CHM 101

ELECTROCHEMISTRY
CONTENTS
Electrochemistry
Electrolytes
Electrochemical cells
Electrolysis
Behaviour of ions in electrolyte
Applications
 Electrochemistry
It is the study of production of electricity from
energy released during spontaneous chemical
reactions (redox) and the use of electrical energy
to bring about non-spontaneous chemical
transformations (in a electrochemical cell).
The science of electron transfer across a solution-
electrode interface.
It is the study of chemical reactions where
electricity is the driving force.
 Such reactions are broadly classified into two
categories:
(i) Production of chemical change by electrical
energy, i.e, the phenomenon of electrolysis
(ii) Conversion of chemical energy into electrical
energy, i.e, the generation of electricity by
spontaneous redox reactions
 Examples: batteries and fuel cells convert
chemical energy into electrical energy.
 Electrolyte
A compound or substance that produces an
electrically conducting solution when dissolved
in a polar solvent such as water. It may be
Strong electrolyte-those that dissociate
completely in dilute solution, eg: salts, mineral
acids, etc. and
Weak electrolyte-those that dissociate partially in
dilute solution, eg: organic acids, aqeous NH 3, etc
 Electrodes
 These are the conductors by which
electrons enter or leave the electrolyte.
There are two types:
 Anode- the positive electrode by which
electrons leave the electroyte
Cathode- the negative electrode by which
electrons enter the electrolyte
Electrochemical cell
 This is a cell where the spontaneous conversion
of chemical energy into electrical energy and
where a non-spontaneous chemical reaction
occurs by supplying electricity occur.
 Types of electrochemical cell are
(i) Galvanic cells and
(ii) Electrolytic cells.
 Galvanic Cell
 This cell converts chemical energy into electrical
energy, i.e, electricity can be obtained with the
help of a redox reaction.
 The oxidation and reduction take place in two
separate compartments.
 Each compartment consists of an electrolyte
solution and a metallic conductor, which acts as
an electrode.
 The compartment containing the electrode and
the solution of the electrolyte is called half cells.
For example, the Daniel cell is a galvanic cell in
which zinc and copper are used for a redox
reaction to take place.
Zn(s) + Cu+2(aq) → Zn+2 + Cu(s)
At anode (oxidation half),
Zn(s) →Zn+2 + 2e–
At cathode( reduction half),
Cu+2(aq) + 2e– → Cu(s)
 Daniel cell:
 Salt bridge: The salt bridge is usually an inverted U-
tube filled with a concentrated solution of inert
electrolytes.
 It is used to maintain the charge balance and to
complete the circuit by allowing the flow of ions
through it.
 It contains a gel in which inert electrolytes like
KNO3 or K2SO4 are mixed.
 Through the salt bridge, negative ion flows towards
the anode and positive ion flows to the cathode, and
the charge balance is maintained, and the cell keeps
on functioning.
 Electrolytic cell
An electrochemical device that uses electrical energy to facilitate a non-
spontaneous reaction.

The three primary components are:

cathode,
anode and
electrolyte
The diagram is the electrolysis of molten NaCl.
 Cathode (-): Na+ + e- Na

 Anode (+): 2 Cl- Cl2 + 2e-

 Overall: 2NaCl(l) 2 Na(l) + Cl2 (g).

 Electrolysis
 It is the chemical decomposition of a compound or
substance by the passage of electricity through it, in either
aqueous or molten state.
Faraday’s laws of electrolysis:
(a) First law states that the mass, M of a given product
discharge at electrode during electrolysis is directly
proportional to the quantity, Q of electricity which passes
via the electrolyte soln.
M α Q and Q = It
M α It and M = ZIt
where Z = a constant known as electrochemical equivalent; I
= current and t = time.
1 gram equivalent = 96,500 Coulomb = Faraday ,F.
Quantity of electricity = nF where n is the valency of
ion.
Eg: 1 mole of silver, Ag+ = 1F
1 mole of copper, Cu2+ = 2F
1 mole of Aluminium, Al3+ = 3F, etc.
At cathode, Ag+ + e- Ag
Cu2+ + 2e- Cu
Al3+ + 3e- Al
 (b) Second law states that when the same masses
of electricity passes via solutions of different
electrolyte, the amounts of the substances
liberated are directly proportional to their
chemical equivalents E.
ie M E
The ratio of mass to chemical equivalent of each
of them are the same. ie
()H = ()Cu = ()Ag or
() = () = ()
 Chemical Equivalent of an element is the mass
obtained divided by valency, n. ie E = .
Electrochemical equivalent is the mass of
substance deposited when a current of 1 A is
passed for 1 s during electrolysis.
 Combining 1st and 2nd laws gives

Q = It = ()F and E =

Therefore, It = (w/())F

It =
 Problems
(1) 0.1978 g of copper is deposited by a current of
0.2 A in 50 minutes. What is the
electrochemical equivalent of copper.
Soln: Q =It = 0.2x50x60 = 600 C
Amount of Cu deposited by 600 C = 0.1978
g
1 C will deposite
= 0.000326 g
(2) When an aqueous solution of copper sulphate is
electrolysed, copper is deposited at the cathode.
Cu(aq) + 2e- Cu(s)
If a constant current was passed for 5 hrs and 404 mg
of Cu was deposited. Calculate the current passed
through CuSO4.

Solns: I = = = 0.0682 A.
 Behaviour of ions in electrolyte
Electrolytes and solvents dissociate or ionize into
various ions (+ve and –ve).
During electrolysis an electric current is passed
through the electrolyte, +ve ions move to the
cathode while –ve ions move to the anode.
Conductivity is the ability of a material to allow the
passage of electric current or heat from one point to
another.
Conductance, C is the ability of the solution to
conduct electricity or the reciprocal of the resistance.
C = unit is ꭥ-1 .
Conductance of an electrolyte depends on
(i) surface area, a
(ii) distance, ꙇ separating the electrodes.
 Conductance, C α ;
hence C = k
where k is called the conductivity or specific
conductance.
 k = C, unit is ꭥ-1 m-1 .
 Applications
In medicine-the use of electrochemical sensors to
determine the resistance of bacteria
In pharmacy-use during drug clinical trials in
medicinal chemistry lab.
In everyday life such as
-battery testing and charging,
-fuel cell,
-corrosion studies,
-treatment of municipal and industrial waters and
wastewaters.
 Assignments:
(i) Explain the term electrochemical series
(ii) Outline the descending order of element in
the series.
(iii) The solution of metal of atomic mass X was
electrolysed for 1 hour with a current of 0.25
ampere. The mass of the metal deposited
was 0.295 g. Find the metal X if its valency is
2.