Electrochemistry

Dr. Majid Majeed Akbar

Institute of Chemical Engineering & Technology

University of the Punjab, Lahore.
Electrochemistry
Electrochemistry is the branch of Physical
Chemistry that studies chemical reactions
which take place at the interface of an
electrode.
These reactions involve electrical charges
moving between the electrodes
electrolytes.
Thus electrolchemistry deals with the
interaction between electrical energy and
chemical change.
Arrhenius Theory of Electrolytic
Dissociation
Main Points of the theory are:
 An electrolyte, when dissolved in water, breaks up into two types
of charged particles, one carrying a positive charge and the other a
negative charge. These charged particles are called ions. Positively
charged ions are termed cations and negatively charged as anions.
In its modern form, the theory assumes that solid electrolytes
are composed of ions which are held together by electrostatic
forces of attraction. When an electrolyte is dissolved in a solvent,
these forces are weakened and the electrolyte undergoes
dissociation into ions. The ions are solvated.
 The process of splitting of the molecules into ions of an electrolyte
is calledionization. The fraction of the total number of molecules
present in solution as ions is known as degree of ionization or
degree of dissociation.
 For weak Electrolytes the theory did not prove
satisfactory.
Debye-Huckel Theory of Interionic
Attraction
 Like Arrhenius, they believe that strong
electrolytes, at least in dilute solution, are
completely ionized.
 They showed that, because of electrostatic
attractions between charged ions, each
positive ion in solution must be surrounded
on an average with more negative ion or
vice versa.
 In other words, each ion in solution is
surrounded by an ionic atmosphere whose
net charge is opposite to that of the central
ion.
Electrolytic Conduction
In electrolytic conductors, electron
transfer takes place by the migration of
ions, both positive and negative. This
migration involves not only a transfer of
electricity from one electrode to another,
but also a transport of matter from one
part of the conductor to another.
Current flow is always accompanied by
chemical changes at the electrodes.
Faraday’s Laws of Electrolysis
Faraday’s Ist Law of Electrolysis
Mass of a substance involved in reaction at
the electrodes is directly proportional to
the quantity of electricity passed through
the solution.
Farady’s Second Law of Electrolysis
Masses of different substances produced
during electrolysis are directly
proportional to their equivalent weight.
Transference and Transference
Numbers
 The quantitative relationship between the
fraction of current carried by an ion and
its speed can be established as;
Hittorf’s Rule
 Changes in concentration at the
electrodes as a result of electrolysis will
be equal only when the ionic speeds are
the same.
Determination of Transference
Numbers
 Hittorf Method
 Moving Boundary Method
 Electromotive Force Measurement