Liquid junction

potential

Liquid junction potential occurs when two

solutions of electrolytes of different
concentrations are in contact with each
other. The more concentrated solution will
have a tendency to diffuse into the
comparatively less concentrated one. The
rate of diffusion of each ion will be roughly
proportional to its speed in an electric
field, or their ion mobility. If the anions
diffuse more rapidly than the cations, they
will diffuse ahead into the dilute solution,
leaving the latter negatively charged and
the concentrated solution positively
charged. This will result in an electrical
double layer of positive and negative
charges at the junction of the two
solutions. Thus at the point of junction, a
potential difference will develop because
of the ionic transfer. This potential is
called liquid junction potential or diffusion
potential which is non-equilibrium
potential. The magnitude of the potential
depends on the relative speeds of the ions'
movement.
Calculation
The liquid junction potential cannot be
measured directly but calculated. The
electromotive force (EMF) of a
concentration cell with transference
includes the liquid junction potential.

The EMF of a concentration cell without

transport is:

where and are activities of HCl in

the two solutions, is the universal gas
constant, is the temperature and is
the Faraday constant.
The EMF of a concentration cell with
transport (including the ion transport
number) is:

where and are activities of HCl

solutions of right and left hand electrodes,
respectively, and is the transport
number of Cl−.

Liquid junction potential is the difference

between the two EMFs of the two
concentration cells, with and without ionic
transport:
Elimination
The liquid junction potential interferes with
the exact measurement of the
electromotive force of a chemical cell, so
its effect should be minimized as much as
possible for accurate measurement. The
most common method of eliminating the
liquid junction potential is to place a salt
bridge consisting of a saturated solution
of potassium chloride (KCl) and
ammonium nitrate (NH4NO3) with lithium
acetate (CH3COOLi) between the two
solutions constituting the junction. When
such a bridge is used, the ions in the
bridge are present in large excess at the
junction and they carry almost the whole
of the current across the boundary. The
efficiency of KCl/NH4NO3 is connected
with the fact that in these salts, the
transport numbers of anions and cations
are the same.

See also
Concentration cell
Ion transport number
ITIES
Electrochemical kinetics
References
Advanced Physical Chemistry by Gurtu
& Snehi
Principles of Physical Chemistry by Puri,
Sharma, Pathania

External links
Open source Liquid Junction Potential
calculator
Junction Potential Explanation Video

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