Block 2

Unit 5 Conductance-I
UNIT 5
Conductance-I
Structure
5.1 Introduction Concentration Dependence of
Molar Conductivity
Expected Learning Outcomes
Kohlrausch’s Law of Independent
5.2 Electrolytic Conductance
Migration of Ions
5.3 Conductivity and Its
5.6 Summary
Measurement
5.7 Terminal Questions
Measurement of Conductivity
5.4 Molar Conductivity 5.8 Answers
5.5 Concentration Dependence of

Conductivity and Molar
Conductivity
5.1 INTRODUCTION
You would recall from BCHCT-133 course that while discussing about ionic
equilibrium we introduced the concept of electrolytes and non-electrolytes. The
electrolytes were defined to be the substances whose aqueous solutions are
electrically conducting in nature. The conduction in such systems is called
electrolytic conduction and forms the subject matter of this and the next unit.
We would begin the unit by explaining the mechanism of electrolytic
conduction and contrast it with that of the metallic conduction which you have
learnt in your earlier classes. Then, we would introduce the concept of
conductivity and outline its significance. In this context, we would differentiate
between conductance and conductivity and establish a relationship between
them. We would then discuss different factors affecting conductivity of
electrolytic solutions. Thereafter, we would describe the principle of
measurement of conductance of electrolytic solutions.
This will be followed by an introduction to the concept of molar conductivity

and its significance. We would then discuss the concentration dependence of
conductivity and molar conductivity of electrolytic solutions. Herein, we would
outline the difference between the behaviour of solutions of weak and strong
electrolytes and explain the reasons for the same. In this context, we would
introduce the concept of limiting molar conductivities and state the
Kohlrausch’s law of independent migration of ions and discuss its applications. 119
Block 2 Conductance and Electrochemistry
In the next unit we would take up the concept of ionic mobility, transference
numbers and their determination along with various applications of
conductivity measurements.

After studying this unit, you should be able to:
❖ define electrolytic and metallic conduction;
❖ describe the mechanism of conduction in metallic and electrolytic

conductors;
❖ define and differentiate between the terms; conductance and

conductivity of a solution of an electrolyte;
❖ list and explain the factors affecting conductivity of electrolytic solutions;
❖ describe the method of measurement of conductivity of electrolytic

solutions;
❖ establish a relationship between conductance and conductivity of a

solution;
❖ define molar conductivity and explain its significance;
❖ discuss the concentration dependence of conductivity and molar

conductivity;
❖ state Kohlrausch’s law of independent migration of ions and give its

significance; and
❖ solve problems based on conductivity, molar conductivity and

Kohlrausch’s law of independent migration of ions.
5.2 ELECTROLYTIC CONDUCTANCE

In order to learn about electrolytic conduction, let us take up a simple
experiment, which you might have learnt, in your earlier classes also. We take
a solution of common salt (NaCl) in water and set up the apparatus as given in
the Fig. (5.1). What will happen when we press the switch? Yes, the bulb
would glow due to the conduction of current by the salt solution.
You have learnt

about electrolytes
and non-electrolytes
in Unit 7 of the
BCHCT-133 course.
It will be advisable if
you could review the
same before
continuing.
Fig. 5.1: A schematic diagram of experimental set up to demonstrate electrolytic

120 conductance.
Let us learn about the processes involved in this experiment. When we press
the switch, the electrons are pushed out of the negative terminal of the battery A battery provides
and these travel to the electrode through the wire. Then, in the solution the the electromotive
current is carried by ions from one electrode to the other; then again, the force that pushes
electrons are carried by the wire to the positive terminal of the battery through electrons out of the
the bulb. The passage of electrons (current) through the bulb makes it glow. negative terminal
and pulls electrons
You may note that in this simple experiment there are two different
into the positive
mechanisms by which the electrical conduction takes place. These are
terminal.
metallic conduction (when the electrons move through the metallic wire) and
electrolytic conduction (when the current is carried through the solution by
ions). In order to understand metallic conduction, we need to recall the
electron sea model according to which a metallic solid can be viewed as a
fixed array of positively charged metal ions, arranged as a solid lattice. These
positively charged ions are surrounded by a sea of mobile electrons, provided
by the valence electrons of the atoms, Fig. (5.2 (a)).
(a) (b)
Fig. 5.2: A schematic diagram of a) electron sea model of metal and
b) illustration of metallic conduction.
When an electrical field is applied across the metal wire, the electrons move
through the lattice of positive ions in response to an applied electric field. A
certain number of electrons enter the metal at one end and an equal number
of electrons come out of the other end, Fig. (5.2 (b)). In this process of moving
through the lattice of positive ions the electrons are scattered away from their
straight-line motion due to collisions amongst them as well as with the positive
ions. At higher temperature, the electrons move faster, and the positive ions
also vibrate more around their mean position. Therefore, the number of
collisions between the electrons and ions increase. Consequently, the mobility
of the electrons and hence the metallic conductance decreases with an
increase in temperature.
On the other hand, in case of aqueous solution of NaCl, the dissolved salt
dissociates into Na+and Cl− ions. The Na+ions are attracted to the negative
electrode, and the Cl− ions to the positive electrode, Fig (5.3).
Fig. 5.3: A schematic diagram showing the movement of different ions towards
the opposite electrodes in an aqueous solution of NaCl. 121
In addition, the ions obtained from the autoprotonation (autoionisation) of
water also move towards opposite electrodes, however as pointed out before,
their concentration is too small. The movement of ions generates an electric
current equivalent to the flow of electrons along the metal wire.
It is important to note that in case of ionic solutions the passage of current is
accompanied by transport of positive and negative ions. In other words, the
passage of current involves not only transfer of electricity (charge) from one
electrode to the other, but also a transport of matter from one part of the
solution to the another. Further, the positive and negative ions have different
capacities to carry current i.e., they carry different amounts of current. As a
consequence, some kind of a concentration gradient develops in the solution.
We will talk more about it later.
When the ions carrying current through the bulk of the solution reach the
electrode, they undergo chemical reactions called electrode reactions. These
reactions are quite characteristic and depend on the nature of the electrolyte
and the electrodes. We would take up such reactions in the next unit. For now,
we can say that the electrolytic conduction is much more complex than the
metallic conduction. Contrary to metallic conduction, the electrolytic
conduction increases with increase in temperature. It is due to a greater
dissociation of electrolyte and higher mobility of ions at higher temperature.
Having learnt the mechanisms of metallic and electrolytic conduction let us

learn about expressing conductivity and its measurement. However, before
that answer the following simple question
SAQ 1
Name the species responsible for carrying current in metallic and electrolytic
conductors.
5.3 CONDUCTIVITY AND ITS MEASUREMENT

You would have learnt about Ohm’s law in your school physics class. This law
According to Ohm’s
law, the current relates the quantity of current flowing through a metallic conductor with the
flowing through the potential applied across it and the resistance offered by it. According to this
conductor is directly law, the strength of an electric current flowing through a conductor, i.e., the
proportional to the quantity of electricity flowing per second through the conductor equals the ratio
difference in potential of difference in potential applied across the conductor and the resistance
and inversely offered by the conductor to the flow of current. This law is valid provided the
proportional to the
temperature and other physical conditions remain unchanged. Mathematically,
resistance.
we can write
V
I = …(5.1)
R
For a uniform conductor the resistance, R (in Ω) is directly proportional to its
length, 𝑙(m), and inversely proportional to the area of its cross-section, A (m2).
That is, we can write
 
Rα R =  …(5.2)
A A
122
Where, 𝜌 is the constant of proportionality and is called resistivity (or specific
resistance) of the conductor. If we have a conductor of unit length and a unit 
area of cross section (𝑙 =1m and 𝐴=1m2) then R =
A
1m 2
 = R () = ( m) …(5.3) 
1m  =R
A
This means that the resistivity is the resistance offered by conductor of unit
length and unit cross-section area. The SI unit of resistivity is ohm meter (Ω m)
though we commonly use ohm centimeter (Ω cm) where the area and the
length of the conductor are in cm2 and cm, respectively.
However, we are interested in conductance of the electrolytic solution. It is
important to note that the solutions containing electrolytes also obey Ohm’s
law like metallic conductors. It is obvious that a solution of electrolyte that
offers lesser resistance to the flow of current would allow more current to pass
through it i.e., would be a better conductor. Thus, we can say that the
conductance would be reciprocal of the resistance. The conductance is
denoted as G and has SI unit, seimens, S (or Ω -1 or mho (now obsolete)). The
measured conductance for a solution of electrolyte depends on the distance (l) (Werner Von Seimens)
between the electrodes and the surface area(A) of each electrode. It is the
conductance due to all the ions present between the two electrodes in the The unit of electrical
conductance,
solution. We can write,
seimens is named
1 1 A A A after Werner von
G= =  =   G =   …(5.4)
R  I I I Siemens–a German
electrical engineer,
Rearranging, we get
inventor, and
 (m) …(5.5) industrialist.
 = G (S) = S m−1
A (m2 )
The reciprocal of resistivity,  is called conductivity (or specific
conductance) and is denoted as kappa,  . The conductivity is an intrinsic
property of the solution and can be visualised as the conductance of the
electrolytic solution present in a unit cube, Fig. 5.4 (a). The SI units of
conductivity is siemens m-1 ( S m -1 or Ω -1m −1 ) and would be the conductance of
the electrolytic solution present in a cube formed by two electrodes having
area of 1 m2 each and separated by 1 meter.
However, for practical purposes we use electrodes of area 1 cm2 and the
distance between them as 1 cm. In such a situation the conductivity would be
the conductance of the electrolytic solution present in a cube having a volume
of 1 cm3, Fig. (5.4 (b)), and its units would be seimen cm-1 (Scm-1 or Ω-1cm−1).
(a) (b)
Fig. 5.4: A schematic representation of conductivity a) in SI units b) in
commonly used units. 123
The SI units of conductivity can be related to common units as
S m−1 = 10 −2 S cm−1
S S …(5.6)
S m−1 = = = 10−2 S cm−1
m 100 cm
In order to understand the physical meaning of conductivity, let’s consider a

cubic conductor having side =1cm. Now if we apply a potential of 1V across
the conductor, then according to the Ohm’s law, the current (in ampere)
flowing through the conductor would be I = V = 1 . Thus, the conductivity
R R
is the amount of current flowing through a conductor having a volume of 1cm3
when a potential of 1V is applied across it.
You would recall about autoprotonation of water from your earlier studies. It is
a consequence of amphoteric nature of water. You know that a sample of pure
water has 1 10 −7 M each of hydronium ions and hydroxide ions. These ions
impart extremely low conductivity (~ 3.5  10 −5 S m–1) to the pure sample of
water. Therefore, the pure water is said to be practically non-conducting.
If a substance can However, when we add an electrolyte to water it dissociates or ionises and
behave as an acid as
provides its own ions in the solution, thereby, increasing the number of ions in
well as a base, it is
the solution. As a consequence, the resistance of the solution decreases and
said to be
amphoteric in the measured current or conductance increases. Thus, we can say that the
nature. conductance of a solution is related to the concentration of ions in it.
In addition to the concentration of the electrolyte, the conductivity of

electrolytic solutions also depends on the following factors
• the nature of the electrolyte;

• the dielectric constant of the solvent;
• interionic interactions;
• viscosity of the solvent;
• size of the ions and their solvation; and
• temperature
Let us discuss these factors briefly
The nature of the electrolyte: different electrolytes dissociate / ionise to

different extent in solution. As a consequence, for a given molar concentration,
the aqueous solution of the strong electrolyte like NaCl will contain more ions
than that of a weak electrolyte like acetic acid. As a result, the solutions of
strong electrolytes generally have a higher conductivity than those of the weak
electrolytes.
The dielectric constant of the solvent: the ionisation of an electrolyte

depends on the nature of the solvent. In solvents of low dielectric constant the
electrostatic forces between opposite ions is large and the electrolyte is not
dissociated completely, thereby, providing fewer ions. Hence the solution
shows smaller conductance. On the other hand, a solvent with higher dielectric
constant is more ionising and the electrolyte provides more ions and hence
higher conductivity. A given electrolyte may be a strong electrolyte in one
solvent due to large dissociation but may behave as weak electrolyte in other
124 solvent due to low degree of dissociation.
Interionic interactions: in a solution of an electrolyte there are forces of
interaction between the oppositely charged ions of the electrolyte. These are
called solute−solute interactions. In dilute solutions, as the constituent ions are
far apart, the forces of attraction between them are negligible. As a
consequence the ions are free to move and the conductivity is high. On the
other hand, in concentrated solutions the forces of interaction are strong.
Therefore, the mobility of the ions falls and the conductivity of the solution
decreases.
Viscosity of the solvent:the viscosity of the solvent is a measure of solvent–

solvent interactions; higher the interaction greater the viscosity. In a solution of
the electrolyte, the ions have to move through the solvent and their mobility
and hence conductivity would depend on the viscosity of the solvent. If the
solvent viscosity is higher the mobility of ions would be low and hence the
conductivity would also be low.
Size of ions and their solvation: the speed with which ions move in an
electrolytic solution under the influence of applied electric field is inversely
proportional to the mass and the size of the ions. A smaller ion would move
faster than a larger one, however, we need to be careful here because smaller
ions with high charge density may be heavily solvated and as a consequence
may have a larger effective size than a large ion that bigger but is not solvated
much.
Temperature: the conductance of a solution generally increases with an

increase in temperature. The rise in conductance with temperature is due to
the decrease in the viscosity of the solution which leads to an increase in the
speed of the ions. Secondly, in case of a weak electrolyte, the extent of
ionisation also increases with temperature thus increasing the number of ions
and hence higher conductivity.
Having learnt about conductivity and the factors affecting it let us now learn
how do we measure conductivity. However, before that answer the following
simple question to assess your understanding of conductivity.
SAQ 2
Define conductivity and give the relationship between conductance and
conductivity of an electrolytic solution.
5.3.1 Measurement of Conductivity

