NEEHAR MEERA NATIONAL SR.

SECONADARY SCHOOL ALIGARH

SUBJECT: CHEMISTRY
TOPIC: ELECTROCHEMISTRY
SUBMITTED BY: DEEPAK KUMAR
CLASS: XII-A
SUBMITTED TO: MISS RUCHI
VARSHNEY
CERTIFICATE
This is to certify that DEEPAK KUMAR,
a student of class XII-E of Science of
Neehar Meera National Senior
Secondary School Aligarh ,has
completed the chemistry project under
the guidance of Miss Ruchi Mam
during the year 2023-2024 in partial
fulfilment of chemistry practical
examination conducted by CBSE, New
Delhi.

Signature of external examination Signature

of internal examination

Principal’s signature
 ACKNOWLEDGEMENT

I would like to express my special thanks of gratitude to

my
School Neehar Meera National Senior Secondary
School,Aligarh, as well as our principal Mrs Kalplata
Chandrahas and my subject teacher Miss Ruchi
Varshney
who gave me the golden opportunity to do a project on
the
topic Electrochemistry which also helped me in doing
lots
of research and came to know about so many things.
I am very thankful to them.
CONTENT
Introduction
1 Galvanic cell or Voltaic cell
1.1 Use of galvanic cell
1.2 Salt Bridge
1.3 Shorthand notation for galvanic cells
1.4 Half cell potential/Electrode potential
1.5 Free energy changes for a cell reaction
1.6 Cell Potential
1.7 Nernst equation
ELECTROCHEMISTRY:-
Introduction
Electrochemistry is 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. The subject is of importance both for
theoretical and practical considerations. A large
number of metals, sodium hydroxide, chlorine, fluorine
and
many other chemicals are produced by
electrochemical methods. Batteries and fuel cells
convert
chemical energy into electrical energy and
are used on a large scale in various instruments and
devices. Therefore, study of electrochemistry is
important for creating new technologies that are eco
friendly.
The transmission of sensory signals
through cells to brain and vice versa and communication
between the cells are known to have
electrochemical origin. Electrochemistry, is therefore, a
very
vast and interdisciplinary subject.

Electrochemical cell
If a metal electrode is immersed in an aqueous solution
containing cations of that metal, an
equilibrium that leads to formation on the electrode and
configuration of electrode and solution
is called a half-cell. Two half-cells can be combined to
form
an electrochemical cell.
Electrochemical cells can be used to determine the
equilibrium constant for the cell
reaction.Electrochemical cells can also be used to
provide power, in
which case they are called batteries.
Electrochemical cells in which the reactants can be
supplied
continuously are called fuel cells.
Electrochemical cell are of two types
Galvanic cells or Voltaic cell
A spontaneous chemical reaction
generates an electric current.

Electrolytic cell
An electric current drives a
non-spontaneous reaction.
1.Galvanic Cell or Voltaic Cell
A galvanic cell is an electrochemical cell that converts
the
chemical energy of a spontaneous

redox reaction into electrical energy. In this device the

Gibbs
energy of the spontaneous redox
reaction is converted into electrical work which may be
used
for running a motor or other
electrical gadgets like heater, fan, geyser, etc.

1.1 Use of galvanic cell

Anode
Some metals (which are reactive) are found to have
tendency to go into the solution
phase when these are placed in contact with their ions
or
their salt solutions.
For example: Zn rod is placed in ZnSO4 solution.
If a Zn electrode is partially immersed in an aqueous
solution of ZnSO4, an equilibrium
is established between Zn(s) and Zn2+(aq) as a small
amount of the Zn goes into solution as Zn2+(aq) ions as

depicted in above figure. Zn(s) = Zn2+ +2e-

However, the electrons remain on the Zn electrode.

