Physical Chemistry

III

Chem 340
Course Instructor: Aafia Sheikh
 Equilibrium electrochemistry
• Electrochemical cell consists of two electrodes or metallic conductor in
contact with an electrolyte, an ionic conductor.
• Electrode compartment
• Inert metal --- act as source or sink of electrons.
• Salt bridge ------ it enables the cell to function.
• Galvanic cell is type of electrochemical cell that produces electricity as
result of spontaneous chemical reaction.
• Electrolytic cell is type of electrochemical cell in which a non-
spontaneous chemical reaction is driven by an external source of
current.
 • Redox reaction is a reaction in which there is
transfer of electron from one species to
another.
• The electron transfer may be accompanied by
atom or ion transfer, but the net effect is
electron transfer and hence change in
Half reactions oxidation number.
and Electrodes • Reducing agent ----- electron donor
• Oxidizing agent ------ electron acceptor
• Redox reaction may be expressed as
difference of two reduction half reactions.
• The reduced and oxidized species in half
reactions form Redox couple
Ox +
Expressing reaction in terms of half
reactions
Varieties of
cell
Varieties of cell
 Varieties of cell

Electrode concentration cell is the

type of cell in which electrodes
themselves have different
concentrations because (1) they are
gas electrodes operating at different
pressures or (2) amalgams with
different concentrations.
Electrolyte concentration cell is
the type of cell in which the
electrode compartments are
similar except for the
concentration of electrolyte.
 Liquid junction potential
In cell with two different electrolyte solutions in contact (Daniel cell), there is an additional source of
potential across the interface of two electrolytes. This is called liquid junction potential.

Another example of junction potential is between two concentrations of hydrochloric acid.

Electrolyte concentration cells always have junction potential electrode concentration cells do not.

The contribution of liquid junction to the potential can be reduced by joining the electrode
compartment with salt bridge.

Reason: The liquid junction potential at either end are largely independent of the concentration of
two dilute solutions, so nearly cancel.
 Salt
Bridge
Notations
The electromotive force
The current produced by galvanic cell
arises from spontaneous chemical
reaction taking place inside it.

The cell reaction is written on the • RHE is cathode ------- the spontaneous reaction is reduction
assumption that • LHE is anode ------- the spontaneous reaction is oxidation

The reverse is true for non-

spontaneous cell reaction.

For a given cell, the two electrodes

and their half reactions are

Hence the overall reaction is

 The Nernst equation

• A cell in which the overall cell reaction has not reached chemical equilibrium
can do electrical work as the reaction drives the electrons through an external
circuit.
• The work done by electron transfer depends on the potential difference
between the two electrodes. This is called cell potential (measured in Volts)
• When cell potential is large, the electron transfer will do large amount of
electrical work.
• When cell potential is small, the electron transfer will do small amount of
electrical work.
• A cell in which overall reaction is at equilibrium, can do no work, cell potential
is equal to zero.
 • The maximum electrical work that a system can do is
given by

• The relation between Gibb’s free energy and emf of

the cell is given by

The Nernst Where F is Faraday constant & is the stoichiometric

coefficient of the electrons in half reactions in which cell
equation reaction can be divided.
• This equation is the key connection between the
electrical work on one hand and thermodynamic
properties on the other.
• Conditions
The cell must be operating reversibly at specific,
constant composition.
The reaction Gibb’s energy is related to specified
composition of reaction mixture.
The Nernst
equation