured cell potential to the reaction quotient and
permits the exact measurement of equilibrium constants.
Let us consider an electrochemical reaction of the following
type:
aA +bB --> cC + dD
Nernst equation for this can be written as follows:
The above equation implies that the value of increases with the
increase in the concentartion of Cu2+ ion increases and decrease
in the concentration Zn2+
Putting the values of R, F at T= 298 K.
the equation becomes
 Nernst equation
Nernst equation is a general equation that
relates the Gibbs free energy and cell
potential in electrochemistry.
It is very helpful in determining cell
potential, equilibrium constant etc.

Slide 57
Nernst Equation for Single Electrode Potential
Ecell = E0 – [RT/nF] ln Q
Where,
Ecell = cell potential of the cell
E0 = cell potential under standard conditions
R = universal gas constant
T = temperature
n = number of electrons transferred in the redox reaction
F = Faraday constant
Q = reaction quotient
The calculation of single electrode reduction potential (Ered) from
the standard single electrode reduction potential (E°red) for an
atom/ion is given by the Nernst equation.
T= 298K:

E = Eo − (0.0592V/n) log10Q
At standard temperature,
T = 298 K,
the 2.303RTF, term equals 0.0592 V.
Hence,
 Nernst equation is a general equation that relates the Gibbs
free energy and cell potential in electrochemistry.
 It is very helpful in determining cell
potential, equilibrium constant etc.

Slide 63
1) Write the cell reaction and calculate the standard potential
of the cell.
Ni(s) I Ni 2+ (1M) II Cl- (1M) I Cl2 (g, 1 atm ) I Pt

E0Cl2 = 1.36 V and E0 Ni = -0.25 V

Solution
Cell reaction :
At anode : Ni -----------------> Ni 2+ + 2e- (Oxidation)
At cathode : Cl2 + 2e- ---------> 2Cl- ( Reduction)
Net cell reaction :
Ni + Cl2 ---------> Ni 2+ + 2Cl-

E 0
Cell = E 0
Cathode - E 0
anode
E0 Cell = 1.36 -(-0.25)
1) Write the cell reaction and calculate the standard potential
of the cell.
Pb(s) I Pb 2+ (1M) II KCl (sat) I Hg2Cl2 I Hg
E0anode - 0.126V and E0 cathode = 0.242 V
Solution
Cell reaction :
At anode : Pb -----------------> Pb 2+ + 2e- (Oxidation)
At cathode : Hg2Cl2 + 2e- ---------> 2Hg +Pb 2+ +2Cl- ( Reduction)
Net cell reaction :
Pb+ Hg2Cl2 ---------> 2Hg +Pb 2+ +2Cl-
E0 Cell = E0 Cathode - E0 anode
E0 Cell = 0242 -(-0.126)
1) Write the cell reaction and calculate the standard potential
of the cell.
Sn(s) I Sn 2+ (0.025M) II Ag+(0.015M) I Ag(s)
E0Sn = - 0.136V and E0 Ag = 0.799 V
Solution
E0 Cell = E0 Cathode - E0 anode
= ( 0.799-(-0.136) = 0.935 V
E = Eo − (0.0592V/n) log10Q

= 0.935- 0.059/2 log 0.025/(0.015)2

Calculate the emf of the cell in which the following reaction
takes place: Ni(s) + 2Ag+ (0.002 M) → Ni2+ (0.160 M) + 2Ag(s).
Given that Eøcell = 1.05 V.
Solution:
By using Nernst equation

1.05 - 0.02955 log 4 × 104

= 1.05 - 0.02955 (log 10000 + log 4)

= 1.05 - 0.02955 (4 + 0.6021)

 Corrosion

Oxidation: Fe(s)  Fe2+(aq) + 2 e–

Reduction: O2(g) + 4 H+(aq) + 4 e–  2 H2O(l)
Overall: 2 Fe(s) + O2(g) + 4 H+(aq)  2 Fe2+(aq) + 2 H2O(l)
Slide 69
 Corrosion
• Galvanizing: is the coating of iron with zinc. Zinc is
more easily oxidized than iron, which protects and
reverses oxidation of the iron.

• Cathodic Protection: is the protection of a metal

from corrosion by connecting it to a metal (a
sacrificial anode) that is more easily oxidized.

• All that is required is an electrical connection to the

sacrificial anode (usually magnesium or zinc).

Slide 70
 Corrosion
• Cathodic Protection with Magnesium Anode

Slide 71
 Corrosion
Cathodic Protection with Zinc Layer

Slide 72
 Electrolysis Applications
• Manufacture of Sodium (Downs Cell):

Slide 73
 Electrolysis Applications
• Manufacture of Cl2 and NaOH (Chlor–Alkali):

Slide 74
 Electrolysis Applications
• Manufacture of Aluminum (Hall– Heroult):

Slide 75
 Electrolysis Applications
• Electrorefining and Electroplating:

Slide 76