Electrochemistry

• Electrolytes
• Non electrolytes
• Electrolysis
• Faraday’s law of electrolysis and applications
• Conductance in electrolytic solutions
• Kohl rash's law and applications
• Electrochemical cell
• EMF of the cell
• Nernst equation
• Cells
• Corrosion
 Electrochemical cells
• Electrochemical cell is a system or arrangement in which two electrodes
are fitted in the same electrolyte or in two different electrolytes which are
joined by a salt bridge to the external circuit.
• These are the devices which are used to convert electrical energy into
chemical energy & Vice versa.
• Electrochemical cells are two types.
a) Electrolytic cell b) Galvanic cell (or) Voltaic cell
a) Electrolytic cell: It is a device used to convert the electrical energy into
chemical energy.

➢ Both anode & cathode are present in

the same electrolyte.
 b) Galvanic cell (or) Voltaic cell: It is a device used to convert the chemical
energy produced in a redox reaction into electrical energy.

➢If a redox reaction is allowed to take place in such a way that the oxidation half reacrtion
takes place in one beaker and the reduction half reaction in another beaker, then
electrons will flow from the former to the latter and a current will flow.
➢Salt bridge is an inverted U-tube filled with a strong electrolyte like KCl in Agar-Agar gel.
Representation of an electrochemical cell:
➢ In general, the electrode at which reduction takes place is written on the
RHS of the salt bridge and the electrode at which oxidation takes place is
written on the LHS of the salt bridge.
➢ The salt bridge linking the aqueous solutions is represented by two
vertical parallel lines having ions on both sides.

➢ In the above system, Zn electrode is written on the LHS while the Cu

electrode on the RHS of the salt bridge.
 Cell Potential (or) EMF of a cell

• The difference between electrode potentials of two half cells is known as

electromotive force (or) cell potential (or) cell voltage.
 Single Electrode
• A metal rod dipped in the aqueous solution of its salt or a gaseous non-metal in
contact with a solution containing its anion in the form of salt (or) acid (or) alkali
functions as single electrode.
Metal electrodes Non-Metal electrodes
• Generally in case of metal electrodes, the electrolyte in a single electrode
is written in the form of the ions of the concerned metal while
representing the half cell.

• In the case of non-metal electrodes, a platinum rod is placed in the

concerned aqueous solution of the ion and along with it the concerned
gas at atmospheric pressure is passed into the solution. These are
represented as
 Electrode potential
• The potential which is established at solid-liquid interface (or) gas-liquid
interface in the given electrodes are called “Electrode potential”.
• The potential established during oxidation reaction is called oxidation
potential & the potential established during reduction is called Reduction
potential.
• The potential which are determined at 250 c & 1 atm pressure in 1 molar
solution of their ions are called “standard electrode potential”
 Standard electrode potential (E0)

• It is potential developed when the pure metal is in contact with its ions at
one molar concentration at 250c or 298 K.
Example: When a zn rod of any length is dipped in 1M ZnSO4 solution,
standard electrode is formed and the potential developed is called
standard zinc electrode (E0 Zn). The standard zinc electrode is represented
as Zn/Zn+2 (1 M).
 Standard Hydrogen Electrode (SHE)
• The potential of a single electrode cannot be determined directly but the difference in potentials
can be determined.
• Standard hydrogen electrode is used as a reference electrode in the determination of electrode
potentials.
• The potential of SHE is ‘’0’’ volts.
Construction:

•This is a gas electrode. It consists of a thin rectangular

platinum foil which is coated with fresh platinum black
to increase the adsorption capacity of the metal. This is
welded and the end of it is fused into the inner tube
through the base.

•In the inner tube, little mercury is taken and a cu wire

is introduced to make the external electrical contact.

•The inner tube is enclosed in an outer jacket having an

inlet tube for sending in H2 gas and has a perforated
wider base for the escape of excess of H2 .