As discussed above, the conductance is the reciprocal of resistance.
Therefore, the conductance and hence the conductivity of an electrolytic
solution can be determined by measuring its resistance. You have learnt
about measurement of resistance of a wire by using a potentiometer based on
Wheatstone bridge, in your school physics class. However, there are two
limitations of using this method for measuring the resistance of ionic solutions.
First limitation is that if we pass direct current (DC) through the solution, this
would cause electrolysis and the composition of the solution would change. In
some cases, there may be liberation of gases on the electrodes. This leads to
errors in the measurement. Secondly, it is not possible to connect a solution of 125
unknown resistance to the bridge like a metallic wire. So, the question comes
up is that, “how do we measure the resistance and hence the conductance of
the given electrolytic solution?”
The first limitation is taken care of by using alternating current (usually a

frequency of 500-2000 Hz is supplied) as suggested by Kohlrausch. As a
result of the reversal of the direction of the symmetrical current about a
thousand times per second, the effects of each pulse of the current is
completely neutralised by the next. The second issue is resolved by using a
specially designed device called conductivity cell. The solution whose
conductance is to be determined is taken in the conductivity cell; in fact, the
cell is dipped in the solution and the resistance of the solution contained
between the two electrodes of the conductivity cell is measured by using
Kohlrausch conductance bridge based on the principle of Wheatstone bridge.
Let us briefly describe the set up for measuring the resistance (and hence
conductance) of an electrolytic solution.
The setup of the apparatus is schematically given in Fig. (5.5). Here R3 and R4
are two fixed resistances, R1 is a variable resistance and fourth arm of the
Wheatstone bridge is the conductivity cell whose resistance needs to be
measured, this unknown resistance is indicated as R2. The a.c. power to the
Wheatstone bridge is provided by an oscillator in the audio frequency range.
As the frequency of the alternating current is within the range of human ear a
set of headphones (or some other electronic device) is used as the detector
for the null point (you would recall that in measuring the resistance of a wire
using dc, a galvanometer is used for this purpose).
Fig. 5.5: A schematic diagram of the set up used for the measurement of
resistance of an electrolytic solution.
The variable resistance is changed to achieve null (balance) state. The

passage of the current through the detector(earphones) produces a buzzing
sound which decreases as we get closer and closer to the balance stage. It
becomes minimum at the balance point. At this stage, the unknown resistance,
R2 is given by the following expression.
R4
R2 = R1 …(5.7)
R3
Conductivity cell
The simplest kind of conductivity cell consists of two platinum electrodes fused
126 in a glass or in an unbreakable epoxy body. In fact, the conductivity cells come
in different shapes and sizes, Fig. (5.6). The platinum electrodes are
electrochemically coated with chloroplatinic acid. This imparts a rough finish to
the electrode and is called platinum black. This rough finish increases the
surface area of measurement and improves the response of the electrode.
These electrodes are separated by a distance ‘l’ and have a surface area
equal to ‘A’. Thus, in a typical measurement the resistance of the solution
confined between these electrodes is measured. For solutions having high
conductivity values the conductivity cells with large distance between the
electrodes are employed. Some commonly used conductivity cells are shown
in Fig. 5.6.
Fig. 5.6: A schematic diagram showing different types of conductivity cells.
From Eq. (5.4) we can find the relationship between conductance and conductivity
as
1 A
=G = …(5.8)
R 
On rearranging we get,
1  
= =G …(5.9)
R A A
In a conductivity cell the electrodes have a constant surface area and their
position is fixed, i.e., they have a constant distance of separation. Thus, the
ratio of distance between the electrodes to the area of the electrode is
constant for a conductivity cell. It is called cell constant and its SI unit is m-1
however practical unit of cell constant is cm-1 because the typical surface
areas and the distance between the electrodes of conductivity cells is quite
small and are expressed in cm2 and cm respectively. So we can rewrite the
Eq. (5.9) as
1
Conductivi ty =  cell constant = conductanc e  cell constant (5.10)
resistance
This implies that to determine conductivity of a solution we need to measure
its resistance, take its reciprocal to obtain conductance and then multiply
conductance with the cell constant. We have learnt above to measure
resistance of a solution so we can easily get the value of conductance.
However, for getting conductivity we need the value of cell constant. Now the
question comes up is that how do we determine the cell constant?
Determination of cell constant
In a typical laboratory conductivity cell, the surface area of the electrode is of

the order of 1-2 cm2 and the distance between them is around 1 cm. If these 127
values are known, we can in principle calculate the cell constant. However, it
is not possible to measure these values accurately, so we use an indirect
method of determining the cell constant. For this, we take a solution of known
conductivity (determined by some other method) and use the given
conductivity cell to measure its resistance and hence the conductance. This
can then be used to determine the cell constant. Generally standard solutions
of KCl with known conductivity values are used for the purpose. Let us
understand it with the help of an example.
Example 5.1: The resistance of a standard solution of 0.1 M KCl at 25oC taken
in a conductivity cell was found to be 72 Ω. If the conductivity of
It is difficult to obtain 0.1 M KCl solution at 298 K is given to be 0.01290 S cm−1
cell constant from the
calculate the cell constant.
geometrical
dimensions of the Solution: As given above,
cell. It is, therefore,
1
calculated indirectly Conductivity =  cell constant
by measuring the resistance
resistance of a
Rearranging, we get
standard solution of
known conductivity. cell constant = conductivity  Resistance
Substituting the values
Cell constant = 0.01290 S cm-1  72
Cell constant = 0.93 cm-1 (You know that Ω = S-1)

Thus, the cell constant = 0.93 cm−1 .
Having learnt about the determination of cell constant, let’s take another
example for the determination of conductivity of an electrolyte.
Example 5.2: The resistance of a conductivity cell containing 0.1M KCl

solution was found to be 100 Ω. If the resistance of the same cell
when filled with an electrolytic solution is observed to be 220 Ω,
calculate the conductivity of the given solution. The conductivity of
0.1 M KCl solution is given as 1.29 S m-1.
Solution: In this problem we are given three data viz., the conductivity and
resistance of 0.1 M KCl and the resistance of the given solution.
We need to determine the conductivity of the given solution.
1
1m −1 = Approach: We would first use the data on 0.1 M KCl as in example 5.1 to
m
determine the value of cell constant and then use it to determine
1
= the conductivity of the given solution.
100 cm
Given: Conductivity (0.1 M KCl) = 1.29 Sm-1 = 0.0129 S cm-1
= 0.01cm−1 Resistance (0.1 M KCl) = 100 Ω= 100 S-1
From example 5.1, cell constant = conductivity  resistance
Substituting the given values for KCl, we get
128 Cell constant = 0.01290 S cm-1 100 S-1 = 1.29 cm-1

-1
Now, for the given solution, resistance= 220 Ω= 220 S
From Eq. (5.10), we know

1
conductivity =  cell constant
resistance
Substituting the value of resistance for the given solution and the value of the
cell constant, we get
1
conductivity = -1
 1.29 cm −1 = 0.00586 S cm −1
220 S
Thus, the conductivity of the given solution would be 0.00586 S cm-1.
Having learnt about conductivity and its measurement let us introduce the
concept of molar conductivity. However, before that answer the following
simple questions to assess your understanding of measurement of
conductivity.
SAQ 3
The resistance of a conductivity cell containing 0.001M KCl solution measured at
298 K was found to be 1500 Ω. If the conductivity of 0.001 M KCl solution at same
temperature is 1.46  10-4 S cm-1 calculate the cell constant for the conductivity
cell used.
SAQ 4
The resistance of 0.01 M solution of KCl taken in a conductivity cell having two
electrodes having an area of 1.8 cm2 each and at a distance of 0.9 cm was
found to be 2800 Ω. Calculate the conductivity of 0.01 M solution of KCl.
5.4 MOLAR CONDUCTIVITY

If we wish to compare the conduction behaviour of different electrolytic
solutions, we find that conductivity, as discussed above, is not a suitable
quantity. This is so because at a given temperature the solutions of different
electrolytes in a given solvent may differ in terms of the charge, size and
concentration of the ions produced; and mobility of the ions-the ease with
which the ions move under the applied potential gradient. Therefore, we need
a property that is characteristic of the electrolyte and is independent of the
concentration of the solution. In other words, in order to compare the F. W. Georg
conduction behavior of different electrolytes, we should compare their Kohlrausch
conductivities in solutions having same concentration in a given solvent at a (1840-1910)
given temperature. Such a quantity was defined by German physicist

Kohlrausch; he introduced the concept of equivalent conductivity, denoted as
 (lambda) that represented the conductance by all the ions produced by one
equivalent of the electrolyte in the solution. This can be visualised as the
conductance per equivalent concentration.
However, now a days we use the term called molar conductivity. It is
denoted by m and represents the conductance by all the ions produced by
one mole of the electrolyte in the given solution. It may be defined as the
conductance of a volume of solution containing the ions obtained from one
mole of a dissolved electrolyte when placed between two parallel electrodes
129
which are at a unit distance and are large enough to contain the whole solution
between them.
To visualise molar conductivity, we can imagine two parallel electrodes that
For uni- univalent are separated by 1 m and are so large that the solution enclosed between
electrolytes the
them contains all the ions produced by 1 mole of the electrolyte. If the
equivalent
conductivity and concentration of the solution is 1molm-3, the volume of hypothetical molar
molar conductivity conductivity cell would be 1m3 and the electrodes would have an area of
values are identical 1 m2 each. On the other hand, if the concentration is 2 mol m−3,the volume of
because 1 mole and hypothetical molar conductivity cell would be 0.5 m3; for a concentration
1 g equivalent of the
electrolyte would be
0.1 mol m−3 the volume will be 10 m3. In general, if the concentration is
same. 𝑐 molm−3, the volume containing all the ions from one mole of the electrolyte
1
would be 𝑐 m3 . That is, higher the concentration, lower the volume and vice-
versa. Therefore, the molar conductivity can be obtained by multiplying the
conductivity by a factor 1/c or V, the volume of solution containing 1 mol of the
electrolyte. Thus, we can mathematically write molar conductivity as
conductivity divided by molar concentration of the solution i.e.,

Λm = =  V …(5.11)
c
Here k is the conductivity, c is the concentration (in mol m−3 ) of the
electrolyte, V is the volume (in m3) of solution containing 1 mole of the
electrolyte and m, the molar conductivity of the electrolyte. As the SI unit of
conductivity is S m−1 , we can derive the SI unit of molar conductivity defined
above as
 (S m-1)
Λm = -3
= S m2 mol -1 …(5.12)
c (mol m )
However, as you would have realised by now that the conductivity cells used
in the laboratory have much smaller dimensions. Also, the concentrations are
expressed in moldm-3. Thus, there is a need to redefine molar conductivity in
terms of commonly used units. In such a case, to visualise molar conductivity,
we can imagine two parallel electrodes that are separated by a distance of
1 cm and are so large that the solution enclosed between them contains all the
ions produced by 1 mole of the electrolyte. If the concentration of the solution
is 1moldm-3, the volume of hypothetical conductivity cell having 1 mole of the
electrolyte would be 1dm3. On the other hand, if the concentration is c moldm-3
the volume containing all the ions from one mole of the electrolyte would be
1 dm3 . A schematic representation of the relationship between conductivity
c
and molar conductivity is given in Fig. (5.7). Here the volume of the solution
contained between two large plates (electrodes) is 1dm3.
Fig. 5.7: A schematic representation of the relationship between molar

