Liquid Junction Potential

Let a cell be formed by combining two electrodes either different electrolytes or

same electrolyte having different concentration.
As an example consider a concentration cell having silver electrodes separated by
a semipermeable membrane
Ag|AgNO3(Conc C1)|AgNO3(Conc C2)|Ag, Where C2> C1.
Here | separating two solutions of AgNO 3 represents the semipermeable
membrane.
A potential develops at the junction of these two solutions. This potential is called
liquid junction potential Ej.
Then Ecell = E RHS - E LHS + Ej
This potential arises due to the diffusion of ions from a region of higher
concentration to a region of lower concentration across the boundary. If the velocities of
ions are different, an electrical double layer is established across the junction. The
potential of this double layer is the liquid junction potential.
Mechanism
Consider the above cell. Because of higher concentration of AgNO3 on the right
hand side, it diffuses to the left hand side. Since AgNO 3 is ionized, actually silver and
nitrate ions diffuse separately. Velocity of nitrate ions is more than that of silver ions,
more nitrate ions cross the junction and accumulate on LHS. This causes the formation of
electrical double layer at the junction as shown in the figure. The potential developed at
this junction is called liquid junction potential. In experiment this is eliminated by
connecting the two solutions by a salt bridge having salt with same velocity of anion and
cation and the cell can be represented as Ag|AgNO3(Conc C1)||AgNO3(Conc C2)|Ag,
where the double line represents the salt bridge

C1 C2
- +
C1 C2
- +
- +
Ag+ - +
- +
- +
NO3- - +
- +
- +
- +
- +
 POTENTIOMETRIC TITRATIONS
The potential of an electrode depends on the concentration of the ion which it is
reversible in accordance to the Nernst Equation. In the titration there is a change in the
ionic concentration which can be followed by measuring the potential of a suitable
electrode. The potentiometric titrations are those titrations which involve the
measurement of electrode potentials with the addition of titrants
Let us consider two important types of potentiometric titrations
1) Acid base titrations 2) Redox titrations

ACID BASE TITRATIONS

Consider the potentiometric titration of HCl against NaOH
Principle : The reaction between HCl and NaOH does not involve oxidation and reduction.
Hence it cannot be directly determined by potentiometric titration. But the reaction
involves the change in the concentration of H+ ions. Hence an electrode responsive to H +
ions, i.e quinhydrone electrode is chosen. Quinhydrone is added to HCl solution .
Platinum wire is dipped into it which is called indicator electrode. This electrode is
connected to saturated calomel electrode to construct a galvanic cell which can be
represented as SCE|| Q, QH2|Pt
The EMF of the cell is given by 𝐸𝐶𝑒𝑙𝑙 = 𝐸𝑅𝐻𝑆 − 𝐸𝐿𝐻𝑆
𝐸𝐶𝑒𝑙𝑙 = 𝐸𝑄 − 𝐸𝑆𝐶𝐸
𝐸𝐶𝑒𝑙𝑙 = (𝐸𝑄𝑜 + 0.0591 log[𝐻 + ]) − 𝐸𝑆𝐶𝐸

