ELECTROCHEMISTRY

 Electro chemistry is the branch of chemistry which deals with

transformation of electrical energy into chemical energy vice
versa.
 Electrochemistry serves as an interface between chemistry and
everyday life. When we switch on calculator, a computer, a radio,
start a car, use mobile phone , use a digital watch, and so on we
are depending upon the electrochemical reactions occurring in
the cells or batteries.
 A number of Electro chemical industries have been established
on the concept of electrochemistry:
 Electro refining(Cu), Electro plating(Ni, Cr, Au, Ag) ,Fused
electrolysis(Al, Mg, Na), Electrolytic furnacing (Alloy steels),
Chemical to electrical Conversion (batteries, fuel cells).
 Electrolyte:
A substance that ionizes when dissolved or
molten to produce an electrically conductive
medium is electrolyte.
Types:
 Strong electrolytes are highly ionized in
solution.
Ex: HCl, H2SO4, NaOH, KOH etc.
 Weak electrolytes are only feebly ionized
in solution.
Ex: H2CO3, CH3COOH, NH4OH etc.
Electrical Conductors:
The substances which allow the passage
of electric current are called as electrical
conductors.

These are of two types:

I. Metallic (or)Electronic Conductors
II.Electrolytic (or) ionic Conductors
Differences between metallic and ionic conductors:-
METALLIC CONDUCTORS IONIC CONDUCTORS
a. Conductance of these conductors is a. Conductance of these conductors is
due to flow of electrons. due to flow of ions.
b. During the conductance, there is no
change in chemical composition of b. During the conductance, there is a
conductor. change in chemical composition of
c. During the conductance, there is no conductor.
flow of matter. c. During the conductance, there is flow
d. Metallic conductance decreases with of matter.
rise of the temperature(because
resistance increases with d. Ionic conductance increases with rise
temperature). of the temperature (because ionization
e. No change of conductance with increases with temperature).
changing time. e. Change of conductance with changing
f. Metals, alloys, certain solid salts, time. Electrolytes like Acids (HCl, H2SO4,
amides.
and CH3COOH), bases (NaOH, KOH),
salts (NaCl, KCl).
 Electrical Conductance(C)
The tendency of a substance to allow
electric current (or) the reciprocal of
resistance is conductance.
1
C 
R

Units for conductance = ohm-1 (or) mho (or)

𝛀-1. In SI system =Siemens
It is expressed in three ways
pecific Conductance:
It is the reciprocal of specific resistance.

1 a
k  where    R
 l

l 1 l
Therefore k  k  C
a R a
l
a
is known as cell constant(x)

Cell constant for given cell with fixed electrodes (l/a)is a

constant.
Units for k are ohm–1cm–1 and SI units are S.m–1 ,where S is
Siemens
Equivalent conductance :
Equivalent conductance is defined as the conductance
of all the ions produced by one gram equivalent of an
electrolyte in a given solution of volume (V).
MOLAR CONDUCTANCE
The molar conductance is defined as the conductance of
all the ions produced by ionization of one mole of an
electrolyte when present in V ml of solution. It is denoted
by
Equivalent and molar conductance both increase with
dilution and reaches a maximum value at infinite
dilution.

 Increasing temperature reduces the resistance, there

by increasing conductance. Hence equivalent
conductance and molar conductance increases with
increasing of temperature.

Specific conductance decreases with increase in

dilution because with increasing of dilution , the no. of
ions present per centimeter cube of electrolyte
decreases.
 EMF:
 The potential difference between two electrodes is known as
electromotive force(EMF) cell potential.
 It can be expressed in terms of both reduction potential and
oxidation potential.
 Tendency to gain electron(reduction potential) at cathode
remains at higher potential. On the other hand , tendency to
lose electron(oxidation potential) at the anode remains at
higher potential
 In terms of reduction potential
E o Cell = E o cathode –E o anode
 In terms of oxidation potential
E o Cell = E o anode - E o cathode
 EMF of the total cell is equal to the sum of oxidation potential
and reduction potential of the right hand electrode minus left
hand electrode.
ECell = ER - EL
 Generally electrode potential refers to the reduction potential.
for example:
Potentials of Right Electrode is Cu+2 / Cu = 0.337V
Potentials of Left Electrode is Zn / Zn+2 = -0.763V
ECell = ER - EL
= 0.337-(-0.763)
= 0.337+0.763
= 1.1V
Applications of Nernst Equation:
• It can be used to study the effect of electrolyte concentration
on electrode potential

• Determination of unknown concentration of one species in a

cell is possible with the help of Nernst equation, provided Ecell
and concentration of other ionic species are known.