130 conductivity and conductivity.
The molar conductivity once again would be defined by Eq. (5.11), but its
expression would get modified and the units will also be different as shown
below.
 (S cm-1 )  (S cm −1 ) 1000 cm3 dm -3 1000 
Λm = -3
= -3
= S cm2 mol -1 …(5.13)
c (mol dm ) c (mol dm ) c
1000 
Λm = S cm 2 mol −1 …(5.14)
c
Remember, the concentration in this expression is in mol d m −3 . Let us take up
an example to learn about the importance of expression given in Eq. (5.14)
Example 5.3: The conductivity of a 0.1 M aqueous solution of acetic acid is

found to be 5.3  10-4 S cm-1. Calculate the molar conductivity of
acetic acid at the given concentration. You may note that
white using the eq.
Solution: We know from Eq. (5.14) that the molar conductivity of a c molar 5.14. we take  in
solution is given by the following expression in which  is the terms of Scm-1 and c
conductivity of the solution in S cm-1. in mol dm-3 (or molar
concentration), the
1000 resulting molar
Λm = 
c conductivity is
obtained in the units
We are given,  = 5.3  10-4 S cm-1 and c = 0.1 M = 0.1 mol dm-3 of S cm mol-1
Substituting the values, we get
1000
Λm = 5.3  10−4  = 5.3 S cm2 mol −1
0.1
Thus, the molar conductivity of acetic acid solution would be 5.3 Scm2mol-1
Let us take one more example
Example 5.4: In a conductivity cell, the two platinum electrodes, each having
an area of 3 cm2 are 1.5 cm apart. The resistance of a 0.05 M
solution of a salt is found to be 50 Ω. Calculate the molar
conductivity of the solution.
Solution: Here, we need to find molar conductivity, which we know is given
by the following expression (where concentration is in mol dm-3 and
 in Scm-1)
1000 
Λm = S cm2 mol −1
c
We know the concentration, so we need to find the conductivity which
according to Eq.(5.9) is given as
1 
=
RA
1 1.5 cm
= = 0.01S cm-1
50S −1 3.0 cm2
Substituting the value of conductivity and concentration in the expression for

molar conductivity we get,
131
1000  0.01
Λm = = 200 S cm2 mol −1
0.05
Alternatively, we could first find cell constant, then conductivity and finally
molar conductivity. Thus, the molar conductivity of the given solution would be
200 S cm2 mol-1
Having learnt about the concept of molar conductivity, its physical significance
and relationship with conductivity and concentration we need to talk about
conductivity water, the water used in preparing solutions for conductivity
determinations. However, before that answer the following simple questions to
assess your learning.
SAQ 5
The resistance of 6.25  10–2 M solution of chloroacetic acid when measured
using a conductivity cell of cell constant 0.6 cm–1 was found to be 180 Ω.
Calculate molar conductivity of chloroacetic acid at this concentration
SAQ 6
The resistance of 0.02 M KCl solution at 298 K was found to be 250 Ω. If the
conductivity of 0.02 M KCl is 0.277 Ω m-1, calculate the distance between the
electrodes of the conductivity cell if they had a surface area of 2 cm2 each.
Conductivity water
As you know, the conductivity of an electrolytic solution depends on all the
ions present in the solution irrespective of their source. In a measurement of
conductivity of a given solution of a particular electrolyte, the trace amount of
impurity present in the water used for preparing the solution would affect the
measured conductance. It is, therefore, important that the water used for
preparing the solution is free from all types of ions as far as possible. Such
water can be obtained by repeated distillation of water and is called
conductivity water. The conductivity of such water is about 10-7 Scm-1. In
precise measurements of conductivity, the conductance of the water used for
preparing the solution is measured separately and is subtracted from the
observed conductance of the solution. Let us take up an example to
understand it.
Example 5.5: A conductivity cell having a cell constant of 0.3 cm–1 when filled
with 0.01 M solution of acetic acid gave a resistance of 1982 Ω.
The water used for preparing the solution had a conductivity of
7.0 × 10–6 S cm–1. Calculate the molar conductivity of 0.01 M
acetic acid solution.
Solution: From Eq. (5.10), we know that
1
conductivity =  cell constant
resistance
We are given, resistance = 1982 Ω = 1982 S–1 and cell constant= 0.3 cm–1
132 Conductivity of 0.01 M acetic acid

1
=  0.3 cm−1 = 1.51 10−4 S cm−1
1982 S-1
This conductivity is due to the ions obtained from acetic acid as well as
contributed by water used for preparing the solution. So, we need to subtract
the contribution from water.
The conductivity due to acetic acid alone
= (1.51 10-4 − 7.0  10 −6 ) S cm−1 = 1.44  10-4 S cm−1
1000 
Now we know that molar conductivity = Λm = S cm2 mol −1
c
Substituting the values of conductivity and concentration, we get
1000 1.44  10−4
= Λm = = 1.44 S cm2 mol −1
0.01
Thus, the molar conductivity of 0.01 M solution of acetic acid is calculated to
be 14.4 S cm2 mol–1
Having learnt about conductance, conductivity, molar conductivity, and their

interrelationships along with their determination let us now take up the
concentration dependence of conductivity and molar conductivity.
5.5 CONCENTRATION DEPENDENCE OF

CONDUCTIVITY AND MOLAR CONDUCTIVITY
Conductivity and molar conductivity of a solution, both vary with change in the The conductivity of an
concentration of the solution. You would recall from above that the conductivity electrolytic solution at
refers to the conductance due to all the ions contained in a unit volume of the any given
concentration is the
solution. As on decreasing the concentration of the solution the number of ions
conductance of unit
in the unit volume of the solution would decrease therefore the conductivity of
volume of solution
an electrolytic solution would decrease with decrease in the concentration. kept between two
This decrease in conductivity is observed both for weak as well as strong electrodes with unit
electrolytes however, the nature of change is different in the two cases. A area of cross section
schematic diagram showing the concentration dependence of conductivity of a and at a distance of
weak and a strong electrolyte is given in Fig. (5.8) unit length.
Fig. 5.8: A schematic diagram showing the concentration dependence of

conductivity for a strong and a weak electrolyte.
The strong electrolytes by definition are completely ionised practically at all

concentrations. So, a decrease in concentration simply decreases the number
of ions and hence the decrease in conductivity. On the other hand, in case of 133
weak electrolytes at moderate concentrations the extent of ionisation is quite
small. You would recall from the course BCHCT-133 that according to
Ostwald’s dilution law, the degree of ionisation of a weak electrolyte increases
on dilution. Thus, in case of weak electrolytes there are two factors which are
operative. First, the decrease in concentration decreases the number of ions in
the unit volume (as in case of strong electrolytes) and second with dilution the
degree of ionisation increases thereby increasing the number of ions in the
unit volume. One of these factors decreases the number of ions in the unit
volume while the other one increases them. However, the decrease in
concentration of ions due to decrease in concentration is much more than the
increase in concentration of ions due to increase in ionisation. Therefore, the
conductivity of the solution of a weak electrolyte decreases on dilution.
However, the decrease in conductivity of weak electrolyte is gradual whereas
that for a strong electrolyte is sharp as shown in the Fig. (5.8).
5.5.1 Concentration Dependence of Molar Conductivity

You would recall from above that the molar conductivity represents the
conductance by all the ions produced by one mole of the electrolyte in a given
solution. It is defined as the conductance of a volume of solution containing
the ions obtained from one mole of a dissolved electrolyte when placed
between two parallel electrodes which are at a unit distance and are large
enough to contain the whole solution between them. Also, from Eq. (5.11) we
can note that molar conductivity is a product of two terms viz., the
conductivity,  and the volume, V of solution containing 1 mole of the
electrolyte.
Λm =   V …(5.11)
This implies that we need to consider the effect of change in concentration on

both the parameters. We have seen above that V=1/c which means that the
volume containing 1 mole of the electrolyte increases with decrease in the
concentration. We have also learnt that the conductivity of solution decreases
with decrease in concentration for the strong as well as weak electrolytes. So,
the two factors viz., conductivity and volume work in opposite direction to
change the molar conductivity; volume tends to increase it with decrease in
concentration and the conductivity tends to decrease it. However, the volume
factor is much stronger, and it can more than compensate the decrease due to
decrease in conductivity. Therefore, the molar conductivity of the strong as
well as weak electrolytes increase on dilution. However, the changes are
different in the two cases let us learn about them.
Strong electrolytes
The molar conductivity depends on the concentrations of ions and the speed
with which the ions move. As stated above, the degree of ionisation of strong
electrolytes is one (100 %) even at moderate concentrations. So, on dilution,
there is no significant increase in the number of ions. However, at moderate
and high concentrations the inter-ionic interactions are quite strong and
therefore the mobility of the ions is slow and hence the conductivity is low. On
diluting the solution, these inter-ionic attractions decrease, and the ions are
relatively free to move and their mobility and hence the conductivity increases.
134
In moderate or high concentration of solutions, the increase in molar
conductivity with dilution is gradual and in the region of low concentration the
molar conductivity increases linearly. At extremely low concentrations (c→0)
(when the ions are effectively infinitely far apart and do not interact with one
another) the molar conductivity becomes maximum. This is called the limiting
molar conductivity or molar conductivity at infinite dilution and is denoted as
𝛬0. The variation of molar conductivity with concentration can be given by the
following equation.
Λ = Λ0 − A c …(5.15)
Thus, if we plot Λ against square root of concentration ( c ) for dilute

solutions we would get a straight line having a negative slope (-A) and an
intercept equal to Λ0 . A schematic diagram showing the variation in the molar
conductivity with concentration for some electrolytes in given in Fig. (5.9).
It is observed that the slope of the line (value of A) depends on the type
(stoichiometry) of the electrolyte for a given solvent and temperature. The
types of strong electrolytes can be understood based on the number of cations
and anions produced on their dissociation in the solution. For example, NaCl
and KCl are 1:1 electrolyte, whereas CaCl2 and BaCl2 are the examples of 2:1
electrolytes. It is important to note that all electrolytes of a given type have the
similar value for ‘A’.
Fig. 5.9: A schematic diagram showing variation in the molar conductivity with
c for some strong and weak electrolytes.
Weak electrolytes
The increase in the
At moderate or high concentrations weak electrolytes have low degree of molar conductivity on
ionisation and therefore, the number of ions and hence the molar conductivity dilution in case of
is low. As the number of ions is small the interionic interactions between the weak electrolytes is
due to the increase in
oppositely charged ions are not as significant as those in case of strong
the number of ions
electrolytes. Therefore, when a solution of a weak electrolyte like acetic acid is due to increase in the
diluted, the degree of ionisation increases as per the Ostwald’s law. This leads degree of ionization
to an increase in the number of ions in the volume of solution containing1 mol of the electrolyte,
of the electrolyte leading to an increase in molar conductivity. As there is a whereas in the case
significant increase in the degree of ionisation of the weak electrolyte on of strong electrolytes,
it is due to the
dilution, the molar conductivity increases sharply.
weakening of the
The increase is quite steep in the region of extremely low concentrations. The interionic interactions.
limiting molar conductivity in case of weak electrolytes is achieved at 135
extremely low concentrations where the degree of ionisation becomes 100 %.
However, at such a low concentration the conductivity of the solution is so low
that it cannot be measured accurately. Also, the molar conductivity versus
concentration graph for weak electrolytes does not allow extrapolation to zero
concentration. Therefore, in such cases the molar conductivity at infinite
dilution is obtained by using Kohlrausch law of independent migration of ions
discussed below.
5.5.2 Kohlrausch’s Law of Independent Migration

of Ions
On the basis of extensive studies of the equivalent conductivity of various
strong and weak electrolytes at extremely low concentrations (c→0)
Kohlrausch observed that the equivalent conductivities at infinite dilution for
pairs of electrolytes having a common ion differed by a constant value. As
mentioned above, now a days we use molar conductivity in place of equivalent
conductivity so the data is given in terms of molar conductivities. For example,
As the data is for 1:1
electrolytes; there will Λm0 (KC l) − Λm0 (LiCl) = 34.9 S cm2 mol −1
not be any difference
between the values of Λm0 (K N O3 ) − Λm
0
(LiNO 3 ) = 34.9 S cm2 mol −1
molar conductivities
and equivalent
Λm0 (K C l) − Λm0 (KNO 3 ) = 4.9 S cm2 mol −1
conductivities
0
Λm 0
(L i Cl) − Λm (KNO 3 ) = 4.9 S cm2 mol −1
Based on such observations, Kohlrausch proposed that at infinite dilution,

where all electrolytes (strong or weak) are completely ionised and the
interionic effects do not exist, each ion migrates independently of its co-ion.
This is the Kohlrausch’s law of independent migration of ions.
At infinite dilution, these ions contribute a definite share to the total molar
conductivity of the electrolyte. The share depends the nature of the ion and is
independent of the counterion in the electrolyte. Under such conditions, the
molar conductivity of an electrolyte at infinite dilution can be represented as
the sum of molar conductivities of individual ions at infinite dilution. That is for
a uni-uni (1:1) electrolyte AB, we can write,
Λm0 (AB) = 0m (A + ) + 0m (B− ) …(5.16)
Where 𝜆0𝑚 (A+ ) 𝑎𝑛𝑑 𝜆0𝑚 (B − ) are the limiting molar conductivities of the A+ and
B- ions. For other than uni-univalent electrolytes, the molar conductivity can be
given by the following expression
0
Λm =  +0+ + −0− …(5.17)
Where,  + and  − are the number of cations and anions generated by the
dissociation / ionisation of the electrolyte and 0+ and 0− are the limiting molar
conductivities of the cation and anion respectively. The limiting molar
136 conductivities of some common ions are given in Table 5.1.
Table 5.1: The limiting molar conductivities of some common ions at 298 K
Ion 0/ S cm2 mol-1 Ion 0/ S cm2 mol-1
H+ 349.6 OH– 199.1
Li+ 38.7 F– 55.4
Na+ 50.1 Cl– 76.3
K+ 73.5 Br – 78.1
Ag+ 61.9 CH3COO– 40.9
Mg2+ 106.0 SO42– 160
Ca2+ 119.0 PO43– 278.4
An important application of Kohlrausch’s law of independent migration of ions

is that it allows us to calculate the molar conductivity of a weak electrolyte at
infinite dilution by suitably adding and subtracting the molar conductivities of
appropriate strong electrolytes. For example, the molar conductivity of acetic
acid at infinite dilution can be obtained by adding the molar conductivities at
infinite dilution for HCl and CH3COONa and subtracting that of NaCl from the
sum as given below.
Λm0 (CH3COOH) = Λm0 (HCl) + Λm0 (CH3COONa) − Λm