𝐸𝐶𝑒𝑙𝑙 = (𝐸𝑄𝑜 − 0.0591pH) − 𝐸𝑆𝐶𝐸

𝐸𝐶𝑒𝑙𝑙 = (𝐸𝑄𝑜 − 𝐸𝑆𝐶𝐸 ) − 0.0591pH

In the above equation both 𝐸Q𝑜 and ESCE are constants. Hence EMF of the cell depends only
on the pH of the solution.
Initially the solution contains high concentration of H+ ions. Hence the pH of the
solution is low. Therefore the value of ECell will be higher. When titrated with NaOH the
pH increases which causes decrease in the EMF. Towards the end point the pH increases
rapidly and hence Ecell decreases rapidly. Beyond the equivalence point the pH of the
solution is practically remains constant. Hence after the end point very little change in
the potential is observed. The end point is obtained by plotting the graph of the cell EMF
∆𝐸
and volume of NaOH added or by plotting the graph of against V.
∆𝑉
Procedure:
A known volume of HCl solution is pipetted out into a beaker. A spoonful of
quinhydrone is added to it and stirred well to prepare a saturated solution. . A platinum
wire is dipped into the solution to pick the potential. This is the experimental electrode.
This is combined with a saturated calomel electrode. The resulting cell is the experimental
cell. Potential of this cell is to be determined.
NaOH solution is added to the HCl solution from the burette and after each addition the
EMF is noted. As the end point is approached the EMF changes faster. Hence NaOH is
added in smaller quantities towards the end point. After the equivalence point two more
∆𝐸
readings are taken. In each case the ratio of calculated and plotted against volume of
∆𝑉
NaOH. The peak of the graph corresponds to the end point. From this the strength of the
HCl solution is calculated.
Calculations :
Volume of NaOH
EMF of the cell
E
V
∆𝐸
∆𝑉
OXIDATION REDUCTION TITRATIONS
Example : Potentiometric titration of Ferrous sulphate Vs Potassium dichromate
Principle : The oxidation reduction electrode Pt|Fe+2, Fe+3 is set up by dipping a platinum
electrode into a known volume of given ferrous sulphate solution. This electrode is
combined with a calomel electrode to obtain experimental cell which can be represented
as follows. SCE|| Fe+3, Fe+2|Pt
The EMF of the cell is given by the expression 𝐸𝐶𝑒𝑙𝑙 = 𝐸𝑅𝐻𝑆 − 𝐸𝐿𝐻𝑆
𝐸𝐶𝑒𝑙𝑙 = 𝐸Fe+3/ Fe+2 − 𝐸𝑆𝐶𝐸
𝑜 [𝐹𝑒 +3 ]
𝐸𝐶𝑒𝑙𝑙 = 𝐸Fe +3 / Fe+2 + 0.0591 𝑙𝑜𝑔 − 𝐸𝑆𝐶𝐸
[𝐹𝑒 +2 ]

𝑜 [𝐹𝑒 +3 ]
𝐸𝐶𝑒𝑙𝑙 = (𝐸Fe +3 / Fe+2 − 𝐸𝑆𝐶𝐸 ) + 0.0591 𝑙𝑜𝑔
[𝐹𝑒 +2 ]
𝑜
In the above equation both 𝐸Fe +3 / Fe+2 and ESCE are constants. Hence EMF of the

