ELECTROCHEMISTRY

ELECTROCHEMISTRY

X
Munil Sir [Link]
 ELECTROCHEMISTRY
Definition- In electrochemistry we study about conversion of chemical energy
into electrical energy and use of electrical energy for non spontaneous
chemical changes

Electrochemical Cell
Electrochemical Cell

Definition- It is a device which Observation- Electrons starts flowing from Zn

converts Chemical Energy into electrode to Cu electrode and Zinc electrode get
Electrical Energy dissolving in the process while Cu electrode gets
plating out
Galvanic Cell
Galvanic Cell

Definition- It is a device which generates current in account of chemical

reaction taking place in it

Daniel Cell
Daniel Cell

Definition- It is a type of Galvanic cell consists of a

zinc rod in a zinc sulphate solution and a copper rod in
a copper sulphate solution.

Function
Function

A cell has two half-cells. In each half-cell, either

oxidation or reduction happens. Oxidation occurs at
the anode, and reduction occurs at the cathode. Half
Ha lf Ce
Cellll is
is aa
com
co mbibina
natio
tionn ofof anan

Half Cell Reactions electro

elect rode
de whwhich
ich is is di
dipp
pped
ed
in it’
it’ss ow
ownn so
solu
→
in
lutio
tionn
Zn(s) Zn²⁺(aq) + 2e⁻ Anode
Cu²⁺(aq) + 2e⁻ Cu(s)→ Cathode
Zn(s) + Cu²⁺(aq) → Zn²⁺(aq) + Cu(s) Overall reaction Tric
Tr ickk
LO
LOA AN
N-:
-: Le
Left
ft

The Electric Potential of 1.1 V is

Oxida
Oxidati
tion
on AAno
node
de
generated from cell if Conc. of Zn²⁺ Neg
Negat
ativ
ivee
and Cu²⁺ ions is 1 mole/ml
 ELECTROCHEMISTRY
Functioning of
Functioning of Cell
Cell in
in presence
presence of
of Ext.
Ext. Voltage
Voltage

Case -1 Applied voltage <Cell

1. e⁻ flow Zn to Cu
2. Current Cu to Zn
3. Zn loses it's weight
2+
4. Cu deposit at cathode

Case -2 Applied Voltage = Cell Voltage

1. No-flow of electron
2. No-flow of current
[Link]-Reaction of anode and cathode

Case -3 Applied voltage >Cell

1. e⁻ flow Cu to Zn
2. Current Zn to Cu
[Link] loses it's weight
4. Zn2+deposit at anode S.E.P
S.E.P

Elect
Ele ctro
rode
de Po
Potetent
ntial
ial is

Electrode Potential
Electrode Potential (E.P)
is

(E.P)
calle
ca lledd St
Stananda
dardrd Ele
Electctro
rode
de
Pote
Po tent
ntial
ial if
if me
meas asur
ured
ed at
at 11
atm
atm prpres
essusure
re ,, 25
25 CC te
temp
mp,,
When charge separates between the electrode metal and 1M
1 M co
conc
nc..
the solution, it creates a potential called electrode
potential.

E°cell= E° Reduction -E°Oxidation

Potential depended on E°cell= E° Cathode - E°Anode

1. Nature of the metal and its. 3. Temperature

2. Concentration of the ions in the solution

 ELECTROCHEMISTRY
Standard Hydrogen
Standard Hydrogen Electrode
Electrode (
( SHE)
SHE)

Its the device that measures the half cell electrode potential of cell

Condition to
Condition to measure
measure :
:

1. Pressure should be 1 atom /1 bar

2. Molarity should be I M.

Disadvantage of
Disadvantage of SHE
SHE :
:

1. I M HCL difficult to maintain

2. I bar pressure difficult to maintain
3. Easily get poisoned in the presence of small impurities.

Representation Electrochemical
Representation Electrochemical cell
cell

Zn+Cu²⁺ Zn²⁺+Cu Function of

Function of Salt
Salt Bridge
Bridge

1. Complete the electrical circuit by joining half cells

2. Maintain the neutrality of two half cells
Zn|Zn²⁺||Cu⁺²|Cu Representation
Salt Bridge
[
[

Anode Cathode
Half Cell, Half Cell,
Left Right
Salt Bridge

It is inverted U-tube joining two half cells

contains a saturated solution which is KCl and
KNO generally prepared in agar-agar and geltain
 ELECTROCHEMISTRY
NERNST Equation
NERNST Equation