0
(NaCl) …(5.18)
(H0 + 0cl- ) + (Na

0
+ + 
0
CH - ) - (Na
0
+ +  - - ) = ( + + 
0 0 0
- ) = Λm0 (CH3COOH)
3 COO Cl H CH
3 COO
The experimental values of molar conductivities at infinite dilution for HCl,

CH3COONa and NaCl are 425.9, 91.0 and 126.4 S cm2 mol–1, respectively.
These can be substituted in the above expression to get the molar conductivity
of acetic acid at infinite dilution as follows
Λm0 (CH3COOH) = 425.9 + 91.0 − 126.4 = 390.5 S cm2 mol −1 …(5.19)

Let us calculate the same by using the limiting molar conductivities of the H+
and CH3COO– ions from Table 5.1.
0
Λm (CH3COOH) = H0 + + 0CH COO- = 349.6 + 40.9 = 390.5 S cm2 mol −1 …(5.20)
3
There is an excellent agreement between the calculated values. Let us now

sum up what have we learnt in this unit. However, before that you may solve
the following simple question to assess your learning.
SAQ 7
Calculate the molar conductivities of sodium sulphate and calcium phosphate
by using the data given in Table 5.1
5.6 SUMMARY
In this unit on conductance, we have basically focused on different aspects of
electrolytic conduction. We started the unit by introducing conduction in
electrolytic solutions and explained the mechanism of electrolytic conduction in 137
terms of movement of ions under the influence of applied potential. This was
compared with metallic conduction wherein the conduction is due to
movement of electrons. Then we introduced the concept of conductance and
conductivity of electrolytic solutions and established the relationship between
them. The conductivity was defined as the conductance of all the ions present
in a unit cube of the electrolytic solution.
Thereafter we discussed different factors affecting conductivity of electrolytic

solutions and explained the principle of measurement of conductance of
electrolytic solutions. This was followed by an introduction to the concept of
molar conductivity which is defined as the conductance of a volume of solution
containing the ions obtained from one mole of a dissolved electrolyte when
placed between two parallel electrodes which are at a unit distance and are
large enough to contain the whole solution between them. Having explained
the concept of conductivity we discussed the concentration dependence of
conductivity and molar conductivity of electrolytic solutions. In this context the
difference in the behaviour of solutions of weak and strong electrolytes was
highlighted and explained. This led to the introduction of the concept of limiting
molar conductivities and the Kohlrausch’s law of independent migration of
ions. The rationale for the law and its applications were also taken up.
5.7 TERMINAL QUESTIONS

1. Explain the mechanism of conduction in metallic conductors.
2. List different factors affecting conductivity of an electrolytic solution.
3. Give the relation between the conductance and conductivity of an

electrolytic solution measured with a conductivity cell having a cell
constant equal to 1.0 cm−1 .
4. The resistance of a 0.10 M solution of potassium chloride taken in a

conductivity cell at 25 °C is found to be 24.96 Ω. If at 25 °C the
conductivity for 0.1 M solution of KCl is 0.011 639 S cm–1; calculate the
cell constant.
5. Define molar conductivity and give its SI units.
6. The resistance of a 0.01 M solution of acetic acid measured at room

temperature with a conductivity cell having a cell constant of 0.40 cm−1
was found to be 2770 Ω. Calculate the molar conductivity of acetic acid at
this concentration.
7. What is conductivity water? Why do we need to use it in the conductance

measurement experiments?
8. State Kohlrausch’s law of independent migration of ions.
9. The molar conductivities at infinite dilution for hydrochloric acid, sodium

monochloroacetate and sodium chloride are observed to be 425.9, 89.8
and 126.4 Scm2 mol–1 respectively. Calculate the molar conductivity of
138 monochloroacetic acid at infinite dilution.
5.8 ANSWERS
Self Assessement Questions
1. In metallic conductors the current is carried by the electrons whereas in
case of electrolytic conductors it is carried by ions.
2. The conductivity of a solution can be defined as the conductance of all the
ions in the electrolytic solution present in a unit cube. The conductance, G
and conductivity,  of a solution is related as
A
G =
l
Where A is the surface area of the electrodes and l is the distance
between them.
3. We know from Eq. (5.10) that
1
Conductivity =  cell constant
resistance
Rearranging, we get Cell constant = conductivity  resistance
Substituting the values, we get,

Cell constant = 1.46  10-4 S cm−1  1500 S−1 = 0.219 cm−1
4. We are given the surface area of electrodes and distance between them
in the conductivity cell. This can be used to calculate the cell constant
distance 0.9 cm
Cell constant = = = 0.5 cm−1
area 1.8 cm2
1
We know that Conductivity =  cell constant
Resistance
Substituting the values of resistance and cell constant we get,
1
Conductivity,  =  0.5 cm−1 = 1.79  10-5 S cm−1
2800 S-1
1
5. We know that Conductivity =  cell constant
Resistance
Given: Resistance= 180 Ω =180 S–1; cell constant = 0.6 cm–1
1
= -1
 0.6 cm−1 = 3.33  10− 3 S cm−1
180 S
Once we know the value of conductivity, we can compute molar
conductivity by using the following expression (where concentration is in
mol dm-3)
1000 
= Λm = S cm2 mol −1
c
Substituting the values,
1000 cm3dm-3  3.33  10-3 S cm-1
= Λm = -2 −3
= 53.28 S cm2 mol −1
6.25  10 mol dm
139
6. We know that
1
Conductivity =  cell constant
resistance
Rearranging we get Cell constant = Conductivity × resistance
Given:
Conductivity = 0.277 Ω–1m–1 = 0.00277 S cm–1 ; Resistance = 250 S–1
Cell constant = 0.00277 S cm−1  250 S−1 = 0.6925cm−1
Now we know that

distance between the electrodes, 
cell constant =
surface area of electrodes, A
Rearranging we get,
Distance between the electrodes =
cell constant  surface area of the electrodes
Distance between the electrodes = 0.6925 cm–1  2 cm2 = 1.385 cm
7. We know that the molar conductivity at infinite dilution for an electrolyte is
given as
= Λm0 =  + 0+ + −0−
Where,  + and  − are the number of cations and anions generated by the
dissociation / ionisation of the electrolyte and 0+ and 0− are the limiting
molar conductivities of the cation and anion respectively.
To calculate the molar conductivity at infinite dilution for sodium sulphate

we write the equation for dissociation of sodium sulphate as
Na 2SO 4 → 2Na + + SO24−
The molar conductivity at infinite dilution would be

Λm0 (Na 2SO 4 ) = 2Na
0
+ + 
0
SO2−
4
Substituting the values of limiting molar conductivities of the ions from

Table 5.1 we get
Λm0 (Na 2SO 4 ) = (2(50.1) + 160) S cm2mol −1 = 260.2 S cm2 mol −1
For calcium phosphate the dissociation of salt would be as
+
Ca3 (PO4 )2 → 3 Ca2 + 2 PO34−
The molar conductivity at infinite dilution would be
Λm0 (Ca3 (PO4 )2 ) = 3 0Ca2+ + 2 PO
0
3−
4
Substituting the values of limiting molar conductivities of the ions from

Table 5.1 we get
140 Λm0 (Ca3 (PO4 )2 ) = (3(119)) + 2(278.4))S cm2 mol −1 = 913.8 S cm2 mol −1
Terminal Questions
1. The mechanism of conduction in metallic conductors can be explained in
terms of the electron sea model. According to this model a metallic solid
can be viewed as a fixed array of positively charged metal ions
surrounded by a sea of mobile electrons, provided by the valence
electrons of the atoms. When an electrical field is applied across the metal
wire, the electrons move through the lattice of positive ions in response to
an applied electric field. A certain number of electrons enter the metal at
one end and an equal number of electrons come out of the other end.
2. The factors affecting the conductivity of an electrolytic solution are as

under:
• the concentration of ions

• the nature of the electrolyte;
• the dielectric constant of the solvent;
• interionic interactions;
• viscosity of the solvent;
• size of the ions and their solvation; and
• temperature
3. The conductivity and conductance of an electrolytic solution are related as

Conductivity = Conductance  cell constant
If the value of cell constant= 1.0 cm−1 then the magnitude of conductivity will
be same as that of measured conductance. However, you must remember
that the units of conductance are S–1 whereas for conductivity it is S–1 cm–1.
4. From Eq. (5.10), we know that
1
Condutivity =  cell constant
resistance
Rearranging, we get
Cell constant = condutivity  resistance
Substituting the values, we get,
Cell constant = 0.011639 S cm-1  24.96 S−1 = 0.29 cm−1
5. Molar conductivity is defined as the conductance of a volume of solution

containing the ions obtained from one mole of a dissolved electrolyte
when placed between two parallel electrodes which are at a unit distance
and are large enough to contain the whole solution between them. The SI
units of molar conductivity are S m2 mol–1.
6. From Eq. (5.10), we know that

1
Condutivity =  cell constant
resistance 141
We are given,
Resistance = 2770 Ω = 2770 S–1 and Cell constant= 0.40 cm–1
Conductivity = 1
 0.40 cm−1 = 1.44  10- 4 S cm-1
2770 S −1
1000 
We know that molar conductivity = Λm = S cm2mol −1
c
Substituting the values of conductivity and concentration, we get
1000cm3 dm −3  1.44  10 −4 cm
= Λm = = 1.44 S cm2 mol -1
0.01 mol dm−3
Thus, the molar conductivity of 0.01 M solution of acetic acid is computed

to be 14.4 S cm2 mol–1
7. A sample of water that is free from all types of ionic impurities and has
negligible conductivity is called conductivity water. It is obtained by
repeated distillation of water. It is important to use conductivity water in
conductance measurement experiments because the conductivity of the
ions contributed by impurities introduce error in the conductivity
measurement of a sample.
8. Kohlrausch law states that at infinite dilution, all electrolytes are

completely ionised and the interionic effects do not exist, therefore each
ion migrates in solution independent of other ions. Under such conditions,
the molar conductivity of an electrolyte at infinite dilution can be
represented as the sum of molar conductivities of individual ions at infinite
dilution.
9. The molar conductivity of a monochloroacetic acid at infinite dilution can

be obtained by adding the molar conductivities at infinite dilution for HCl
and ClCH2COONa and subtracting that of NaCl from the sum as given
below.
Λm0 (ClCH2COOH) = Λm0 (HCl ) + Λm0 (ClCH2COONa ) − Λm0 (NaCl )
( ΛH0 + 0cl− ) + (Na

0
+ +
0
ClCH COO−
) − (Na
0
+ +  − ) = ( + + 
0
Cl
0
H
0
ClCH COO−
)
2 2
= Λm0 (ClCH2 COOH)
The values of molar conductivities at infinite dilution for HCl,

ClCH2COONa and NaCl are given as 425.9, 89.8 and 126.4 S cm2 mol–1,
respectively.
Substituting these values in the above expression we get
Λm0 (ClCH2COOH) = 425.9 + 89.8 − 126.4 = 389.3 S cm2 mol −1
142
Unit 6 Conductance-II
UNIT 6
Conductance-II
Structure
6.1 Introduction Determination of Solubility and
Solubility Product of Sparingly
Soluble Salts
6.2 Ionic Mobilities and
Determination of Ionic Product of
Transference Number
Water
6.3 Determination of Transference
Determination of Hydrolysis
Numbers
Constant of a Salt
Hittorf’s Method
6.5 Conductometric Titrations
Moving Boundary Method
6.6 Summary
6.4 Applications of Conductivity
Measurements
6.8 Answers
Determination of Ionisation
Constant of a Weak acid
6.1 INTRODUCTION
In the previous unit you have learnt about some aspects of electrolytic
conduction. You have learnt about basic concepts like conductance,
conductivity, and molar conductivity in terms of interrelations between them,
their significance, determination, and factors affecting them. In this unit we
would continue our learning of electrolytic conduction and take up two main
aspects viz., the migration of ions and the application of conductance
measurements.
We would begin the unit by discussing migration of ions in an electrolytic

solution under the influence of applied potential. In this context we would
introduce the concepts of ionic mobility and transference numbers. We would
then take up the principle and experimental methods of determination of
transference numbers. This will be followed by different applications of
conductance measurements. These include determination of: ionisation
constant of weak acids, ionic product of water, solubility and solubility product
of sparingly soluble salts and degree of hydrolysis and hydrolysis constant for
a salt. In addition, we would also take up conductometric titrations as
application of conductance measurements. 143
In the next unit we would take up electrochemical cells in terms of their types,
representation and emf etc.