Therefore, a negative charge builds

up on the Zn electrode, and a corresponding positive
charge
builds up in the surrounding
solution. This charging leads to a difference in the
electrical
potential between the
electrode and the solution, which we call the half-cell
potential or electrode potential.
This particular electrode is known as anode.• On anode
oxidation will take place. (release of electrons).
• It acts as source of electrons.
• It is negative polarity.
Some metals (Cu, Ag, Au etc.,) are found to have the
opposite tendency i.e., when placed
Cathode
in contact with their aqueous ions, the ions from the
solution
will get deposited on the metal rod.
The following equilibrium will be established:
Cu2+ + 2e- = Cu(s).
So rod will have deficiency of electron (positive charge).
Extra negative charge will
surround this positively charged rod and form double
layer.
An electrical double layer is
developed in the system and hence a potential
difference is
created between the rod and the solution which is
known as
half cell potential or electrode potential. This will be
known
as cathode.
• At cathode reduction will take place. (gain of electrons
will
take place)
• It acts as sink of electron.
• Positive charge is will be developed on cathode

Anode:
(Is where oxidation occurs
Is where electrons are produced.
Has a negative sign)
Cathode:
(Is where reduction occurs
Is where electrons are consumed.
Has a positive sign)
Half-cell potentials cannot be measured directly. They
are
measured relative to one another rather than absolutely.
To
understand how this is done, it is useful to consider an
electrochemical cell, which consists of two half-cells,
such
as the one shown figure. This particular cell is known as
the
Daniell cell, on the left, a Zn electrode is immersed in a
solution of ZnSO4(aq). The solute is completely
dissociated
to form Zn(aq) and SO42- (aq). On the right, a Cu
electrode
is immersed in a solution of CuSO4, which is completely

dissociated to form Cu2+(aq) and SO42− (aq) . The two

half-
cells are connected by an ionic conductor known as a
salt

bridge. The salt bridge consists of an electrolyte such as

KCl
suspended in a gel. A salt bridge allows current to flow
between the half-cells while preventing the mixing of the
solutions. A metal wire fastened to each electrode
allows the
electron current to flow through the external part of the
circuit.

1.2 Salt bridge

A salt bridge is a U shaped inverted tube that contains a
gel
permeated with an inert electrolyte. Generally tube is
filled
with a paste of agar-agar powder with a natural
electrolyte/
generally not common to anodic/cathodic compartment
with
porous plugs at each mouth of tube. The ions of the
inert
electrolyte do not react with other ion in the solution and
the
ions are not oxidised or reduced at the electrodes.The
electrolyte in salt bridge should be such that speed of
it's
cation equals speed of it's anion in electrical field. For
that
charge and sign of the ions should be almost equal i.e.
Mobility of cation = Mobility of anion KCl is generally
preferred but KNO3 or NH4NO3can also be used.
• If Ag+, Hg22+, Pb2+, Tl+ ions are present in a cell then
in salt
bridge KCl is not used because there can be formation
of
precipitate of AgCl, Hg2C2,l PbCl2 or TlCl at mouth of
tube
which will prevent the migration of ions and its
functioningwill stop.

Functions of Salt Bridge

(i) It connects the solution of two half cell to complete
the
circuit.
(ii) It minimises the liquid junction potential. The
potential
difference between the junction of two liquids. (Liquid-
Liquid
Junction Potential : The potential difference which
arises
between two solutions (during the progress of reaction)
when in contact with each other.)
(iii) It maintains the electrical neutrality of the solution in
order to give continuous
flow or generation of current.
"The simultaneous electrical neutrality of the anodic
oxidation chamber and
cathodic reduction chamber is due to same mobility or
velocity of K+

and NO3
ions taken into salt bridge.
(iv) If the salt bridge is removed then voltage drops to
zero.
(v) It prevents mechanical mixing of two electrolytic
solution.
1.3 Shorthand Notation for Galvanic Cells
We require two half cells to produce an electrochemical
cell,
which can be represented
by following few rules;
• The anode half-cell is always written on the left
followed on
the right by cathode
half cell.

