ELECTROCHEMICAL CELL OR GALVANIC CELL

The cells, which are used to convert chemical energy into electrical energy, are
called electrochemical or galvanic cells or voltaic cell. In these types of cells
oxidation and reduction take place in separate containers called half-cells and
the redox reaction is spontaneous. For example:

This arrangement contains two beakers, one of which contains 1 M solution of

ZnSO4 and other 1M solution of CuSO4. Zinc rod is dipped in ZnSO4 solution and
Copper rod is dipped in CuSO4 solution. These metallic rods are called
electrodes. Further these electrodes are connected to the ammeter with the help
of conducting wires through a key ammeter helps in giving the passage of
electric current which flows in opposite direction to the flow of electrons.

Both the beakers containing solutions are connected two each other with the help
of a U–shaped tube called salt bridge. This salt bridge is filled with saturated
solution of strong electrolyte like KCl, KNO3, NH4NO3, which does not under, go
any change during chemical reaction. The saturated solution is mixed with agar
gar or gelatin. The two openings of the U tube are plugged with some porous
material such as glass wool or cotton. This U-tube is salt bridge. When electric
current is allowed to pass through the cell then the flow of current is indicated by
the ammeter.
The following observations are made:

a) Zinc rod gradually loses its weight

b) The concentration of the Zinc ions (Zn2+ aq) in the ZnSO4 solution
increases
c) Copper gets deposited on the electrode.
d) The concentration of Cu2+ decrease in Cu SO4 (aq) solution
e) There is a flow of electron in the external circuit from zinc rod to copper
rod while the current flows from copper electrode to zinc electrode. It may
be noted as a convention, the flow of electric current is taken opposite to
the flow of electrons.
These observations can be explained as follow:

Zinc is oxidized to Zn2+, which goes to the solution.

The zinc rod gradually loses its weight. The electrons released at the
electrode move towards the other electrode through outer circuit. Here, these
electrons are accepted by Cu2+ ions of CuSO4 solution, which get reduced to
copper. So, the metal gets deposited on the copper electrode.

Zinc acts as anode because electrons are released i.e. oxidation occurs
copper electrode behaves as a cathode because electrons are gained i.e.
reduction occurs.

The zinc rod is regarded as –ve terminal and copper electrode is regarded as
+ve terminal. Electrons flow from negative terminal (anode) to positive
terminal (cathode)
The containers in which oxidation and reduction half reactions are occurring
are called half-cells. The container in which zinc rod is dipped into a ZnSO4
solution is oxidation half-cell and the other in which copper electrode is
dipped into a CuSO4 solution is reduction half-cell.

Salt Bridge and its Function:

It plays an important role in an electrochemical cell. It is basically a U shaped

tube filed with concentrated inert electrolyte.

The electrolyte added in the U tube should have following characteristics

1) The mobility of cation and anion of the electrolyte should be almost same.
2) The ions of the electrolyte should not involve in electrochemical change.
3) The ions don’t react chemically with the species of the cell.
4) The electrolytes generally used are KCl, KNO3, and NH4NO3 etc. The
saturated solution of these electrolytes is prepared in agar-agar jelly or
gelatin. The jelly keeps the electrolyte in semi solid phase and thus
prevents mixing.

Functions of Salt Bridge:

1) It completes the electrical circuit. The salt bridge connects the solution of
two half-cells and their electrodes are connected by the means of a wire.
Therefore salt will complete the circuit

2) It maintains the electrical neutrality of two half-cell solutions. This can be

explained by taking an example of electro chemical cells without a salt
bridge. The electrons released by the oxidation of Zn to Zn2+ ions will be
accepted by Cu2+ ions of CuSO4. In the other half-cell and get reduced to
copper.
3) The positively charged Zn2+ ions pass into the solution, which results into
accumulation of extra positive charge in the solution around the anode.
Similarly reduction of Cu2+ ions to Cu, there will be extra negative charge
around cathode due to excess of SO42- ions.

The accumulation of positive charge around zinc rod will prevent the
further flow of electrons from the zinc rod. Similarly the accumulation of
negative charge around copper electrode will prevent the flow of electrons
to the copper ions. Thus the flow of electrons will occur only for a short
period of time and after that cell will stop working.

This accumulation of charges in the two half cells is prevented by using

salt bridge because salt bridge provides the passage for the flow of charge
in the internal circuit. When there is increase in the concentration of Zn2+
ions around anode then salt bridge provides Cl- ions to the anode half-cell
and neutralizes the excess positive charge.