❖ define ionic mobility and outline its significance;
❖ list and explain factors affecting ionic mobility;
❖ define transference numbers and relate them to ionic mobilities;
❖ explain the principles of Hittorf’s and moving boundary methods for the
determination of transference numbers;
❖ describe the procedure of Hittorf’s method and moving boundary method

for the determination of transference numbers;
❖ define indicator electrolyte and list the requirements for an electrolyte to

be indicator electrolyte in the moving boundary method;
❖ solve problems based on Hittorf’s and moving boundary methods;
❖ list some important applications of conductivity measurements;
❖ explain the conductometric determination of ionisation constant of a

weak acid;
❖ determine solubility and solubility product of a sparingly soluble salt

using conductance measurement data;
❖ explain the method of determination of ionic product of water using

conductance measurements;
❖ state the importance of conductometric titrations; and
❖ explain the titration curves for the titration of weak (or strong) acids with
a strong base.
6.2 IONIC MOBILITIES AND TRANSFERENCE

NUMBERS
In any measurement of conductance of an electrolytic solution we get the
amount of current carried by all the ions present in the solution. However,
fraction of the total current carried by each type of ions is not necessarily the
same. It has been found that in dilute solutions of magnesium sulfate the
fraction of current carried by magnesium ion is about 0.38 (38%) of the total
current, whereas the sulfate ions carry the remaining 62%. The difference in
the amount of current carried by the cation and anion can also be inferred by
the limiting molar conductivities of ions about which you have learnt in the
previous unit. You would recall that in an aqueous solution of acetic acid at
infinite dilution the molar conductivities of hydrogen ions and acetate ions are
349.6 S cm2 mol−1 and 40.9 S cm2 mol−1 respectively. Since at infinite dilution,
144 the ions are free from interionic interactions, the difference in these values can
be attributed to their different speeds or velocities. However, at ordinary
concentrations though the ions do not move independent of other ions, yet
they have different speeds and carry different amount of current. The speed of
different ions is identified in terms of their ionic mobilities. Let us understand
what is ionic mobility of an ion?
6.2.1 Ionic Mobility
In a solution of an electrolyte the ions move randomly. However, in an any act
of measurement of conductivity of the solution an electric field is applied
across the electrodes. The ions then move under the influence of the applied
electrical field. The applied field provides a direction to the ions and
accelerates them. This causes a net migration of ions in the solution towards
oppositely charged electrodes; cations towards cathode and anions towards
anode. In addition, as mentioned above, at moderate concentrations the ions
are not free from interionic interactions. Therefore, the ions experience a
frictional retardation from other ions. Thus, the ions experience two types of
forces viz., electrical field and frictional retardation and these two forces act in
opposite directions. When the acceleration due to the applied electric field
becomes equal to the frictional retardation force the ions drift towards the
opposite electrodes with a net speed called drift speed or drift velocity
denoted by𝑠. The drift speed is proportional to the electrical field, E and we
can write
s = uE …(6.1)
where, the proportionality constant, u is called ionic mobility. If the electrodes
are at a distance of 1m apart and a potential of 1V is applied across them i.e.,
the potential gradient is 1 Vm−1 then we can write
s =u …(6.2)
Thus, we can define ionic mobility to be the velocity with which an ion in a
solution would move under a potential gradient of 1 Vm−1. The SI unit for ionic
mobility can be obtained as follows
s m s −1
u= = = m2 V −1s −1 …(6.3)
E V m −1
The ionic mobilities of some common ions are given in Table 6.1.
Table 6.1: Ionic Mobilities of Some Ions in Water at 298 K
Cation u / (10–8m2s–1V–1) Anions u / (10–8m2s–1V–1)

H+ 36.23 OH– 20.64
Li+ 4.01 F– 5.74
Na+ 5.19 Cl– 7.92
K+ 7.62 Br– 8.09
Mg2+ 5.50 NO3– 7.41
Ca2+ 6.17 SO42– 8.29
The significance of ionic mobilities is that these provide a link between

measurable and theoretical quantities. The theoretical quantity, ionic mobility
(u) is related to measurable quantity, molar conductivity () of the ions as
follows: 145
 = zuF …(6.4)
Where, F is the Faraday’s constant, (F = NA e = 96485 C). For the solution of

an electrolyte at infinite dilution (when interionic interactions do not exist), we
know that
Λm0 = v + 0+ + v −0− …(6.5)
Substituting for molar conductivities of ions from Eq. (6.4) we get,
Λm0 = ( z+u+v + + z−u−v − ) F …(6.6)
Having learnt about ionic mobility and its significance, let us learn about the
factors affecting ionic mobilities
Factors affecting ionic mobilities
The ionic mobility of an ion depends on several factors, some of the important
factors are as under:
• Charge on the ion: an ion with a higher charge has higher ionic mobility
as it would experience a greater force due to electric field (F = zeE),
where z is the charge on the ion, e is the elementary charge and E is the
electric field strength.
• Radius of ion: smaller the ion higher the ionic mobility as a smaller ion
due to smaller surface area experiences lesser friction and can move
easily through the solvent.
• Viscosity of the medium: higher the viscosity, lower the ionic mobility
because the ion will experience a greater frictional force
We can make two important observations from the data given in Table 6.1.
First, that the ionic mobilities of hydrogen and hydroxide ions are exceptionally
high; more than that can be attributed to the small size. Secondly, the trend in
case of alkali metal ions and halide ions are contrary to that expected from
variation in their sizes. Let us learn about the explanation for the observations.
First, we take up high ionic mobilities of hydrogen and hydroxide ions.
The exceptionally high ionic mobilities of hydrogen and hydroxide ions was
explained initially by suggesting that in case of these ions in water there are
two mechanisms by which the conduction takes place. The first one is same
as discussed above for any other ion. The second mechanism called
Grotthus conduction mechanism and is specific to hydrogen and hydroxide
ions. According to this mechanism the proton binds to a neighbouring water
molecule and momentarily converts it to a hydronium ion. This in turn transfers
its proton to another molecule in neighborhood which does the same to
another molecule and this process continues. As a result, a proton in any
region of the solution is effectively transported very quickly to another part.
This mechanism is also known as proton hopping mechanism. A schematic
representation of such a mechanism for movement of proton and hydroxide
ions is given in Fig. 6.1. It is important to note here that the actual mechanism
146 is still under investigation.
(a) (b)
Fig. 6.1: Schematic representation of Grotthus conduction mechanism for (a) H+

and (b) OH– ions.
Now, we take up the second observation. That is, the trend in the ionic
mobilities of alkali metal ions and halide ions. The observed trend is opposite
to the expected trend because these ions get hydrated and their effective size
increases. The extent of hydration depends on the charge density [charge /
(radius)2] of the ions. The charge on all alkali metal ions is same (1unit positive
charge) but since Li+ ion is the smallest it is heavily hydrated. This makes the
hydrated ion large, and hence it moves only slowly. In comparison though the
Na+ and K+ ions are larger in size; the extent of their hydration is lesser and
hence their effective size is smaller than that of hydrated lithium ion. The sizes
of some alkali metal ions in unhydrated and hydrated state and their ionic
mobilities are given below.
Ion Ionic radius of Approximate radius of Ionic mobility /

unhydrated ion / pm) hydrated ion / pm (10–8m2s–1V–1)
Li+ 76 340 4.01
Na+ 102 276 5.19
K+ 138 232 7.62
6.2.2 Transference Numbers

As discussed above, the current is transported through a solution by migration
of positive as well as negative ions and the ionic mobility or speed of ions are
different. The question comes up is that out of the total current carried in the
solution what is the contribution of different ions? Are these same or different?
How do we determine it? For this we define a new parameter called
transference number (also called transport number). It is defined as the
fraction of current carried by a given type of ion.
In order to derive an expression for transference number, we consider two
electrodes that are separated by a distance d and contain a solution of an
electrolyte between them. Let the solution have n+ positive ions having a
charge of z+ units each and have n− negative ions having a charge of z− units
each. When we apply a unit potential difference across the electrodes these
ions move towards the oppositely charged electrodes. Let us assume that the
cations have a mobility of u+ whereas the anions have a mobility equal to u−. A 147
schematic set up to establish a relationship between ionic mobility and

transference number is given in Fig. 6.2.
Fig. 6.2: A schematic set up to establish a relationship between ionic mobility

and transference number.
Now, let us try to calculate the current transferred by the cations and anions in
one second. We find that all the cations present in the volume of solution
enclosed between the negative electrode (cathode) and the plane A’B’C’D’ in
the figure (this plane is at a distance of u+ from the negative electrode) would
move to the electrode. The current carried by the cations can be calculated as
follows:
Total number of positive ions present in the solution: n+ …(6.7)
Volume of the solution = area ABCD  d …(6.8)
n+
Number of positive ions per unit volume = …(6.9)
area ABCD  d
Volume of the solution from which all the postive ions will reach the
negative electrode = area ABCD  u+ …(6.10)
The number of positive ions reaching electrode in one sec =

n+ nu
=  area ABCD u+ = + + …(6.11)
area ABCD  d d
Quantity of electricity associated with each positive ion = z+e …(6.12)
n+u+ z+e
➔ the current carried by positive ions in one sec = I + = …(6.13)
d
Similarly, in one second all the negative ions between the positive electrode
(anode) and the plane ABCD would reach the electrode. As above, we can
show that
n−u− z−e
➔ the current carried by negative ions in one sec = I − = …(6.14)
d
Total current conducted by the ions in one second =
n+u+ z+e + n−u− z−e
I = I+ + I− = …(6.15)
d
As the overall solution has to be neutral, n+ z+e = n−z−e …(6.16)
Substituting in Eq. (6.15), we get total current conducted in one sec =
n+ z+e(u+ + u− )
I= …(6.17)
148 d
The fraction of current carried by cations =
I + n+ z+e(u+ ) d u+
t+ = =  = …(6.18)
I d n+ z+e (u+ + u− ) u+ + u−
Similarly, the fraction of current carried by anions =

I − n− z−e(u− ) d u−
t− = =  = …(6.19)
I d n− z−e (u+ + u− ) u+ + u−
u+ u−
Thus, t+ = and t− = …(6.20)
u+ + u− u+ + u−
There are two important corollaries of the expressions for transport numbers.
t+ u+ u + u− u+
=  + = …(6.21)
t − u+ + u− u− u−
i.e., the ratio of transport numbers of two ions in an electrolyte is same as the
ratio of their ionic mobilities
u+ u− u + u−
t+ + t− = + = + =1 …(6.22)
u+ + u− u+ + u− u+ + u−
i.e., the sum of transport number of the cation and the anion is equal to one.
You may note that in this derivation we have assumed that the potential
difference between the two electrodes is 1V therefore the expressions for the
transport numbers are in terms of ionic mobilities which are the ionic velocities
per unit potential. If we use the potential difference other than 1V, then the
expressions would have velocities in place of ionic mobilities; i.e.,
v+ v−
t+ = and t − = …(6.23)
v+ + v− v+ + v−
You would recall that in the beginning of Section 6.2 we mentioned that in a
measurement of electrical conductivity we get the total current carried by the
cations and the anions. To evaluate the contribution of individual ions we
defined the concept of ionic mobility and related it to the molar ionic
conductivity through Eq. (6.6). However, we cannot measure the ionic
mobilities directly. Therefore, we have defined a new parameter viz., transport
number that represents the fraction of total current carried by a given ion in
solution. The transference numbers are related to the ionic mobilities by
Eq. (6.20). The transference numbers can be measured experimentally and
provide a way of getting the individual ionic mobilities. Let us learn about their
experimental determination. However, before that solve the following simple
questions to gauge your understanding.
SAQ 1
Define ionic mobility and give its SI unit.
SAQ 2
What are transference numbers? How are these related to ionic mobilities?
149
6.3 DETERMINATION OF TRANSFERENCE