• The separation of two phases (state of matter) is

shown by
a vertical line.
• The various materials present in the same phase are
shown together using
commas.
• The salt bridge is represented by a double slash (||).
• The significant features of the substance viz. pressure
of a
gas, concentration of
ions etc. are indicated in brackets immediately after
writing
the substance.
• For a gas electrode, the gas is indicated after the
electrode
for anode and before
the electrode in case of cathode. (i.e Pt/H2/H+ or
H+/H2/Pt)

Cu(s) | Cu2+ (aq. CH) || Cl | Cl2 (P atm) | Pt (s)

1.4 Half cell potential/ Electrode Potential

The potential difference developed between metal
electrode
and its ions in solution is known as electrode potential.
The potential difference developed between metal
electrodes and the solution in standard conditions (i.e.
1M
concentration of its ions at 1 bar pressure and at a
particular
temperature) is known as standard electrode potential.
According to convention, standard reduction potentials
are
also called standard electrode potentials.

1.5 Free Energy Changes for Cell Reaction

The free energy change

G (a thermochemical quantity)

and the cell potential

E(an electrochemical quantity) both measure the driving
force of a chemical reaction.
The values of

G and E are directly proportional and are

related by the equation,

G = -nFE
where n = Number of moles of electron transferred in
the
reaction.

F = Faraday constant = 96485 C/mole e-

1.6 Cell potential
The cell potential is the difference between the
electrode
potentials (reduction
potentials) of the cathode and anode. It is called the cell
electromotive force (emf) of
the cell when no current is drawn through the cell.
The emf of the cell or cell potential can be calculated
from
the values of electrodepotential of the two half cell
constituting the cell. The following three method are in
use:
(i) When oxidation potential of anode and reduction
potential
of cathode are taken
into account:Eo
cell = oxidation potential of anode + reduction potential
of
cathode
= Eox (anode) + Ered (cathode)
• In standard conditions
Eo cell = SOP of anode + SRP of cathode
Eo cell = Eo cell (anode) +Eo cell (cathode)
(ii) When reduction potential of both electrodes are
taken
into account :
Ecell = Reduction potential of cathode -Reduction
potential of
anode
= Ered (cathode)- Ered (anode)
• In standard conditions
E0cell = SRP of cathode + SRP of anode
Eocell = Eored (cathode) + Eored (anode)
E°cell is intensive property so on multiplying/Dividing
cell
reaction by any number, the E°cell value would not
change.

1.4.1 Measurement of Electrode Potential

The potential of individual half-cell cannot be measured.
We
can measure only the difference between the two half-
cell
potentials that gives the emf of the cell.If we arbitrarily
choose the potential of one electrode (half-cell) then
that of
the other can be determined with respect to this.
According
to convention, a half-cell called standard hydrogen
electrode
(Reference electrode) is assigned a zero potential at all
temperatures corresponding to the reaction
2H+ (aq, 1M) + 2e-→ H2 (g, 1 bar) Eo

H+/H2 = 0V

H2(g, 1bar) ⎯→ 2H+ (aq, 1M) + 2e. Eo

H2/H+ = 0V

0
H /H E + = 0 V
•delfG [H+ (aq.)] = 0
The standard hydrogen electrode consists of a platinum
electrode coated with platinum black. To achieve
equilibrium
on a short timescale, this reaction
2H+ + 2e-→ H2 is carried out over a platinum black
catalyst
electrode.The electrode is dipped in an acidic solution
and
pure hydrogen gas is bubbled through it. The
concentration
of both the reduced and oxidised 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.
At 298 K, the emf of the cell, standard hydrogen
electrode
with second half-cell constructed by taking standard
hydrogen electrode as anode (reference half-cell)
and the other half-cell as cathode, gives the reduction
potential of the other half-cell. If the concentrations of
the
oxidised and the reduced forms of the species in the
right
hand half-cell are unity, then the cell potential is equal to
standard electrode potential,

Eocell = (E0ox)SHE + (E0red)ELECTRODE

Eocell = 0 +(E0red)ELECTRODE =(E0red)ELECTRODE
The measured emf of the cell:
Pt(s) | H2(g, 1 bar) | H+ (aq, 1 M) || Cu2+ (aq, 1 M) | Cu
is 0.34 V and it is also the value for the standard
electrode
potential of the half-cell corresponding to the reaction:
Cu2+ (aq, 1 M) + 2e- → Cu(s)
Similarly, the measured emf of the cell:
Pt(s) | H2(g, 1 bar) | H+ (aq, 1 M) || Zn2+ (aq, 1 M) | Zn
is 0.76 V corresponding to the standard electrode
potential
of the half-cell reaction:
Zn2+ (aq, 1 M) + 2e-→ Zn(s)
Electrode Reaction SRP(at 298K)
Li Li+ + e → Li(s)