cell depends only on the relative concentration of ferric and ferrous ions present in the
solution.
Initially the solution in the ferric-ferrous electrode contain only ferrous ions. When
titrated with potassium dichromate some if the ferrous ions get oxidized to ferric ions.
[𝐹𝑒 +3 ]
Hence the ratio of increases. Addition of more amount of dichromate solution from
[𝐹𝑒 +2 ]
[𝐹𝑒 +3 ]
the burette causes further increase in the EMF. Towards the end point the value of
[𝐹𝑒 +2 ]
increases rapidly and beyond the equivalence point the concentration of ferrous ions in
the solution is practically zero. The EMF of the cell now depend on the ratio of dichromate
and Cr+3 ions. Hence after the end point very little change in the potential is observed.
The end point is obtained by plotting the graph of the cell EMF and volume of dichromate
∆𝐸
added or by plotting the graph of against V.
∆𝑉
Procedure:
A known volume of ferrous sulphate solution is pipetted out into a beaker. Equal
volume of dilute sulphuric acid is added. A platinum wire is dipped into the solution to
pick the potential. This is the experimental electrode. This is combined with a saturated
calomel electrode. The resulting cell is the experimental cell. Potential of this cell is to be
determined.
Dichromate solution is added to the ferrous sulphate solution from the burette
and after each addition the EMF is noted. As the end point is approached the EMF
changes faster. Hence dichromate is added in smaller quantities towards the end point .
∆𝐸
After the equivalence point two more readings are taken. In each case the ratio of
∆𝑉
calculated and plotted against volume of dichromate. The peak of the graph corresponds
to the end point. From this the strength of the ferrous sulphate solution is calculated.
Calculations :
Volume of
dichromate
EMF of the cell
E
V
∆𝐸
∆𝑉
CONCENTRATION CELLS
In galvanic cells the EMF develops due to the chemical reaction taking place in the
cell. However, there is another category of cells in which the EMF arises due to the
transfer of matter from one half cell to the another because of the difference in the
concentration between the two. Such cells are called concentration cells
Concentration cells are of two types
1. Electrode concentration cells 2. Electrolyte concentration cells
1. Electrode concentration cells
In these cells two like electrodes at different concentration are dipping in the same
solution.
Example 1: Two hydrogen electrodes at unequal gas pressures immersed in the same
solution of hydrogen ions which can be represented as
Pt|H2(P1)|HCl|H2(P2)|Pt
Expression for Ecell.
𝐸𝐶𝑒𝑙𝑙 = 𝐸𝑅𝐻𝑆 − 𝐸𝐿𝐻𝑆
2.303 𝑅 𝑇 [𝐻 + ]2 2.303 𝑅 𝑇 [𝐻 + ]2
= (𝐸𝐻𝑜2 + log 𝑜
) − (𝐸𝐻2 + log )
2𝐹 𝑝𝐻2(𝑅𝐻𝑆) 2𝐹 𝑝𝐻2 (𝐿𝐻𝑆)

Since [H+] is same for both LHS and RHS and 𝐸𝐻𝑜2 is same we get
0.0591 𝑝𝐻 (𝐿𝐻𝑆)
𝐸𝐶𝑒𝑙𝑙 = log 2
2 𝑝𝐻2(𝑅𝐻𝑆)
0.0591 𝑝1
𝐸𝐶𝑒𝑙𝑙 = log
2 𝑝2
Example 2:
Electrode concentration cell containing amalgam with two different concentration of
the same metal
Hg-Pb(C1)| PbSO4(solution)|Hg-Pb(C2)
Expression for Ecell.
𝐸𝐶𝑒𝑙𝑙 = 𝐸𝑅𝐻𝑆 − 𝐸𝐿𝐻𝑆

𝑜
2.303 𝑅 𝑇 [𝑃𝑏𝑆𝑂4 ] 𝑜
2.303 𝑅 𝑇 [𝑃𝑏𝑆𝑂4 ]
= (𝐸𝑃𝑏 + log ) − (𝐸𝑃𝑏 + log )
2𝐹 [𝐻𝑔 − 𝑃𝑏]𝑅𝐻𝑆 2𝐹 [𝐻𝑔 − 𝑃𝑏]𝐿𝐻𝑆
𝑜
Since PbSO4 solution is common and 𝐸𝑃𝑏 is same we get
 0.0591 [𝐻𝑔 − 𝑃𝑏]𝐿𝐻𝑆
𝐸𝐶𝑒𝑙𝑙 = log
2 [𝐻𝑔 − 𝑃𝑏]𝑅𝐻𝑆
0.0591 𝐶1
𝐸𝐶𝑒𝑙𝑙 = log
2 𝐶2

Electrolyte concentration cells

In these cells the two electrodes of the same metal are dipping in a solution of
metal ions of different concentration and hence of different activities. Consider a
metal M is dipped into its own salt solution. An electrode M|Mn+ is obtained. The
concentration cell can be represented as
M|Mn+ (C1)|| Mn+ (C2)|M
Expression for Ecell.
𝐸𝐶𝑒𝑙𝑙 = 𝐸𝑅𝐻𝑆 − 𝐸𝐿𝐻𝑆