• The pH of a solution can be calculated from the measurement

of EMF and Nernst equation

• Nernst equation can also be used for finding the valency of

an ion or the number of electrons involved in the electrode
reaction.
Single electrode potential:-
The potential difference between metal and its salt solution,
when it is in contact with solution is called single electrode
potential.
Zn | ZnSo4 || CuSo4 | Cu
(Single electrode ) (Single electrode)
EMF = Reduction potentials of cathode – Reduction potentials
of anode
 However, in practices it is not possible to calculate single
electrode potentials. Because single electrode potentials
depends on concentration of ions and temperature. However,
these are changing during the cell reaction.
 The single electrode potential is measured by combining the
half-cell with standard electrode.
 Metal – Metal insoluble salt electrode(SCE)
 Calomel electrode is commonly used as secondary
reference electrode for potential measurements.
 SCE consists of a metal, an insoluble salt of the same metal a
solution of a soluble salt with common anion
 It consists of a glass tube with two side tubes each side.
 Mercury of high purity is placed at the bottom of the tube
and connected to the circuit by means of a Pt wire sealed
in glass tube.
 The surface of mercury is covered with a paste of calomel
(Hg2Cl2) and mercury.
 A solution of KCl is then placed over the paste.
 The calomel electrode is only used as reducing electrode.
The corresponding electrode reaction is
Hg2Cl2 + 2e-  2Hg + 2 Cl-

The Nernst equation will be

EHg2Cl2|Cl- = E0 Hg2Cl2|Cl- – 2.303RT/2F log [Cl-]2

= E0 Hg2Cl2|Cl- – 0.0591 log [Cl-] at 25 0C

 The potentials of calomel electrode depend on activity of Cl- ions.

 As the activity of Cl - increases the potentials decreases.

 For saturated KCl solution, electrode potential is 0.2415 V.

Quinhydrone electrode:-
This is a reversible redox electrode in the presence of
hydrogen ions.
Quinhydrone electrode is a 1:1 molar mixture of quinone
and hydroquinone.
The electrode consists of platinum rod dipped in a acid
solution which is saturated with quinhydrone.
Since the electrode potential of the Quinhydrone electrode
depends on conc.of H+ ions. So we can use in the determination of
pH value of the solutions.
The standard oxidation potentials of Quinhydrone electrode at
250C is 0.6994 volts.
Advantages:
•Easy to set up no need to remove air
•The equilibrium is achieved faster than the hydrogen gas electrode
•pH values of solutions containing reducible substances like Cu2+,
unsaturated acids can be measured, where hydrogen electrode
cannot be used
Limitations:
•Electrode cannot be used at pH values greater than 8
•The electrode fails in presence of strong oxidizing and reducing
agents (Fe+2 ,MnO2)
 D. Ion selective electrode(glass electrode)
 Ion –selective electrodes (ISE) have a membrane, which is
sensitive to a particular chemical ion present in the mixture.
 ISE have an ability to develop potential with that ion in the
mixture. From this potential, the conc. of selective ion in the
mixture is calculated.
 The glass electrode is made of a special glass of 22% Na2O, 6%
CaO and 72% SiO2.
 The glass electrode consists of a thin glass bulb filled with 0.1N
HCl and Ag wire coated with silver chloride (AgCl) immersed
in it. Here Ag/AgCl acts as an internal reference electrode. The
glass electrode represented as Ag/AgCl(S) /0.1M HCl/glass.
 When the glass electrode is immersed in another solution
whose PH value is to be determined, there develops a potential
between the two surfaces of the membrane. This is equal to
difference in PH value.
At 25 0C the Nernst equation is given by
EG = E0G - 0.0591 log [H+]

EG = E0G + 0.0591pH
For the determination of pH, an SCE electrode is immersed as a
reference electrode in the buffer solution of HCl.
The e.m.f. of the cell is given by

Ecell = ESCE – Eglass

 Ecell = 0.2422v – [E0G + 0.0591pH]

pH = 0.2422v – E cell - E0G

0.0591
 BATTERIES
 An electric battery is a device consisting of
one or more electrochemical cells that
convert stored chemical energy into
electrical energy.
 We may alternatively define a battery is an
electrochemical cell or often
electrochemical cells connected in a series,
that can be used as a source of direct
electric current at a constant voltage.
Types of batteries
Batteries are classified into three types.