NUMBERS
As stated above, an experimental determination of transference numbers of
ions in an electrolyte are important to evaluate the contribution of individual
ions to the overall electrical conductivity of the solution of an electrolyte. Three
methods are generally employed for the experimental determination of
transference numbers. These are
• Hittorf’s method
• Moving boundary method
• Emf measurement method
We would take up the first two methods here. The Hittorf’s method is based on
the measurement of change in concentration in the vicinity of the electrodes
whereas in the moving boundary method we study the rate of movement of the
boundary between two solutions under the influence of current. Let us learn
about these methods one by one.
6.3.1 Hittorf’s Method
As mentioned above, in Hittorf’s method we measure the changes in the
concentration of electrolyte in the vicinity of electrode in an electrolytic cell. We
need to first understand why the concentration around the electrodes changes
and how is it related to the transport numbers. For this we consider an
electrolytic cell which has an equivalent number of positive and negative ions,
as shown schematically in Fig. 6.3 (A).
The arguments that follow will be valid for any kind of electrolyte but for
simplicity we are considering a simple uni-univalent electrolyte. This cell is
arbitrarily divided by the imaginary planes into three compartments, which can
be called cathodic, central, and anodic compartments. Before we apply
potential and the electrolysis begins, the condition of the cell is represented by
the upper part of Fig. 6.3 (A) in which each compartment has five equivalents
each of positive and negative ions.
In the first case we assume that only the cations can move under the influence
of an applied potential, and further, two equivalents of these ions move from
the anodic compartment to the cathode. The anions on the other hand are
practically immobile. The situation can be represented by lower part of
Fig. 6.3 (A), where we find that there are two equivalents of unpaired ions
each around the two electrodes. The anions get discharged on the anode by
giving their electrons and these electrons travel through the external circuit to
the cathode where they are taken up by the cations to get discharged. It is
interesting to note that though only the positive ions were able to move (i.e.,
carry current), equivalent amounts of the cation and anions are discharged at
the respective electrodes. This is in accordance with Faraday’s law which you
would have learnt in your school chemistry.
Let us now consider second case where we assume that the cations as well
as the anions can move and move with same velocity (mobility). The initial and
final situation in this case will be represented by Fig. 6.3 (B). Here we have
150 assumed that two equivalents of cations have moved from anodic
compartment to the cathode and two equivalents of anions have moved from
the cathodic compartment to the anode. As a consequence, there are four
equivalents of unpaired ions each at the two electrodes and as in the first case
these would get discharged at the respective electrodes. Once again, we find
that the amounts of the cation and anions discharged at the electrodes are
equal.
Fig. 6.3: A schematic illustration of depletion around anode and cathode.
In the third case represented by Fig. 6.3 (C) we have assumed that the cations
and anions move at different velocities. The cation to anion velocity is in the
ratio of 2:3. In other words, when in certain time two equivalents of cations
have moved from anodic compartment to cathode, three equivalents of anions
have moved from cathodic compartment to anode. Thus, there are five
equivalents of unpaired ions each at the two electrodes and get discharged
there.
So, what do we find in these illustrative cases? First, we find that the current is This statement is
called as Hittorf’s
carried by those ions which move and secondly the amount of current carried
rule and forms the
by a given kind of ion is proportional to its speed. We can also say that the basis of determination
fraction of current carried by a given type of ion i.e., its transference number is of transference
proportional to its speed. In all these arguments we have made an important numbers by Hittorf’s
assumption that the discharged ions do not react with the material of the method.
electrodes. If we look at Fig. 6.3 again, we can make one more observation
that the loss of concentration of electrolyte around any electrode is
151
proportional to the speed of the ion moving away from it. We can, therefore,
write
Moles of electrolyte lost from the anodic compartmen t t
= + …(6.24)
Moles of electrolyte lost from the cathodic compartmen t t −
This is valid only for a 1:1 electrolyte. Now, the total moles of electrolyte lost
will be sum of the electrolyte lost from the anodic and cathodic compartments.
These can also be obtained from the total amount of current passed through
the cell. We can write,
Moles of electrolyte lost from the anodic compartmen t
t+ = …(6.25)
Total number of moles of electrolyte lost
Moles of electrolyte lost from the cathodic compartmen t
t− = …(6.26)
Let’s learn about the experimental method of determination of transference

numbers by Hittorf’s method.
Experimental determination of transference numbers by Hittorf’s method
The Hittorf’s apparatus for the determination of transference numbers consists
of two vertical glass tubes joined through a U-tube with stopcocks at the tops
of the two limbs of the U-tube. The two vertical glass tubes represent the
anodic and cathodic compartments whereas the U-tube represents the middle
compartment. Each of these tubes is provided with stopcocks at the bottom.
The stopcocks in the two limbs of the U-tube are used to connect / disconnect
the solutions in the cathodic and anodic compartments with the middle
compartment.
Fig. 6.4: Hittorf’s experimental set up for the determination of transport numbers.
The three-tube apparatus (also called Hittorf cell or transport cell) is connected
in series with a silver coulometer through a variable resistance, a milli
ammeter and battery as shown in Fig. 6.4. The milliammeter allows to adjust
the current to any desired value. The anodic and cathodic tubes are provided
with an electrode each. (these could be platinum electrodes or metal
electrodes depending on the system). The cell is filled with the electrolyte for
which the transport numbers are to be determined. The current is turned on,
and the solution is allowed to undergo electrolysis for sufficient amount of time
152 such that there is appreciable change in the concentrations in the anodic and
cathodic compartments. Thereafter, the solution is drained from each
electrode compartments and analysed. The total quantity of electricity passed
(or total amount of electrolyte discharged) is obtained from the increase in
weight of the cathode in the coulometer attached in series. The analysis of the
solution from the central compartment provides the initial concentration of the
electrolyte (as it is not expected to change). However, if the initial
concentration is known, the analysis of solution from the central compartment
may be skipped. The changes in the amount of electrolyte in the electrode
compartments are then used to determine the transference numbers as
discussed above. Let us understand it with the help of an example.
Example 6.1: A solution containing 19.23 g of silver nitrate in 50 cm3 of solution

was taken in a Hittorf cell using platinum electrodes for the
determination of transport numbers. After the experiment 50 cm3 of
anodic compartment solution contained 18.47 g of silver nitrate. If
0.982 g of metallic silver was deposited on the cathode, calculate
the transport number of the ions.
Solution: We know that the transport number of the cation is defined as
t+ =
First, we would calculate the total number moles of electrolytes lost. You have
learnt above that it is equal to the total amount of electricity passed. This can
be calculated from the amount of silver deposited on the cathode.
0.982 g
The amount of silver deposited on cathode = = 0.00912 mol
107.88 g mol −1
Decrease in the amount of AgNO3 in the anode compartment =

(19.23 −18.47) = 0.76 g
0.76 g
In terms of number of moles = = 0.00447 mol
169.87 g mol −1
0.00447 mol
Substituting in the expression for t + : t Ag+ = = 0.49
0.00912 mol
We know that t + + t − = 1 So tNO− = 1 − 0.49 = 0.51
3
This was quite a simple and straightforward problem because platinum

electrodes are used, and it is not affected in the anode compartment.
However, if we use silver electrodes then the calculation becomes a little more
involved. Let us take one more example.
Example 6.2: In the determination of transport number a solution of silver nitrate

containing 0.00739 g of silver nitrate per gram of water was taken
in the Hittorf cell using silver electrodes. After a certain amount of
current was passed for enough time, 0.0624 g of silver was
deposited on the cathode. An analysis of the solution from anode
compartment showed that the solution contained18.5 g of water
and 189 mg of silver nitrate. Calculate the transport number of the
silver and nitrate ions.
Solution: We know that the transport number of the cation is defined as 153
t+ =
Once again, first we would calculate the total number moles of electrolytes
lost. This can be calculated from the amount of silver deposited on cathode.
0.0624 g
The amount of silver deposited on cathode = = 0.000578 mol
107.88 gmol −1
Since in this case we are using silver electrodes, so an equivalent amount of

silver will dissolve from the silver anode i.e., 0.000578 moles. Thus, the
concentration of silver nitrate would increase by 0.000578 moles in the anode
compartment.
We are given the final amount of silver nitrate in the anode compartment as
189 mg of silver nitrate and 18.5 g of water i.e.,
0.189 g
Final number of moles of silver nitrate = = 0.00111mol
169.87 g mol −1
Initial number of moles of silver nitrate in the anode compartment can be

obtained by calculating silver nitrate in 18.5 g of water
18.5 g water  0.00739 g AgNO 3 per g water

= 0.0008 mol
169.87 g mol −1
The number of moles of silver nitrate transferred from anode compartment =
= Initial no. of moles + Moles formed by dissolution of electrode

– final no. of moles
= 0.0008 + 0.000578 – 0.00110 = 0.000278 mol
Substituting in the expression for transport number, we get
0.000278 mol
t A+ = = 0.48
g 0.000578mol
We know that
t+ + t− = 1
So tNO− = 1 − 0.48 = 0.52

3
Having learnt about the Hittorf’s method let us now take up moving boundary
method. However, before that answer the following questions to assess your
understanding.
SAQ 3
List different experimental methods for the determination of transference
numbers.
154
SAQ 4
A 0.2000 molal solution of copper sulphate was taken in a Hittorf cell having
copper electrodes. After passing suitable current for sufficient time the
cathode solution from the cell was analysed. It was found to weigh 36.4340 g
and contained 0.44125 g of copper. On the other hand, the cathode in the
coulometer showed a deposition of 0.0405 g of silver. Calculate the
transference numbers of the copper and sulphate ions.
6.3.2 Moving Boundary Method

As the name suggests, in the moving boundary method the motion of ions
under the influence of an applied potential is observed in terms of a moving
boundary. It is relatively simple and accurate method and used extensively. In
one of the variants of this method we use two electrolytes, one whose
transference numbers are to be determined (called principal electrolyte) and
the other electrolyte that acts as indicator electrolyte.
The indicator electrolyte must meet the following criteria
• If we wish to measure the cation of the electrolyte, then the indicator
electrolyte must have an anion common with it. For example, if we wish to
determine the transference number of the cation of the electrolyte MA
then the indicator electrolyte would be MA. For anion, it would be MA.
• The speed of the M+ ion shall be less than that of M+ and that of A−
shall be less than that of the A − ion.
In a typical determination, the solutions of these electrolytes are taken in the
moving boundary apparatus. It is a glass tube having uniform diameter
mounted vertically with two electrodes at the ends. Similar to the Hittorf’s
method, these electrodes are connected in series with a silver coulometer
through a variable resistance, a milli ammeter and battery as shown in
Fig. 6.5 (a). The solutions are so arranged that the boundary between them is
quite sharp. The boundary between the solutions is generally located due to
the difference in their refractive indices or the colour. Further, to avoid mixing
of solutions and loss of the boundary, the solutions are placed in the order of
decreasing density.
Fig. 6.5: Schematic experimental set up for the determination of transport

numbers by moving boundary method. 155
Now, once the suitable indicator electrolyte is identified the two solutions are
loaded as shown schematically in the Fig. 6.5 (b), a distinct boundary is
formed at b. On applying potential, the M+ and M+ ions move towards cathode
and the boundary between them also moves.
After sufficient time the boundary reaches b'. As the mobility of M+ ions is
lesser than the M+ ions these are sometimes called following ions.
The distance bb’ would depend on the speeds of the ions being determined
(M+ ). As there is a uniform potential through the solution MA, distance bb’ will
be proportional to the ionic mobility u+ of the M+ ion and can be used to
determine the transference number. Let us understand it with the experimental
determination of the transference number of hydrogen ions.
Experimental determination of transference numbers by moving

boundary method
In the determination of transference number of hydrogen ions in HCl we use

cadmium chloride as the indicator electrolyte having a common anion. The cell
is filled first with cadmium chloride and HCl is added on top of it and a sharp
boundary is obtained. A platinum wire is inserted at the top of the cell to act
as the cathode and a stick of cadmium metal is used as the anode at the
bottom of the cell. A silver coulometer is connected with the cell in series
through a variable resistance, a milli ammeter and battery as shown in
Fig. 6.6.
Fig. 6.6: Schematic diagram showing experimental set up for the determination
of transference numbers of HCl by moving boundary method.
On applying potential, the hydrogen ions move towards the cathode at the top
of the cell and get discharged as hydrogen gas. As hydrogen ions move
toward the cathode their place is taken by cadmium ions, and the boundary
between two electrolytic solutions also moves upward. After suitable amount
of current is passed for sufficient amount of time the distance moved by the
boundary is used along with the cross-section area of the cell to obtain the
volume swept out by the moving boundary. This along with the total quantity of
electricity passed (as measured from coulometer) is then used to calculate the
transference number of hydrogen ion.
If the distance between b and b′, is 𝑙 cm and a cm2 is the cross-sectional area
156 of the tube, then the volume displaced by the moving boundary is 𝑙a cm3. If the
–3
concentration of HCl is c mol dm , the number of moles of HCl contained in
this volume would be 10-3 lac. If Q Coulombs of charge is passed through the
cell, then the charge carried by hydrogen ions would be t+Q. Further, as the
charge carried by 10-3 lac moles of H+ ions will be10-3 lacF, we can write
t +Q = 10−3 l  a  c  F …(6.27)
Rearranging we get,
10−3 l  a  c  F
t+ = …(6.28)
Q
Let us take an example to see the application of this expression.
Example 6.3: In the determination of transference numbers of HCl by moving

boundary method a 0.10 M solution of HCl was taken in a cell
having uniform area of cross section of 1.25 cm2. At the end of
experiment the boundary moved by 7.5 cm and 0.12 g of silver
was deposited on the cathode of silver coulometer. Calculate the
transference numbers of ions of HCl.
Solution: We know that for determination of transference number by moving
boundary method,
10−3 l  a  c  F
t+ =
Q
We have been given the values as:
𝑙 = 7.5 cm a = 1.25 cm2 and c = 0.1 mol dm−3
Let us first find the quantity of charge (Q) passed from the coulometer data.
We know that 1 F of charge would have deposited 107.88 g of silver. In other
words
107.88 g Ag  96485 C
96485 C  0.12 g
 0.12 g Ag  = 107.32C
107.88 g
Substituting the data in the expression for t+, we get

