ELECTROCHEMI

CAL CELL
An electrochemical cell is a device in which the redox
reaction is carried indirectly and chemical energy is
converted to electrical energy. It is also called Galvanic
cell or Voltaic cell.
For example - a standard 1.5-volt cell which is used to
power many electrical appliances such as TV remotes
and clocks.
Electrochemical cells generally consist of a cathode and
an anode.

Galvanic cells
A galvanic cell, or voltaic cell, named after Luigi
Galvani or Alessandro Volta respectively. 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.

Zn(s)+Cu 2+¿(aq)¿
→ Z n (aq) + Cu(s)
2 +¿¿
This reaction is a combination of two half reactions
whose addition gives the overall cell reaction:
(Reduction half reaction)
−¿→ Cu (s ) ¿
2 +¿+2 ⅇ ¿
Cu

(Oxidation half reaction)

−¿¿
2+¿+2 ⅇ ¿
Zn ( s ) → Zn

These reactions occur in two different portions of

the Daniell cell. The reduction half reaction occurs
on the copper electrode while the oxidation half
reaction occurs on the zinc electrode. These two
portions of the cell are also called half-cells or redox
couples. The copper electrode may be called the
reduction half-cell and the zinc electrode, the
oxidation half-cell.

Salt Bridge
It is an inverted U-shaped glass tube which contains
a suitable salt in the form of a thick paste made in
agar-agar. It performs following functions –
 It completes inner cell circuit.
 It prevents transference of electrolyte from one
half-cell to the other.
 It maintains the electrical neutrality of the
electrolytes in the two half-cells.

Electrode potential
It is the potential difference set up between the
metal and solution of its own ions. It shows the
 tendency of an electrode to either lose or gain
electrons.

Standard Electrode
Potential
When the concentrations of all the species
involved in a half-cell is unity then the electrode
potential is known as standard electrode
potential.

Cell Potential and Cell EMF

The potential difference between the two
electrodes of a galvanic cell is called the cell
potential and is measured in volts. 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 key features of the cathode and the anode are

tabulated below.

Cathode Anode
 Denoted by a
 Denoted by a negative
positive sign since
sign since electrons are
electrons are
liberated here
consumed here
 A reduction
 An oxidation reaction
reaction occurs in
occurs in the anode of
the cathode of an
an electrochemical cell
electrochemical cell
 Electrons move into  Electrons move out of
the cathode the anode

General convention dictates that the cathode

must be represented on the right-hand side
whereas the anode is represented on the left-
hand side while denoting an electrochemical cell.

Half-Cells and Cell Potential

 Electrochemical Cells are made up of two half-cells
or redox couples, each consisting of an electrode
which is dipped in an electrolyte. The same
electrolyte can be used for both half cells.
 These half cells are connected by a salt bridge
which provides the platform for ionic contact
between them without allowing them to mix with
each other.
 One of the half cells of the electrochemical cell
loses electrons due to oxidation and the other gains
electrons in a reduction process. It can be noted
that an equilibrium reaction occurs in both the half
cells, and once the equilibrium is reached, the net
voltage becomes 0 and the cell stops producing
electricity.
 The tendency of an electrode which is in contact
with an electrolyte to lose or gain electrons is
described by its electrode potential. The values of
these potentials can be used to predict the overall
cell potential. Generally, the electrode potentials
are measured with the help of the Standard
Hydrogen Electrode as a reference electrode.

Primary and Secondary Cells

 Primary cells are basically use-and-throw
galvanic cells. The electrochemical reactions
that take place in these cells are irreversible in
nature. Hence, the reactants are consumed for
the generation of electrical energy and the cell
stops producing an electric current once the
reactants are completely depleted.
 Secondary cells (also known as rechargeable
batteries) are electrochemical cells in which the
cell has a reversible reaction, i.e., the cell can
function as a Galvanic cell as well as an
Electrolytic cell.
  Most of the primary batteries (multiple cells
connected in series, parallel, or a combination of
the two) are considered wasteful and
environmentally harmful devices. This is
because they require about 50 times the energy,
they contain in their manufacturing process.
They also contain many toxic metals and are
considered to be hazardous waste.

Types of Electrochemical Cells

The two primary types of electrochemical cells are
1.  Galvanic cells (also known as Voltaic cells)
2. Electrolytic cells

The key differences between Galvanic cells and

electrolytic cells are tabulated below.

Galvanic Cell /
Electrolytic Cell
Voltaic Cell
 Chemical energy  Electrical energy is
is transformed transformed into
into electrical chemical energy in
energy in these these cells.
 electrochemical
cells.
 The redox  An input of energy is
reactions that required for the redox
take place in reactions to proceed in
these cells are these cells, i.e., the
spontaneous in reactions are non-
nature. spontaneous.
 In these
electrochemical
cells, the anode is  These cells feature a
negatively positively charged
charged and the anode and a negatively
cathode is charged cathode.
positively
charged.
 The electrons
 Electrons originate
originate from
from an external
the species that
source (such as a
undergoes
battery).
oxidation.

Applications of
Electrochemical Cells
 Electrolytic cells are used in the electrorefining of
many non-ferrous metals.
 In comparing relative reducing or oxidising power
of the elements.
 In predicting the feasibility of spontaneity of a
redox reaction.
 The production of high-purity lead, zinc,
aluminium, and copper involves the use of
electrolytic cells.
 In predicting whether a metal can evolve hydrogen
from an acid or not.
 Many commercially important batteries (such as
the lead-acid battery) are made up of Galvanic
cells.
 Comparison of reactivities of metals and non-
metals.
 Determination of standard Gibbs energy change.
 Determination of equilibrium constant

ACTIVITY
 To set up a simple voltaic cell and
measure its emf
AIM
To set up a simple voltaic cell and measure
its emf
MATERIALS REQUIRED
Beaker (250 ml), Porous pot, Connecting
wires, Voltmeter, Zinc strip, Sand paper,
Copper strip, 1 M ZnSO4 solution, 1M
CuSO4 solution
Concentration of Electrolyte Voltmeter
ZnSO4 CuSO4 Reading
1M 1M 1.1 V
1M 0.1 M 1.07 V
1M 0.01 M 1.04 V
OBSERVATIONS

Time (in min) 0 5 10 15 20 25 30

Reading of 1.1 1.1 1.09 1.07 1.05 1.03 1.0
voltmeter
RESULTS
The emf of the assembled cell is “x” volts. The
emf decreases after passage of time.
The emf of a cell change with change in
concentration of electrolytes.