𝑜
2.303 𝑅 𝑇 [𝑀𝑛+ ]𝑅𝐻𝑆 𝑜
2.303 𝑅 𝑇 [𝑀𝑛+ ]𝐿𝐻𝑆
= (𝐸𝑀 + log ) − (𝐸𝑀 + log )
𝑛𝐹 [𝑀 ] 𝑛𝐹 [𝑀 ]
𝑜
Since metal is a solid [M] = 1and 𝐸𝑀 is same we get

2.303 𝑅 𝑇 [𝑀𝑛+ ]𝑅𝐻𝑆

𝐸𝐶𝑒𝑙𝑙 = log 𝑛+
𝑛𝐹 [𝑀 ]𝐿𝐻𝑆
2.303 𝑅 𝑇 𝐶2
𝐸𝐶𝑒𝑙𝑙 = log
𝑛𝐹 𝐶1

Determination of solubility product of a sparingly soluble salt using concentration

cells
Principle : Consider the determination of solubility product of sparingly soluble salt
AgCl.
A concentration cell is set up using two silver half cells in which the concentration
of one of the solution is known. This electrode is prepared by taking known
concentration of silver nitrate solution. As the concentration of silver ions is high in
this electrode this electrode becomes the RHS electrode. The second silver electrode
is prepared by taking saturated solution of silver chloride whose solubility product to
be determined. The concentration cell can be represented as
Ag|AgCl solution (saturated)||AgNO 3|Ag
The EMF of the above cell is given by
2.303 𝑅 𝑇 [𝑎𝐴𝑔+ ]𝑅𝐻𝑆
𝐸𝐶𝑒𝑙𝑙 = log
𝑛𝐹 [𝑎𝐴𝑔+ ]𝐿𝐻𝑆

In dilute solution the activity can be replaced with concentration and hence the
expression becomes
2.303 × 8.314 × 298 [𝐴𝑔+ ]𝑅𝐻𝑆
𝐸𝐶𝑒𝑙𝑙 = log
1 × 96500 [𝐴𝑔+ ]𝐿𝐻𝑆
[𝐴𝑔 + ]𝑅𝐻𝑆
𝐸𝐶𝑒𝑙𝑙 = 0.0591 log
[𝐴𝑔+ ]𝐿𝐻𝑆
Here [𝐴𝑔+ ]𝐿𝐻𝑆 is the concentration of Ag+ ions in saturated AgCl solution.
Assuming that all dissolved AgCl has ionized [𝐴𝑔+ ]𝐿𝐻𝑆 = 𝑠 where s is the solubility of
AgCl.
Then by knowing the concentration of AgNO3 solution the solubility can be
calculated using the expression.
[𝐴𝑔𝑁𝑂3 ]
𝐸𝐶𝑒𝑙𝑙 = 0.0591 log
𝑠
Problem:
Calculate the solubility of AgCl using the following concentration cell which has cell
potential of 0.1182V
Ag|AgCl solution (saturated)||AgNO3(0.001N)|Ag
Solution:
[𝐴𝑔 + ]𝑅𝐻𝑆
𝐸𝐶𝑒𝑙𝑙 = 0.0591 log
[𝐴𝑔+ ]𝐿𝐻𝑆
0.001
0.1182 = 0.0591 log
𝑠
0.1182 0.001
= log
0.0591 𝑠
0.001
log =2
𝑠
 0.001
= 102
𝑠
𝑠 = 10−5 𝑚𝑜𝑙. 𝑑𝑚 −3
𝐵𝑢𝑡 𝑓𝑜𝑟 𝐴𝑔𝐶𝑙, 𝐾𝑠𝑝 = 𝑠 2

𝐾𝑠𝑝 = (10−5 )2 = 10−10

Activity and Activity coefficient

Activity ‘a’ of a species is defined as the effective concentration of the species in a
given system. And it is related to the concentration as
Activity = Activity coefficient x Concentration
If the concentration is expressed as molality then the activity coefficient is denoted as

Then we get, a =  x m
For dilute solutions  =1 and hence a = m