10−3  7.5 cm  1.25 cm2  0.1 mol dm−3  96485 C mol −1
t+ = = 0.84
107.32 C
Once we know the transference number of hydrogen ions, we can calculate

the same for chloride ions as
 t − = 1 − 0.84 = 0.16
The data on measurements of the transference number over a range of

concentration of electrolyte in dilute solutions shows that the plot between the
transference number versus square root of concentration is linear. The plot
can be extrapolated to c = 0 to obtain the value of the transference number at
infinite dilution.
Having learnt about transference numbers and their experimental
determination let us take up different applications of conductivity
measurements. However, before that solve the following simple questions to
assess your understanding. 157
SAQ 5
What is an indicator electrolyte? What is its role in moving boundary method?
SAQ 6
In the determination of transference number of Li+ ion by moving boundary
method a 0.10 M solution of LiCl was taken in a cell having uniform area of
cross section of 1.17 cm2. At the end of experiment the boundary moved by
2.1 cm and 0.083 g of silver was deposited on the cathode of silver
coulometer. Calculate the transference numbers Li+ ion.
6.4 APPLICATIONS OF CONDUCTIVITY

MEASUREMENTS
Conductivity measurement finds application in several analytical
determinations. In Unit 5 you have learnt about Kohlrausch’s law of
independent migration of ions according to which at infinite dilution, where all
electrolytes (strong or weak) are completely ionised and the interionic effects
do not exist, each ion migrates independently of its co-ion. There are a
number of important applications of conductivity measurement based on
Kohlrausch’s law of independent migration of ions. Some of these are
• Determination of ionisation constant for a weak acid
• Determination of solubility and solubility product of sparingly soluble salts
• Determination of ionic product of water
• Determination of hydrolysis constant of a salt
Let’s learn about these applications of conductivity measurements one by one
6.4.1 Determination of Ionisation Constant

of a Weak Acid
As discussed in Unit 5, the molar conductivity of a weak electrolyte (e.g., a
weak acid) at a given concentration is low due to its partial ionisation. The
molar conductivity increases with dilution due to further ionisation and at
infinite dilution it becomes maximum where the ionisation is complete (100%).
We can therefore say that the ratio of molar conductivity of a weak electrolyte
at a given concentration to that at infinite dilution would be a measure of
degree of ionisation of the weak electrolyte. In other words, we can say that
Λmc
= …(6.29)
Λm0
The ionisation of a weak acid HA can be represented as
HA (aq) ⇌ H+ (aq) + A − (aq) …(6.30)
If the degree of ionisation of the acid having concentration as c mol dm−3 is 

158 then the equilibrium concentrations of different species would be
HA (aq) ⇌ +
H (aq) + −
A (aq)
…(6.31)
c(1 −  ) c c
You would recall from Unit 8 of BCHCT-133 course that the ionisation constant
of a weak acid (a weak electrolyte) is given as
c 2
Ka = …(6.32)
(1 −  )
Where, c is the concentration and  is the degree of ionisation of the weak
acid. Substituting the expression for  in ionisation constant expression and
simplifying we get
2
 Λc 
c  m0 
Λ c( Λmc )2 c( Λmc )2
K a =  m c = = …(6.33)
 Λ   Λ0 − Λc  ( Λm0 ) ( Λm0 − Λmc )
1 − m0  ( Λm0 )2  m 0 m 
 Λm   Λ 
  m 
Let us take an example to see its application.
Example 6.4: The molar conductivity of a 0.1 M aqueous solution of acetic acid
is found to be 5.3 S cm2 mol−1. If the molar conductivity at infinite
dilution for acetic acid is 390.5 S cm2 mol−1, calculate the
ionisation constant of acetic acid.
Solution: We are given the following data:
c = 0.1 M, Λmc = 5.3 S cm2mol −1 and Λm0 = 390.5 S cm2mol −1
We know from Eq. (6.33) that ionisation constant is given as

c( Λmc )2
Ka =
( Λm0 ) ( Λm0 − Λmc )
Substituting the values in the above expression we get

0.1 (5.3 S cm2mol −1 )2
Ka =
(390.5 S cm2mol −1 ) (390.5 − 5.3) S cm2mol −1
Ka = 1.87  10−5
6.4.2 Determination of Solubility and Solubility

Product of Sparingly Soluble Salts
You would recall from Unit 9 of the BCHCT-133 course that when a sparingly
soluble salt MX is added to water an extremely small fraction of it dissolves
and generates ions by dissociation. These ions may combine back to give
solid salt. Over a period of time an equilibrium is established between the ions
obtained from the dissociation of dissolved salt and the solid salt i.e., we get a
saturated solution of the salt along with the undissolved solid salt. Such
equilibrium for a salt of MX type in aqueous solution can be represented as
MX(s) + H2O ⇌ M+ (aq) + A − (aq) …(6.34)
As the salt happens to be sparingly soluble, i.e., having extremely low

solubility and all the dissolved salt is ionised we can say that the solution can
159
be taken to be at infinite dilution. In other words, the measured molar

conductivity will be same as the molar conductivity at infinite dilution. We know
that
1000cm3dm−3 
Molar conductivity = S cm2 mol −1 …(6.35)
c
If, s is the molar solubility of the sparingly soluble salt i.e., c = s, we can write
1000 cm3dm−3 
Molar conductivity = Λm = S cm2mol −1 …(6.36)
s
Equating the measured molar conductivity with molar conductivity at infinite
dilution, we get
1000 cm3dm−3 
= Λm0 = S cm2mol −1 …(6.37)
s
Rearranging, the expression for solubility becomes
1000 cm 3 dm −3  ( S cm −1 ) 1000 
S= −1
= …(6.38)
0m 2
( S cm mol ) Λm0
The molar conductivity at infinite dilution can be obtained by using the molar
conductivities of the respective ions at infinite dilution by the following
expression.
Λm0 = v +0+ + v −0− …(6.39)
For the salt, MX we can write

Λm0 (MX) = 0m (M+ ) + 0m ( X− ) …(6.40)
The solubility product of the sparingly soluble salt (MX) can be written as
KSP = [ M+ ] [ X− ] = s 2 …(6.41)
Substituting the value of solubility in the solubility product expression, the

solubility product for the salt MX can be obtained as
2
 1000  
Solubility product = K SP =  0
 (mol 2 dm− 6 )
 …(6.42)
 Λm 
We have taken a 1:1 salt as an example; similar expressions can be obtained

for other types of salts.
Note: It is important to note here that since the solubility of sparingly soluble
salt is extremely low, its solution will have very low value of conductivity. In
such a case we cannot ignore the conductivity of water used for preparing the
solution. Therefore, the value of conductivity to be used in the expression for
solubility and solubility product must be corrected for water. That is,
 (salt ) =  (solution) −  ( water ) …(6.43)
Let us understand it with the help of an example.
Example 6.5: The conductivity of a saturated solution of AgCl in water (having

conductivity = 1.06  10−6 S cm−1) at a temperature of 291 K was
found to be = 2.47  10−6 S cm−1.The molar conductivities of
160 AgNO3, NaCl and NaNO3 at infinite dilution are given as 133.5,
2 −1
126.3 and 121.6 S cm mol respectively. Calculate the solubility
and solubility product of AgCl.
Solution: According to Eq. (6.38) the solubility in mol dm−3, conductivity and
molar conductivity at infinite dilution are related as
1000 cm3 dm−3   (S cm −1 )
s=
Λm0 (S cm2mol −1)
Let us first calculate the conductivity of the salt. As per Eq. (6.43) the
conductivity is given as
 (salt) =  (solution) −  (water )
 ( AgCl) = (2.47  10−6 S cm−1) − (1.06  10−6 S cm−1) = 1.41 10−6 S cm−1
Now, the molar conductivity at infinite dilution can be obtained by using

Kohlrausch’s law of independent migration of ions as follows:
Λm0 ( AgCl) = Λm0 ( AgNO 3 ) + Λm0 (NaCl ) − Λm0 (NaNO 3 )

Λm0 ( AgCl) = (133.5 + 126.3 − 121.6) S cm2 mol −1 = 138.2 S cm2 mol −1
Substituting the values of conductivity and molar conductivity at infinite dilution

in Eq. (6.38) we get
1000 cm3 dm−3   (S cm −1 ) 1000  1.41 10 −6 S cm−1
s= 0 2 −1
= 2 −1
= 1.02  10−5 mol dm−3
Λm (S cm mol ) 138.2 S cm mol
Now for AgCl the expression for solubility product can be written as
K sp = [ Ag + ] [Cl− ] = s 2
Substituting the value of solubility, we get

K sp = (1.02  10 −5 mol dm−3 )2 = 1.04  10 −10 mol 2 dm−6
SAQ 7
The molar conductivity of 0.01 M solution of acetic acid at 298 K was found to
be = 6.80 S cm2mol−1. If the molar conductivities of hydrogen and acetate ions
at infinite dilutions are = 349.8 and 40.9 S cm2mol−1, respectively. What
percentage of acetic acid is ionised at this temperature and concentration?
SAQ 8
Derive an expression for the solubility product of the salt MX2 from conductivity
measurement; assuming the solubility to be s mol dm−3.
6.4.3 Determination of Ionic Product of Water

You have learnt in the Unit-7 of BCHCT-133 course that water is amphoteric in
nature i.e., it can act as a weak acid as well as a weak base. In a sample of
water, a small number of water molecules donate a proton (thus acting as an 161
acid), which is accepted by equal number of other water molecules (acting as

base) as shown below
H2 O (𝑙) + H2O (𝑙) ⇌ H3O+ (aq) + OH− (aq) …(6.44)
As a consequence, a small concentration of H3O+ ions and OH− ions are

formed in a sample of water and this process is called autoprotolysis (or
autoionisation) of water. The product of the molar concentrations of H3O+ and
OH− ions in pure water sample at a given temperature is called the ionic-
product constant of water and is denoted as Kw
K w = [ H3O + ] [ OH− ] …(6.45)
We know that
The value of Kw can be experimentally determined from the measurement of
 electrical conductivity of highly purified samples of distilled water. From
Λ=
c Eq. (6.44) we can see that the concentrations of hydrogen and hydroxide ions
If we express  in are equal. So, we can write,
the units of S m−1
and c in mol m−3, [ H3O+ ] = [ OH− ] = (K w )1/ 2 …(6.46)
then,  = c
On the other hand, the conductivity of pure water is related to the
concentration of ions by the following equation.
( H2O) = (H+ ) + ( OH− )  ( H2O) = [H3O+ ] H + [OH − ] OH− …(6.47)
Substituting for the concentration of hydronium and hydroxide ions we can

write,
( H2O) = (K w )1/ 2 (H+ + OH− ) …(6.48)
Since the degree of ionisation of water is exceedingly small, the concentration

of the ions is also exceedingly small. Therefore, the conductivity of the ions
can be taken to be at infinite dilution. We can then write,
( H2O) = (K w )1/ 2 (0H+ + 0OH− ) …(6.49)
The value of  (H2O) has been found to be 5.5  10−6 (S m−1) by Kohlrausch
and Heydweiller. Substituting this value in the above equation along with the
molar ionic conductivities of hydrogen and hydroxide ions we get
5.5  10−6 (S m−1) = (K w )1/ 2 (349.81 10−4 + 198.3  10−4 ) S m2 mol −1 …(6.50)
1 mol Rearranging we get,

1 mol m − 3 =
3
m
5.5  10−6 (S m−1 )
1 mol (K w )1/ 2 = …(6.51)
= (548.1 10− 4 ) S m2 mol −1
3
(10 dm)
1 mol
= Taking squares, we get
1000 dm3
2
= 10 −3 mol dm−3  5.5  10 − 6 (S m−1 ) 
(K w ) =  −1 
= 1.007  10 − 8 mol 2m− 6 …(6.52)
(1 mol m−3 )2 ( 548. 1  10 −4
) S m 2
mol
 
= (10 −3 mol dm−3 )2
= 10 −6 mol2 dm−6 (K w ) = 1.007  10−8 mol 2m−6 = 1.007  10−14 mol 2 dm−6 …(6.53)
Thus, we find that the value of ionic product of water at 298 K is found to be
162 1.007  10−14 mol2 dm−6 on the basis of conductance measurements.
−14 2 −6
However, generally 1.00  10 mol dm is used as the value of ionic
product of water at 298 K.
6.4.4 Determination of Hydrolysis Constant of a Salt

You have learnt in Unit 9 of BCHCT-133 course that the reaction of anions
or/and cations produced by the salts with water is called salt hydrolysis. On
hydrolysis, the anions of weak acids produce the conjugate acid and hydroxide
ion whereas the cations of weak bases give the conjugate base and
hydronium ion. For example, let us take the hydrolysis of the salt anilinium
hydrochloride-a salt of weak base and strong acid. The salt would ionise as
C6H5NH3Cl (aq) → C6H5NH3+ (aq) + Cl− (aq) …(6.54)
The anilinium ion so produced would react with water and get hydrolysed as
C6H5NH3+ (aq) + H2O(I) ⇌ C6H5NH3OH (aq) + H+ (aq) …(6.55)
The overall reaction of anilinium hydrochloride with water can be given as