1. Primary battery (primary cells)

2. Secondary battery (secondary cells)

3. Fuel cells (Flow battery)

 PRIMARY BATTERIES

Dry cell (Leclanche Cell)

 The Leclanché cell is a battery invented and patented by
the French Scientist Georges Leclanche in 1866.
 It is a cell without fluid component is perhaps the most
familiar of all batteries.
 The anode of the cell is Zinc container containing an
electrolyte consisting of NH4Cl, ZnCl2, MnO2 to which
starch is added to make it thick paste.
 A carbon rod (graphite) serves as a cathode, which is
immersed in the electrolyte in the centre of the cell.
Reactions:
At anode(Oxidation ):
Zn(s)  Zn+2(aq)+2e-
At cathode(Reduction):
2MnO2(s) + H2O + 2e-  Mn2O3(s) + 2OH –

The net cell reaction:

Zn(s) + 2MnO2(s) +H2O  Zn (OH)2+ Mn2O3
Side reactions
NH4+ + OH- NH3 + H2O

2NH3 + Zn+2 + 2Cl- [Zn(NH3) 2Cl2]

Dry cell is represented as
Zn/Zn+2,NH4+/MnO2/C
The nominal cell potential of dry cell is
about 1.5 volts.
Disadvantages:
When the current is drawn rapidly from it,
products build up on electrodes thereby
causing drop in voltage.
 Since the electrolytic medium is acidic, zinc
metal dissolves slowly, thereby the cell run
down slowly, even it is not in use.
Uses:
Dry cell finds an applications in flash lights,
transistor radios, calculators, etc……
Lithium battery
 Lithium is the lightest metal. The electrochemical properties of
lithium are excellent. These properties give Lithium the potential
to achieve very high energy.
 Lithium batteries are primary batteries in which lithium metal
(or) lithium compound acts as a Anode.
1. Lithium primary cell with Liquid cathode
2. Lithium primary cell with solid cathode
Liquid cathode cells:

Anode : Li
Cathode : SOCl2
Electrolyte : LiAlCl2

Anode : 4Li 4Li+ +4 e-

Cathode : 4Li+ + 4e- +2 SOCl2  4 LiCl + SO2 + S
Overall reaction : 4Li+ + 2SOCl2  4 LiCl + SO2 + S
 The discharging voltage is 3.3- 3.5 V.
Uses:
1. They are used for military and space
application.
2. used In Medicinal devices like neuro-
stimulators and drug delivery system.
3. They perform best in low current applications
and have a very long service life. For this
reason they are used in pacemaker(The
primary purpose of a pacemaker is to
maintain an adequate heart rate).
 Solid cathode (LiMnO2) cell:
Anode : Li
Cathode : MnO2
Electrolyte : propylene carbonate & 1,2-di-
methoxy ethane
Anode : Li Li+ + e-
Cathode : Li+ + e- + MnO2  LiMnO2
Li + MnO2  LiMnO2
 SECONDARY BATTERIES or ACCUMULATIRS
LEAD ACID BATTERY
Construction
 This battery consists of a number of spongy lead
anodes and a grid of lead dioxide coated on lead-
antimony alloy cathode.
 The electrode pairs separated by inert porus partitions
are kept immersed in the electrolyte sulphuric acid.
Discharging:
At Pb electrode: Pb(s) → Pb+2 + 2e-
Pb+2 + SO4-2 → PbSO4(s) ↓
At PbO2 electrode :
PbO2(s) + 2H+ (aq) + 2e- → Pb+2 + 2H2O(l)
Pb+2 + SO4-2 → PbSO4(s) ↓

The total reaction can be written:

Pb(s) +PbO2(s) + 4H+ +2SO4-2 →2PbSO4(s) +2H2O(l) +E

Charging
When both electrodes covered by PbSO4, cell
cease to function as voltaic cell. To recharge,
the reactions during discharge reversed by
passing external emf greater than 2V.
Cathode: PbSO4(s) +2e- → Pb(s) + SO4-2

Anode:PbSO4(s) + 2H2O(l) +2e- →PbO2(s) +4H+ +SO4-2

The total reaction can be written:

2PbSO4(s) + 2H2O(l) +E →Pb(s) + PbO2(s) +4H+ + 2SO4-2

Disadvantages
 If the cell voltages exceed 2.39V, the water breaks
down into H2 and O2 and may lead to explosion.
 Fumes from the acid solution may have a
corrosive effect on the area surrounding the
battery.
 These cells have a low life
 Applications:
 These cells are used for supplying current to electrical
vehicles, railway, mines, laboratories, cars , buses,
lorry,hospitals, automobiles, power stations,
broadcasting stations, in telephone exchanges, gas
engine ignition, automobiles etc.
Lithium-ion battery
 Generally, the anode of a lithium-ion cell is made
up of carbon. The cathode is a metal oxide, and
the electrolyte is a lithium salt in an organic
solvent.
 The most commercially popular anode is
graphite.
 The cathode material is made from Li liberating
comps, typically one of the following metal oxide
materials.
• Lithium Cobalt-oxide (LiCoO2)
• Lithium Manganese-oxide (LiMn2 O4)
• Lithium Nickel-oxide (LiNiO2)
Electrodes have open crystal structure
• Which allow the insertion and extraction of lithium ions.This
type of electrodes are called intercalation hosts
•
• The electrolyte is typically a mixture of organic carbonates such
as ethylene carbonate or diethyl carbonate containing
complexes of lithium ions such as lithium hexa fluoro
phosphate, lithium perchlorate, lithium tetra fluoro borate.
•
During charging, Li in positive electrode material is
ionized and moves from layer to layer and inserted into
the negative electrode.
During discharge Li ions are dissociated from the anode
and migrate across the electrolyte and are inserted into
the crystal structure of the host compound of cathode.
At the same time the compensating electrons travel in
the external circuit and are accepted by the host to
balance the reaction. The process is completely
reversible. Thus the lithium ions migrate reversibly
between the electrodes during charging and
discharging.
Cell reactions:
The chemical reaction that takes place inside the
battery is as follows, during charge and
discharge operation:

At anode: LinC  nLi+ + C + ne-

At cathode: Li1-n CoO2 + ne-+ nLi+ +  LiCoO2

Over all reaction :LinC+Li1-nCoO2C + LiCoO2

Advantages
They are less weight.
They produce high voltage about 4V as compared with other
batteries.
No liquid electrolyte means they are immune from leaking.
Fast charge and discharge rate
Disadvantage
They are expensive
They are not available in standard cell types.
Applications
They are used in cardiac pacemakers and other implantable
device.
They are used in telecommunication equipment, TVs, laptop
computers, mobile phones and aerospace application
 FUEL CELL OR FLOW BATTERY
Fuel cell is a voltaic cell. It converts chemical energy of the
fuels directly intoelectricity without combustion. In these
cells, the reactants and electrolytes are continuously
supplied to the cell.
Working principle
In fuel cell chemical energy is provided by fuel and oxidants
Fuel & oxidising agents are continuosly and seperately
passed through the electrodes of the cell these undergoes
reactons , produce electricity
HYDROGEN – OXYGEN FUEL CELL

It consists of two inert porous

electrodes

(graphite
with finely divided Pt) and
electrolyte solution which is
25% KOH solution.
Through the anode, hydrogen
gas is
bubbled and through the
cathode, oxygen gas is
bubbled, where the following
 The electron, proton, and oxygen combine
to form the harmless by product of water.
Cell reactions:
At anode : 2H2(g) + 4OH- (g)  4H2O(l) + 4e-

At cathode : O2(g) + 2H2O(l) + 4e-  4 OH-(aq)

Net reaction: 2H2(g) + O2(g)  2H2O(l).

Advantages
1. They are efficient and instant in operation.
2. They are pollution free.
3. They produce electric current directly from the reaction
of a fuel and an oxidiser.
4. They are light in weight
Disadvantages
1. Fuel cells cannot store electric energy.
2. Electrodes are expensive and short lived.
3. H2 should be pure.
Applications
1. H2 - O2 fuel cells are used in space crafts, submarines to
get electricity
2. In H2 - O2 fuel cell, the product water is a valuable
source of fresh water for astronauts
 Methanol – Oxygen Fuel Cell

• Direct methanol fuel cells or DMFCs are a

subcategory of proton-exchange fuel cells in which
methanol is used as the fuel.
• It consists of anodic and cathodic compartments.
• Methanol and H2O is passed through anodic
compartment. Oxygen is passed through cathodic
compartment.
• Electrolyte consists of sulphuric acid. A membrane is
provided which prevents the diffusion of methanol
into the cathode.
Anode:
CH3OH + H2O CO2 + 6H + + 6e-
Cathode:
3/2 O2 + 6H+ + 6e- 3H2O
Overall reaction:
CH3OH + 3/2 O2 CO2 + 2H2O
Advantages:
Methanol has low carbon content
The OH group is easily oxidisable
Methanol is highly soluble in water.
Uses: in military applications.
Difference b/w Priprima,Secondary, Fuel cells