•This unit is dipped in HCl taken in a beaker such that

the metal foil remains in the solution.
Working:
• When pure and dry H2 gas is passed through
the inlet tube, a part of the gas gets adsorbed
and the excess bubbles out through the
perforations.
• Between the H2 gas absorbed on the surface
of the metal and H+ of the solution,
equilibrium is established and potential will be
developed.
• The potential developed is called H2
electrode potential.
•In the above system, when the H2 gas at a
pressure of 1 atm is bubbled through 1M HCl,
the electrode formed is called STANDARD
HYDROGEN ELECTRODE or NORMAL
HYDROGEN ELECTRODE. This represents as
Pt,H2 (1 atm) / H+ (1 M).

The standard H2 electrode potential is defined as the potential that is developed

between H2 gas adsorbed on the Pt metal and H+ of the solution when the H2 gas at a
pressure of 760 mm of Hg is in equilibrium with H+ of unit concentration.
• The magnitude of SHE potential is considered to be zero. It is used-
1. For the determination of electrode potential of metal electrode system.
2. For the determination of PH of the solution.

Limitations:

1. It is rather difficult to regulate the pressure of the H2 gas to be at exactly

1 atm throughout the experiment.
2. Excess of H2 bubbling out carries little HCl with it and hence the H+
concentration decreases. In such a system, it is difficult to maintain the
concentration of HCl at 1M.
3. Platinum foil gets easily poisoned by the impurities present in the gas
and HCl.
Measurement of electrode potentials
• The absolute value of a single electrode cannot be measured
experimentally because a half-cell reaction cannot take place
independently.
• One can measure only the difference between the electrode potential for
one of the half-cell reaction are known, the electrode potential of the
other electrode can be calculated.
• Therefore, a standard hydrogen electrode is chosen and all other cell
reactions are compared with this standard and a set of E0 values are
obtained.
 Measurement of Electrode potential of Cu+2 /Cu
Electrode
• In order to obtain a cell reaction one must
know the oxidized and reduced species to
determine the cathode and anode in the
cell.
• In a galvanic cell the cathode is the positive
electrode while the anode is the negative
electrode.
• When a cell consisting of copper electrode
immersed in 1 M CuSO4 solution and
standard hydrogen electrode are
connected to a voltmeter, the emf of the
cell is observed to be 0.34 V.
• Oxidation occurs at the standard Hydrogen
Electrode, which acts as the anode
whereas reduction occurs at the copper
electrode, which acts as the cathode.
• The potential of the cell:
• We can conclude that in case, the electron accepting tendency of the electrode
is more than that of a standard Hydrogen Electrode, its standard reduction
potential gets a positive sign and in case the electron accepting tendency of
the metal electrode is lesser than that of standard Hydrogen Electrode., its
standard reduction potential gets a negative sign. It must be remembered that
according to latest convention standard potentials are taken as reduction
potentials.
• The electrode at which reduction occurs with respect to standard Hydrogen
Electrode has +ve reduction potential.
• The electrode at which oxidation occurs with respect to standard Hydrogen
Electrode has –ve reduction potential.
Electrochemical series:

A series which shown an increasing

order of standard reduction potential
values of electrode is called
Electrochemical series.
• The electrodes with positive electrode potentials show greater tendency
towards reduction than the tendency shown by H+ reduction.
• The electrodes with negative electrode potentials show lesser tendency towards
reduction than the tendency of H+ ions for reduction.

Characteristics of electrochemical series:

1. Reactive metal are placed on top (e.g., Li) and they have a great tendency to
get oxidized. Non-reactive metals like Ag and Au are placed at the bottom.
2. The elements (or) metals which are present above Hydrogen in ECS liberates H2
from acids.
Applications of electrochemical series:
1. In electrochemical series, the topper elements have lower standard reduction
potential values. So, they have more tendency to undergo oxidation & they act
as powerful reducing agents.
2. In electrochemical series, the bottom elements have higher standard
reduction potential values. So, they have more tendency to undergo reduction
& they acts as powerful oxidizing agents.
3. The element having highest Reducing ability is Lithium. It is due to its lowest
standard reduction potential.
4. The element having highest oxidizing ability is Fluorine. It is due to its highest
standard reduction potential.
5. A metal system occurring above H2 , displaces H2 from dilute acids.
6. A metal system occurring below H2 does not displace H2 from dilute acids.
 EMF of the cell & Nernst equation
Gibbs free energy:
When a cell reaction takes place electrical energy is produced which
results in decrease in the free energy of the system.

