1.

Interface
Electrochemistry is the study of reactions in
which
charged
particles
(ions
and/or
electrons) cross the interface between two
phases of
matter, such as the interface
between a solid and a liquid (=electrode
/electrolyte).

2.1. Overview
(1) Electrochemistry is a study of redox
reaction:
-

Reduction [a reactant gains electron(s)]

Oxidation [a reactant loses electron(s)]
Oxidation:
Zn(s) Zn2+(aq) +
2eReduction:
Cu2+(aq) + 2e-
Cu(s)
Total Cell Reaction:
Zn(s)+Cu2+(aq) Zn2+(aq)
+Cu(s)

The metallic rods in the beaker are connected to the

ammeter by means of an insulated wire through a
key. Ammeter is used to know the passage of current
which moves in opposite direction to the flow of
electrons. The solution in the two beakers are
connected by an inverted U-tube containing
saturated solution of some electrolyte such as Kl,
KNO3, NH4OH which does not undergo a chemical
change during the process.
The two openings of the U-tube are plugged with
some porous material such as glass wood or cotton.
The U-tube which connects the two glass beakers is
called a salt-bridge.

When the circuit is completed by inserting the key in

the circuit, it is observed that electric current flows
through external circuit as indicated by the ammeter.
The following observations are made:

Therefore, the current flows from copper to zinc

N.B. The flow of electric current is taken opposite to
the flows of electrons

There observation can be explained as:

During the reaction, zinc is oxidized to Zn 2+ ions
which go into the solution. Therefore,
the zinc rod gradually loses its weight. The electrons
released at the zinc electrode move towards the other
electrode through outer circuit. Here, these are
accepted by Cu2+ ions of CuSO4 solution which are
reduced to copper.

The zinc electrode where electrons are released or

oxidation occurs s called anode while the copper
electrode where electrons are accepted or reduction
occurs is called cathode.

The two containers involving oxidation and reduction

half reactions are called half cells. The zinc rod
dipping into a ZnSO4 solution is oxidation half cell
and the copper electrode dipping into a CuSO 4
solution is reduction half cell

2.1. Overview
(2) Reduction reactions take place
heterogeneously at Interfaces between
electrodes and electrolyte(s):
-

Anode at which oxidation reaction(s) take(s)

place.
- -Cathode at which reduction reaction(s) take(s)
eeplace.

Zn(s)
Cu(s)
Zn2+(aq)

Cu2+(aq)

1. Interface

N.B. The galvanic cells which consists of the zinc rod dipping
into a ZnSO4 solution and the copper electrode dipping
into a CuSO4 solution is Daniell cell.
Its formula is:
Salt bridge and its function. Its usually an inverted U-tube
filled with concentrated solution of inert electrolyte. The
essential requirements of electrolyte are:
a) The mobility of the anion and cation of the electrolyte
should be almost same.
b) The ions of the electrolyte are not involved in
electrochemical change.
c) The ions do not react chemically with the species of the
cell.

Generally, salts like KCl, KNO3, etc. are used. The seturated
solutions of these electrolytes are prepared in agar agar
jelly or gelatin. The jelly keeps the electrolyte in semisolid phase and thus prevents mixing.
The important functions of the salt bridge are:
a) Salt bridge completes the electrical circuit.
b) Salt bridge maintains electrical neutrality of two half cell
solution.
The accumulation of charges in the two half cells
(accumulation of extra positive charge in the solution
around the anode according to the realizing of Zn2+ in
excess and accumulation of extra negative charge in the
solution around the catode due to excess of SO42- ) is
prevented by using salt bridge, which provides a passage
for the flow of the charge in the internal circuit.

REPRESENTATION OF AN ELECTROCHEMICAL CELL

An electrochemical cells or galvanic cell consists of two

electrodes: anode and cathode. The electrolyte solution
containing these electrodes are called half cells.
The following conventions are used in representing an
electrochemical cell:
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 the electrolyte (or the cation of
the electrolyte) while the cathode is represented by
writing the electrolyte first and then metal or solid phase.
3. The salt bridge which separates the two half cells is
indicated by two vertical lines.

Electrode Potential and E.M.F. of a galvanic cell

Electrode Potential
The flow of electric current in an electrochemical cell
indicates that a potential difference exists between two
electrodes.

If the metal has relatively high tendency to get oxidised, its

atom will lose electrons readily and form Cu2+ ions, which
go into the solution. The electrons lost on the electrode
would be accumulated on the metal electrode and the
electrode acquires a slight negative charge with respect to
the solution. Some of the Cu2+ ions from the solution will
take up electrons and become Cu atoms. After some time, an
equilibrium will be established as:

When such an equilibrium is attained, it results in separation

of charges (negative on the electrode with respect to the
solution).

Forming the double layer

Cu

1- metal
2solution

Similarly, if the metal ions have relatively greater

tendency to get reduced, they will take electrons
from the electrode. As a result, a net positive
charge will be developed on the electrode with
respect to the solution. This will also result into
separation of charges (positive on the electrode
with respect to the solution).
Due to separation of charges between the electrode
and the solution, an electrical potential is set up
between metal electrode and its solution.
The electrical potential difference set up between the
metal and its solution is known as electrode
potential.

The electrode potential may be of two

types:
1. Oxidation potential:
The tendency of an electrolyte to lose
electrons or to get oxidised
2. Reduction potential. The tendency of an
electrode to gain electrons or to get reduced.

E.M.F. or Cell Potential of a Cell

The difference between the electrode potentials of the two
electrodes constituting an electrochemical cell is known as
electromotive force (e.m.f.) or cell potential of a cell. This
acts as a driving force for the cell reaction. The potential
difference is expressed in volts.

Zn2+(aq) + 2e-
Zn(s)

-0.76
V

Cu2+(aq) + 2e-

+0.34

Standard
Reduction
Potential
20

2.2. Thermodynamics

In electrochemistry,
the standard
hydrogen electrode
(SHE) potential is
taken as a
reference point.
21