SEP is measured in standard conditions but practically standard

conditions cannot be achieved so we use Nernst Eqn
where, R = 8.314 J/K
Ecell = E°cell - 2.303RT log Q 1F = 96500 C
nF n = total no. of electrons lost or gained

At Equilibrium condition
Qc =Kc E cell =0
0= E°cell -0.0591 logKc/n
E°cell = 0.0591 logKc /n
Kc = Equilibrium constant

Gibbs Free
Gibbs Free energy
energy

It is the maximum useful work obtainable from a system

o
G= -nFE G= -nFE F=96500 C/mol
Gibbs free Standard Gibbs
energy free energy n = no. of electron
G=0 {equilibrium }
G= negative {spontaneous }
lost or gained
G=positive { non- spontaneous } E= Emf of cell
Resistance
Resistance o
E= Standard E.P
It is the hindrance generated by the conductor or electrolyte

Resistivity
Resistivity

Conductivity
Conductivity

Conductance
Conductance Conductivity shows how well a solution conducts
It is reciprocal of Resistance electricity. It depends on the number of ions.
1
G= X =G X
 ELECTROCHEMISTRY
Cell Constant
Cell Constant

In electrochemistry, it describes the shape of a cell by showing the ratio

of the distance between the electrodes ('L') to their cross-sectional area
('A').
G= AL

|
Molar Conductivity
Molar Conductivity

Molar conductivity measures how well an electrolyte solution Molar conductivity

conducts electricity. It is found by dividing the solution’s
increases with
conductivity by the electrolyte’s molar concentration.
dilution but
Conductivity
decrease
Equivalent Conductivity
Equivalent Conductivity

Molar conductivity measures how well an electrolyte solution

conducts electricity. It is found by dividing the solution’s
conductivity by the electrolyte’s molar concentration.

Limiting Molar
Limiting Molar Conductivity
Conductivity

When the dilution is too much and concentration approaches

zero, the molar conductivity reaches a limiting value known as
limiting molar conductivity

Variation of
Variation of Limiting
Limiting Molar
Molar Conductivity
Conductivity

For weak electrolytes, dilution increases the degree of

dissociation, meaning more ions are formed. This leads to a
sharp (parabolic) increase in molar conductivity. In contrast,
strong electrolytes are already fully dissociated, so dilution
doesn't increase the number of ions. However, it reduces the
attraction between ions, making them move more freely, which
causes a slow increase in molar conductivity.
 ELECTROCHEMISTRY
° ° °
Kohlrausch law
Kohlrausch law
ΛAB=ΛA + Λ B
According to Kohlrausch's law, the limiting molar conductivity
of a weak electrolyte is the sum of the conductivities of its
anion and cation

Application of
Application of Kohlrausch
Kohlrausch law
law

1. Using Kohlrausch law of independent migration of ion, is possible

° °
to calculate Λmand Λ of individual ions .
2. It is possible to find the value of degree of dissociation and
°
dissociation constant after we found Λm and Λm .

Degree of
Degree of Dissociation
Dissociation Dissociation Constant
Dissociation Constant

Λm C α
2
α= K=
|

Λ°m

|
1- α
Electrolysis
Electrolysis

In electrolytic cell, electrical energy is used to carry out non spontaneous

chemical reaction. This process take place in a electrolytic cell is called
electrolysis

Faraday's law
Faraday's law

1st law
1st law 2nd law
2nd law

It state
It state that
that weight
weight of
of product
product
When the
When the same
same charge
charge passes
passes

during electrolysis
during electrolysis at
at electrode
electrode
through different
through different electrolytes
electrolytes

in series,
series, the
the mass
mass deposited
deposited is
is
is directly
directly proportional
proportional to
to the
the
in
is
proportional to
proportional to their
their
charge supplied
charge supplied
equivalent weights.
equivalent weights.