Similarly the excess negative charge is neutralized by sufficient number

of K+ ions migrated from the salt bridge to the half-cell. Thus, the salt
bridge provides cations and anions to replace lost or produced in the two
half-cells.

Representation of an Electrochemical Cell:

An electrochemical cell or galvanic cell consists of two electrodes – anode
and cathode. The electrolyte solution having these electrodes is called
half-cells. When two half-cells combine they form a cell. For representing
electrochemical cells the following conventions are to be used

1) A galvanic cell is represented by writing the anode (where oxidation

occurs) on the left hand side and cathode (where reduction occurs) on the
right hand side.

2) The anode of the cell is represented by writing metal or solid phase first
and then cation of the electrolyte, while cathode is represented by writing
cation first and then metal in solid phase.
3) The metal and the cation are separated by a semi colon (;) or by a vertical
line. The concentration of the electrolyte (cation) should also be
mentioned within brackets after the cation.

4) The two half cells are separated by salt bridge which is indicated by two
vertical lines
Representation of Some Common Cells by Cell Notation:
(i)

(ii)
iii)

ELECTRODE POTENTIAL AND E.M.F OF A GALVANIC CELL

Electric potential: The flow of electric current in an electrochemical cell

shows that a potential difference exists between two electrodes. Consider a
redox reaction occurring at these electrodes.

When an electrode, for example, copper, is dipped in a solution of its ion, any
of the following three possibilities can take place.

a) The metal ions (Cu2+) may collide with the electrode and
don’t undergo any change.

b) Cu2+ ions may collide with electrode, gain electrons and

get reduced to metal atoms.
Cu2+ + 2e- → Cu (reduction)
c) Cu atoms on the electrode may loose electrons and get
oxidized to Cu2+

Cu → Cu2+ + 2e- (oxidation)

Now, if the metal has relatively high tendency to get oxidized then its atoms will
lose electrons and form Cu2+ ions, which go into the solution and get
accumulated on the metal electrode. As a result the electrode acquires slightly
negative charge with respect to the solution.

Some of the Cu2+ ions from the solution take up some electrons and become
copper atoms. After sometimes, equilibrium will be established.
Such equilibrium results in the separation of charges (negative on the electrode
with respect to solution).

Now, if the metal ions have relatively greater tendency to get reduced they will
take up electrons from the electrode. This results in the development of positive
charge on the electrode with respect to solution and also creates a separation of
charges (positive on the electrode with respect to solution)

Due to the separation of charges between the electrode and the solution, an
electric potential is developed between metal electrode and its solution. This
electrical potential difference which is set up between metal and its solution is
called electrode potential. The electrode potential may be of two types

Oxidation potential: The tendency of an electrode to loose electrons or to get

oxidized is called its oxidation potential. e.g.

Reduction potential: The tendency of an electrode to gain electrons or to get

reduced is called its reduction potential. e.g.

The electrode potential depends upon a) the nature of the metal and its ions b)
concentration of ions in the solution c) temperature
E.M.F. or Cell Potential of a Cell
Since electrochemical cells consist of two half cells, their electrodes in these half-
cells have different reduction potentials. They have different tendency to loose or
gain electrons.

The electrode having high reduction potential will have the high tendency to gain
electrons as compared to the other electrode with low reduction potential. In
other words the electrode having low reduction potential has the higher tendency
to loose electrons.

As a result of this potential difference between the two electrodes there is a flow
of electrons from the electrode with low reduction potential to the electrode with
high reduction potential

The difference between the electrodes potential of the two electrodes

constituting electrochemical cells is called as electromotive force (E.M.F.)
or cell potential of a cell. This is the driving force for the cell reaction and
expressed in volts.

Therefore the cell potential or e.m.f. arises from the difference in the tendencies
of the two ions to get reduced. It is equal to the reduction potential for the
substance that actually undergoes reduction minus the reduction potential of the
substance that undergoes oxidation i.e.
As assigned, convention cathode is written on the right hand side and anode on
the left hand side. Therefore e.m.f. of the cell may be written as

Thus, e.m.f. of a cell may be defined as the potential difference between two
electrodes of the cell when either no or negligible current is allowed to flow in
the circuit.

Note: For calculating e.m.f. of a cell, the electrode potentials are always taken
as reduction potentials (as a convention) for both the electrodes.

The e.m.f. of a cell is measured with the help of potentiometer. It depends

upon the nature of the electrodes, temperature and concentration of the
solution in the two half-cells.
Difference between e.m.f. and Potential Difference:
Difference between Electrochemical and Electrolytic Cell:

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