-3.05 V
K K+ + e → K (s) -2.93 V
Ba
Ca Ca+2 + 2e → Ca(s) -2.87 V
Na Na+ + e → Na(s) -2.71 V
Mg Mg+2 + 2e → Mg(s) - 2.71 V
Al
Electrolytes(H2O) H2O(l) + e → H2 + OH - 0.828 V
Zn Zn+2 + 2e → Zn(s) - 0.76 V
Cr Cr+3 + 3e → Cr(s) - 0.74 V
Fe Fe2+ + 2e- → Fe -0.44 V
Cd Cd+2 +2e → Cd(s) -0.41 V
Co
Ni Ni+2 + 2e → Ni(s) -0.24 V
Sn Sn+2 + 2e → Sn(s) -0.14 V
Pb Pb+2 + 2e → Pb(s) -0.13 V
H2 2H+ + 2e → H2(g) 0.00V
Cu Cu2+ + 2e → Cu(s) 0.34 V
I2
Fe Fe3+ + e → Fe2+ 0.77 V
Hg Hg2

2+ + 2e- → Hg(l) 0.79 V

Ag Ag+ + e → Ag 0.80 V
Hg Hg2+ → Hg(l) 0.85 V
Br2 Br2 + 2e → 2Br 1.06 V

*L

1.4.2 Calculation of Electrode Potential of unknown

electrode with the help of given
(two) electrode.
(i) Obtain the reaction of the 3rd electrode with the help
of
some algebraic
operations on reactions of the given electrodes.
(ii) Then calculate delG° of the 3rd reaction with the help
of
some algebraic operations of delGo of 1st and 2nd
reactions.
(iii) Use delGo = -nFEo

elec. to calculate unknown E.P.

0 cell E is intensive property so if we multiply/divide
electrode reaction by any number the 0 cell E value
would
not changed
i.e. Zn2+ + 2e- → Zn(s) E° = 0.76 V
Multiply by 2 2Zn2+ + 4e- → 2Zn(s) E° = 0.76 V (remain
same)

1.7 Nernst Equation

Cell potentials depend on temperature and on the
composition of the reaction mixtures.
It depends upon the concentration of the solute and the
partial pressure of the gas, if
any. The dependence upon the concentration can be
derived from thermodynamics.
From thermodynamics
delG = delG° + RT ln Q
nFE = nFE° + 2.303 R T log Q
E = E° (-2.303RT/nF) log Q
Take T = 298 K , R = 8.314 J/mol K, F = 96500 C
Now we get, E = E°- (0.059/n) log Q.
Where n = number of transferred electron, Q = reaction
quotient
• Nernst equation can be used to calculate cell
potentials
for non standard conditions also.
• Nernst equations can be applied to half cell reactions
also.
Applications of Nernst equation
1.5.1 Nernst Equation for Electrode Potential
Mn+(aq) + ne = M(s)
ERed = Eo

red -(RT/nF) ln[M(s)/Mn+]

ERed = Eo

red -2.303(RT/nF) log[M(s)/Mn+]

at 298K, ERed = ERed- (0.059/n) log[1/Mn+]
• Hydrogen Electrode
H2(g)= 2H+(aq) + 2e
E = E0 0.0591/2 log[(H+)2/PH2]
• Metal-metal soluble salt electrode.
Zn2+ + 2e → Zn(s)
ERed = Eo

red − (2.303RT/nF) log[1/Zn+2] at 298K

ERed = Eo

red -(0.059/2) log[1/Zn+2]

• Gas-electrode Hydrogen electrode.
2H+ + 2e → H2(g)
ERed = Eo

red −(0.059/2) log[PH2/[H+]2

• Redox electrode
4H2O + Mn2+ → MnO4− + 8H+ + 5e
Eox = Eox
o − (0.059/5) log{[MnO4−][H+]8}/[Mn2+]

Bibliography

Websites: unacademy.com
Self notes