W Q ∝ W1 Z1
=
|
|

W=Zit W2 Z2
 ELECTROCHEMISTRY
Electrolytic cell
Electrolytic cell

When cell convert electrical energy to chemical

energy are called electrolytic cell

Batteries
Batteries

A battery contains one or more than one cell connected

in series. also it is an electrochemical cell which
converts chemical energy into electrical energy

Primary Batteries
Primary Batteries

Its is simply a battery which cannot be recharged

Leclanche Cell
Leclanche Cell

Anode : Zinc Container

Cathode : Carbon rod { surrounded by MnO + Carbon }
Electrolytes : ZnCl2 and NH4 Cl
_
RXn at Anode : Zn Zn + 2e
2+

_
Rxn at Cathode : MnO2 + NH4 + e MnO(OH) + NH
+
3

+ 2+
Overall Reaction : Zn+NH +MnO2 4 Mn2O3 +H2O + [Zn(NH3 )2 ]
Mercury Cell
Mercury Cell

Anode : Zn - Hg amalgam
Cathode : Paste of HgO and Carbon
Electrolytes : Paste of ZnO and KOH
_ _
RXn at Anode : Zn(Mg) + OH ZnO + H2O + e
_
Rxn at Cathode : HgO + H2O + e
_
Hg + OH

Overall Reaction : Zn(Hg) +HgO ZnO +Hg

 ELECTROCHEMISTRY
ELECTROCHEMISTRY
Secondary Batteries
Secondary Batteries

Its is simply a battery which can be recharged

Lead Storage
Lead Storage Battery
Battery Anode

Anode : Lead
Cathode : A grid of lead with of PbO2
Electrolytes : 30% of H2 SO solution by mass Negative plates:
_ lead grids filled with
RXn at Anode : Pb + SO4 2-
PbSO4 + e spongy lead
_
Rxn at Cathode : PbO2 + SO4 + 4H ++ e
2-
PbSO4 + H2O 38% sulphuric
acid solution
Positive plates:
lead grids filled
with PbO2

Overall Reaction : Pb + PbO2 + H2SO4 PbSO4 + H2O

Nickel Cadmium
Nickel Cadmium Battery
Battery

Anode : Cadmium
Cathode : A grid of NiO2
Electrolytes : KOH solution
_ _
RXn at Anode : Cd + OH Cd(OH)2 + e
_ _
Rxn at Cathode : NiO2 + H2O + e Ni(OH)2 + OH

Overall Reaction : Cd + NiO2 + H2O Cd(OH)2 + Ni(OH)2

Fuel Cell
Fuel Cell

It is a galvanic cell in which chemical energy from combustion of fuels like

methane, ethanol, hydrogen.

Fuel : Hydrogen and Oxygen

_ _
RXn at Anode : Cd + OH Cd(OH)2 + e
_ _
Rxn at Cathode : NiO2 + H2O + e Ni(OH)2 + OH
 ELECTROCHEMISTRY
ELECTROCHEMISTRY
Electrochemical Series
Electrochemical Series

When electrodes comes in contact with their ions arranged in a series of

increasing order of their SRP,this series is known as Electrochemical Series

Characteristics of
Characteristics of Electrochemical
Electrochemical Series
Series

1. The negative sign of SRP indicates that electrode when connected with SHE
behaves as anode, positive ones act as cathode

2. The elements which are place above hydrogen are good oxidising agent and
the lower ones are good reducing agent

Applications of
Applications of Electrochemical
Electrochemical Series
Series

1. The metal having high SRP value are more electronegative

2. Metals with low SRP value are highly reactive

3. Metals with low SRP can replace other metals from its salt

4. Elements having high SRP value are strong oxidising agent

 ELECTROCHEMISTRY
ELECTROCHEMISTRY
Corrosion
Corrosion

It is an electrochemical process in which a metal is oxidised to metal oxide

and forms a coating by losing an electron to oxygen

Anode : Point on metal where oxidation happens

Cathode : Point on metal where reduction happens
Electrolytes : KOH solution
_
Oxidation : Fe (s) Fe2+(aq) + 2e
Reduction : O2 (g) + 4H +(aq) + 4e- 2H2O (l)

Prevention of
Prevention of Corrosion
Corrosion

1. Barrier protection :- Metal can be protected by doing a coating of

barriers like paints, oil or grease
2. Galvanisation :- It is a process of protecting metal by doing coating of
Zinc on it
3. Electroplating :- It is a process of preventing corrosion thorough plating
the metal with the help of electricity

Product of
Product of Electrolysis
Electrolysis