In an electrochemical cell,

Produced for one mole of electrons, the quantity of current is equal to 1 F (96500 coulomb)

Therefore for n moles of electrons, it is nF.

E = potential at non standard
conditions

E0 = Potential at standard
conditions ( 250 c, 1 atm, 1M
For equilibrium establishment in a redox reaction. The decrease in the free
energy is given by

Where Kc = equilibrium constant

 Nernst equation
• This equation tells us the effect of temperature and concentration of the
electrolyte on electrode potential.
Equilibrium constant (Kc) from Nernst equation:

The concentration of CuSO4 decreases while that of ZnSO4 increases. As

electrode potential depends upon concentration, a stage comes where
both the electrode potentials are equal. Current stops flowing and the cell
is said to have attained equilibrium.
 Significance of Kc
• It tells us about the extent to which the reaction has been completed. Kc
for Zn-Cu cell at 298 k is 2 x 107 which shows that the reaction has nearly
gone to completion.
 Primary, secondary and Fuel Cells
Battery:
A number of cells connected in series forms a battery.

Primary cells:
In these the redox reaction occur only once and cannot be used again.
Example: Dry cells, Mercury cells

Secondary cells:
These can be recharged by passing current and can be used again and again.
Example: Lead storage cell, Ni-Cd storage cell.

Fuel cell:
Energy produced by combustion of fuels like H2 , CO, CH4 can be directly
converted to electrical energy.
 Fuel cells
• These are devices which convert the energy
produced during the combustion of fuels like
H2, CO, and CH4 directly into electrical energy.
• The most successful fuel cell is the H2 - O2
fuel cell.
• It was used in the Apollo space programmer
and the water produced used as drinking water
for the astronauts.
 Corrosion
• The process of slowly eating away of the metals due to attack of the
atmospheric gases on the surface of metals; forming oxides, carbonates,
sulphides is called corrosion.
• Examples of corrosion is rusting of iron, development of a green coating
on Cu, etc...
• It causes enormous damage to buildings, bridges, ships and to all objects
made of metals especially that of iron.
• In corrosion, a metal is oxidized by loss of electrons to oxygen and formation of
oxides.
• Corrosion of iron (commonly known as rusting) occurs in presence of water and
air.
• Corrosion is an electrochemical phenomenon.

• At a particular spot of an object made of iron, oxidation takes place and spot
behaves as anode and we can write the reaction

• Electrons released at anodic spot move through the metal and go to another
spot on the metal and reduce oxygen in presence of H+ (H+ ions are obtained by
H2CO3 ,which is obtained by CO2 and H2o in air). This spot behaves as cathode
with the reaction
• The overall reaction being :

• The ferrous ions are further oxidized by atmospheric oxygen to ferric ions
which come out as rust in the form of hydrated ferric oxide (Fe2O3.x H2O). In
this reaction H+ions are obtained.
Factors which promote corrosion:
1. Reactivity of metal
2. Presence of impurities
3. Presence of air, moisture, gases
4. Presence of electrolytes

Prevention of Rusting:
▪ Prevention of corrosion is of prime importance. It not only saves money
but also helps in preventing accidents such as a bridge collapse.
▪ One of the simplest methods of preventing corrosion is to prevent the
surface of the metallic object to come contact with atmosphere. This can
be done by covering the surface with paint or by some chemicals.
▪ Another simple method is to cover the surface by other metals (sn,Zn, etc)
that are inert or react to save the object. An electrochemical method is to
provide a sacrificial electrode of another metal (like Mg,Zn, etc.) which
corrodes itself but saves the object.