Electrochemical Methods of Analysis

Electrochemical methods depend on

measuring of electrical quantity which
is in direct relation to concentration of
substance analysed.

Advantages of electrochemical
method:
1-Short time needed for analysis.
2- It is suitable for determination of

colored or turbid solution.

Electrochemical Methods of
Analysis
When a piece of metal is immersed in a
solution of its own ions:
a potential difference will be created
at interface of metal and solution.
Magnitude of potential difference is
the measure of the tendency of an
element or ion to undergo an oxidation
or reduction,
i.e. to lose or gain electrons.

Electrochemical Methods of
Analysis
The element-ion, M and M2+
combination is a half- cell,
The reaction is a half reaction,
The immersed metal is an electrode,
and the
Potential due to the reaction at the
interface of electrode and the solution
is the electrode potential.

An electrode, which in the figure are the plates of zinc (Zn) and
copper (Cu).

An electrolyte, which in the figure are

aqueous solutions of zinc sulfate (ZnSO4)
and copper(II) sulfate (CuSO4).

Electrochemical Methods of Analysis

Two systems are in use for the
expression of an electrode potential.
1-Oxidation potentials in which product
of the half cell is in the oxidized state
M

M2+ + 2emetal ion

2- Reduction potential in which product
is in the reduced form

M2+ + 2e
M

 Electrochemical cells:
An electrochemical cell consists of
two conductors called electrodes
each of which is immersed in an
electrolyte solution.

 Cathodes and Anodes:

Cathode is the electrode at which a
reduction reaction occurs.
Anode is the electrode at which an
oxidation takes place.
Examples of typical cathodic reactions
include:

Ag+ + e- Ag(s)

Fe3+ + e- Fe2+

NO3- + 10H+ + 8e- NH4+ + 3H2O

 Typical anode reaction includes:

Cu(s)
Cu2+ + 2e
2ClCl2(g) + 2e
Fe2 +
Fe3 + + e-

Types of electrochemical cells

Electrochemical cells are either

Galvanic
or electrolytic.
Galvanic or voltaic, cells store electrical energy.
An electrolytic cell ,in contrast, requires an
external source of electrical energy for
operation.(consume electricity)
For both galvanic and electrolytic cells,
Reduction always takes place at the cathode
&
Oxidation always takes place at the anode.

Galvanic cell

- Chemical reaction occurs to

produce electrical energy
( store energy)
chemical
reversed.

Electrolytic cell
-Electrical energy is used
to force
non-spontaneous
reaction occur.
.
- Direction of current is

Galvanic cell (A) : Chemical reaction occurs to produce

electrical
energy
Electrolytic cell (B): electrical energy is used to force
Non spontaneous chemical reaction occur
-Direction of the current is reverse
-The reaction at the electrodes are reversed

Galvanic Cell -- an electrochemical cell in which a spontaneous reaction

generates electricity.

 Electrolytic Cell -- an electrochemical cell in

which electricity (an external voltage) is used to
drive a nonspontaneous reaction.

Anode -- This is the electrode that takes up electrons from the

solution (do not think of it in terms of positive or negative
because that changes depending on whether it is a galvanic or
electrolytic cell).
Cathode -- This is the electrode that gives off electrons into
the solution

Electrolytic cell

Electrolytic cell
Galvanic cell

Electrolytic cell:
- electrical energy is used to
force nonspontaneous
chemical reaction occur.
-direction of the current is
reversed

-the reaction at the

electrodes are reversed