C6H5NH 3Cl (aq) + H2O(I) ⇌ C6H5NH 3OH (aq) + HCl(aq) …(6.56)
If we start with 1 mol dm−3 of the salt and assume that the degree of
hydrolysis of the salt at this concentration is  , then at equilibrium the
concentration of different species would be
C6H5NH 3Cl (aq) + H2O(l ) ⇌ C6H5NH 3OH (aq) + HCl (aq)
…(6.57)
(1 −  )  
If we further assume that the base C6H5NH3OH obtained by hydrolysis is very

weak and does not ionise appreciably. Therefore, it will not contribute to the
conductivity of the solution. Thus, the conductivity () of the solution would be
due to (1−) moles of the salt that is ionised but not hydrolysed, and  moles
of the strong acid (HCl). We can write,
0
Λ = (1 − ) Λsalt +  ΛHCl …(6.58)
0
Where, ΛHCl is the molar conductivity of hydrochloric acid at infinite dilution. As
it is a strong acid, it is assumed to be completely ionised. The molar
conductivity (Λ) of the solution can be experimentally measured. On the other
hand, Λsalt, the molar conductivity of anilinium hydrochloride when it is ionised
but not hydrolysed can be obtained by measuring the conductivity of the salt in
presence of excess of aniline. This would completely suppress the hydrolysis
of the salt. Once these values are known, these can be substituted in the
expression and the value of degree of hydrolysis can be obtained as follows.
0
Λsolution = (1 − ) Λsalt + ΛHCl …(6.59)
By rearranging, we get
0
Λsolution − Λsalt =  ( ΛHCl − Λsalt ) …(6.60)
This gives,
Λsolution − Λsalt
= 0
…(6.61)
( ΛHCl − Λsalt )
Now, for the equilibrium reaction given in Eq. (6.57) we can write the
expression for hydrolysis constant as 163
2
Kh = …(6.62)
(1 −  )
Substituting the value of  we can calculate hydrolysis constant. Let’s

understand it with the help of an example.
Example 6.6: The molar conductivity of a 0.011 M solution of aniline

hydrochloride was observed to be 120 S cm2 mol−1. The solution
on saturating with excess of aniline reduced the molar
conductivity to 104 S cm2 mol−1. If the molar conductivity of HCl at
infinite dilution is 410 S cm2 mol−1, calculate the degree of
hydrolysis and the hydrolysis constant for aniline hydrochloride.
Solution: We are given
Λsolution = 120 S cm2 mol −1; Λsalt = 104 S cm2 mol −1; and ΛHCl
0
= 410 S cm2 mol −1
( Λsolution − Λsalt )
From Eq. (6.61) we know that  = 0
( ΛHCl − Λsalt )

(120 − 104) Scm 2mol −1
= = 0.052
( 410 − 104) Scm 2mol −1
2
From Eq. (6.62) we have, K h =
(1 −  )
Since the degree of hydrolysis is exceedingly small, we can ignore it in the

denominator and also the concentration in this problem is different from 1 so
we can write
Kh = c2
Substituting the value of , and c we get
K h = 0.011 (0.052)2 = 2.97  10−5
Thus, the degree of hydrolysis and hydrolysis constants would be 0.052 and
2.97  10 −5 respectively.
In addition, the conductance measurements can also be used for the

determination of equivalence point in a number of titrimetric determinations.
Let us learn about the principle of different titrimetric determinations using
conductance measurements.
6.5 CONDUCTOMETRIC TITRATIONS

As discussed in Unit 5, the electrical conductance of a solution is a measure of
its current carrying capacity of the ions present in the solution. It is determined
by the type and concentration of ions present in the solution. In the
conductometric titrations we measure the conductance of analyte solution as a
function of the volume of titrant added and use it for the determination of
equivalence point of the titration. This method of the determination of
164 equivalence point becomes relevant when either the solutions are of very low
concentration or the analyte sample has a dark colour that does not permit the
use of common visual indicators.
In a typical conductometric titration the ionic species to be determined are
converted to non-ionic forms by a suitable reaction. For this purpose, a
measured volume of the solution to be titrated is taken in a beaker and a
conductivity cell is dipped into it. The titrant is added from a burette into the
solution and the conductance readings corresponding to the various additions
of the titrant are measured and plotted against the volume of the titrant. This is
then used to determine the equivalence point. Conductometric determination
of the equivalence point is commonly employed for acid-base and precipitation
titrations. Let us learn about these.
Acid-base titrations
In a typical determination of an acid, the hydrogen ions, mainly responsible for
the conductance, can be neutralised by reacting with a base in an acid-base
titration. Let us understand the changes in the conductance of the solution of a
strong acid say hydrochloric acid with a strong base like sodium hydroxide. To
begin with, in an aqueous solution of hydrochloric acid, the conductance will
be due to the hydrogen ions and chloride ions obtained by the ionisation of the
acid.
HCl (aq) → H+ (aq) + Cl− (aq) …(6.63)
As you know, the hydrogen ions have extremely high conductivity (due to
small size and Grotthus mechanism) whereas the chloride ions are bulkier and
relatively slow moving. Therefore, to begin with, the solution containing
hydrochloric acid would have high conductance. When we add a solution of
sodium hydroxide, it would provide slow moving sodium ions and hydroxide
ions with high mobility as follows.
NaOH (aq) → Na + (aq) + OH− (aq) …(6.64)
The hydroxide ions provided by NaOH would neutralise the hydrogen ions and
produce practically unionised water molecules as per the following reaction.
H+ (aq) + OH− (aq) ⇌ H2O(l) …(6.65)
The overall reaction can be given as

H+ (aq) + Cl− (aq) + Na + (aq) + OH− (aq) → Na + (aq) + Cl− (aq) + H2O …(6.66)
If we see the ions in the reaction carefully, we find that effectively the
hydrogen ions having high conductivity are replaced by relatively slow-moving
sodium ions. As a consequence, the conductance of the solution would
decrease. Adding more and more amount of NaOH solution would neutralise
more and more of hydrogen ions and the conductance would continue to
decrease. This trend would continue till all the hydrogen ions are neutralised
i.e., the equivalence point is reached.
Adding a drop of NaOH solution at this stage would provide additional sodium
ions and hydroxide ions. Therefore, the conductance of the solution would
start to increase; and the trend would continue with addition of more and more
of NaOH solution. If we plot a graph between the conductance of the solution
versus the volume of NaOH solution, we will get the titration curve as given in
Fig. 6.7 (a). 165
(a) (b)
Fig. 6.7: Schematic graphs showing the expected conductometric titration
curves for a) HCl versus sodium hydroxide and b) acetic acid versus
sodium hydroxide titration.
Let us consider another example, viz. conductometric titration between acetic

acid (a weak acid) and NaOH (a strong base). To begin with, in an aqueous
solution of acetic acid, the conductance will be due to the hydrogen ions and
acetate ions obtained from the ionisation of the acid as given below.
CH3COOH (aq) ⇌ CH3COO− (aq) + H+ (aq) …(6.67)
As the acid is weak there will be a small fraction of acetic acid in the ionised
form accordingly the solution will have a low concentration of hydrogen ions
and acetate ions. Therefore, the overall conductance will be low. On adding a
drop of sodium hydroxide, the few hydrogen ions present will combine with the
hydroxide ions provided by the base as shown below.
CH3COO− (aq) + H+ (aq) + Na + (aq) + OH− (aq) → Na + (aq) + CH3COO− (aq) + H2O …(6.68)
Effectively, what happens is that the fast-moving hydrogen ions are replaced
by slower sodium ions and the conductance decreases a bit. The acetate ions
will suppress the ionisation of acetic acid by common ion effect. Once all the
free hydrogen ions are neutralised, further addition of sodium hydroxide reacts
with the unionised acetic acid molecules. The reaction can be represented a
follow.
CH3COOH (aq) + Na + (aq) + OH− (aq) → CH3COO− (aq) + Na + (aq) + H2O …(6.69)
As a result of the reaction, the number of ions in the solution would increase
and the conductance would also increase.
With the addition of more and more of sodium hydroxide this process will
continue, and the conductance of the solution will continue to increase
gradually. This process will continue till the equivalence point where all the
undissociated acetic acid would have reacted with the base. The solution at
this stage will contain sodium and acetate ions in concentration equal to the
initial concentration of the acetic acid.
As in case of titration of HCl, any further addition of sodium hydroxide will

provide additional sodium and hydroxide ions. This would cause a further
increase in the conductance of the solution. However, as the hydroxide ions
166 have quite a high mobility, the increase in the conductance now will be much
faster. This change in the rate of increase of the conductance marks the
equivalence point of the titration. A typical conductometric titration curve
expected for the titration of acetic acid and sodium hydroxide is given in
Fig. 6.7(b).
As you have learnt earlier that in the measurement of conductance, we

measure the conductance of all the ions present in the column of solution
contained within the electrodes of the conductivity cell. During the titration, the
measured conductance changes due to the change in the concentration of the
ions in the region due to the reaction taking place. In addition to the reaction,
the dilution of the solution during the titration also affects the conductance. It
is, therefore, advantageous to use a titrant solution in a relatively higher
concentration. Generally, in conductometric titrations the titrant is taken about
ten times stronger than the titrand to minimise the dilution effect.
Precipitation titrations
As a typical case of conductometric precipitation titrations, we take the

example of titration of BaCl2 with sulphuric acid. A schematic titration curve for
the titration of barium chloride with sulphuric acid is given in Fig.6.8.
Fig. 6.8: A schematic graph showing the expected conductometric titration

curve for barium chloride versus sulphuric acid titration.
Let us understand the changes in the conductance of the solution of barium

chloride during its titration with sulphuric acid. In a solution containing barium
chloride, initially the conductance of the solution is due to the barium and
chloride ions obtained from the dissociation of BaCl2. Barium chloride being a
strong electrolyte is completely dissociated; dissociation of one mole of barium
chloride generates one mole of barium ions and two moles of chloride ions as
per the following equation.
BaCl2 (aq) → Ba 2+ (aq) + 2 Cl− (aq) …(6.70)
Addition of sulphuric acid provides hydrogen ions and sulphate ions. The
sulphate ions precipitate out the barium ions as per the following equation.
Ba 2+ (aq) + 2Cl− (aq) + 2H+ (aq) + SO24− (aq) → BaSO 4  + 2Cl− (aq) + 2H+ (aq) …(6.71)
The net result of the reaction is that each barium ion present in the solution is
replaced by two hydrogen ions. As the conductivity of two hydrogen ions is
much more than that of a single barium ion; the conductance of the solution 167
increases. This trend continues with further addition of the titrant sulphuric
acid. Once all the barium ions are precipitated i.e., at the equivalence point,
further addition of the titrant provides additional ions in the form of sulphate
and hydrogen ions. This leads to a sharper increase in the solution
conductance. This switchover from a slower increase in conductance to a
sharper increase in the conductance marks the equivalence point. Let us sum
up what have we discussed in this unit. However, before that answer the
following simple question to assess your learning of conductometric titration.
SAQ 9
Draw a schematic conductometric titration curve for the neutralisation of oxalic
acid by NaOH.
6.6 SUMMARY
In this unit we continued our discussion on electrolytic conduction and took up
two main aspects viz., the migration of ions and the application of conductance
measurements. We started the unit by discussing about migration of ions in an
electrolytic solution under the influence of applied potential. In this context we
introduced the concepts of ionic mobility and transference numbers. The ionic
mobility has been defined as the velocity with which an ion moves in a solution
under a potential gradient of 1 V m−1 whereas transference numbers refer to
the fraction of total current carried by a given type of ion in solution. We
established relationship between the two. This was followed by a discussion
on the principle and experimental determination of transference numbers.
Herein, we have explained in detail the principles of Hittorf’s method and
moving boundary method and described the procedure for the determination
of transference numbers by these methods. We used examples to clarify these
methods.
In the context of applications of conductivity measurement, we took up a

number of applications, like determination of ionisation constant of a weak
acid, determination of solubility and solubility product of sparingly soluble salts,
determination of ionic product of water and determination of hydrolysis
constant of a salt. In addition to explaining the principle of these applications
we showed their importance with the help of examples. In the end we took up
another important application of conductivity measurement, viz.,
conductometric titrations and discussed their significance.

1. List and explain different factors affecting ionic mobility.
2. Explain exceptionally high ionic mobilities of hydrogen ions.
3. The molar ionic conductivities of Li+ ions and Na+ ions at 298 K are
3.87  10−3 S m2 mol−1 and 5.01  10−3 S m2 mol−1 respectively. Calculate
their ionic mobilities.
4. In the determination of transport number, a solution of silver nitrate having
1.19 mg of silver nitrate per gram of water was taken in the Hittorf cell
using silver electrodes. After a certain amount of current was passed for
168 enough time, 20.37 mg of silver was deposited on the cathode. An
analysis of the solution from anode compartment showed that the solution
contained18 g of water and 38.8 mg of silver nitrate. Calculate the
transport number of the silver and nitrate ions.
5. The molar conductivity of 0.001028 M acetic acid solution at 298 K is
observed to be 48.15 S cm−2 mol−1. If the same at infinite dilution is found
to be 390.6 S cm−2 mol−1 calculate the degree of ionisation of acetic acid
at this concentration.
6. The conductivity of a saturated solution of AgCl at 298 K was found to be

3.41  10−6 S cm−1. The water used for dissolving AgCl had a conductivity
of 1.6  10−6 S cm−1. If the molar conductivity at infinite dilution for AgCl at
298 K is given as 138.2 S cm−2 mol−1 calculate the solubility and solubility
product of AgCl at 298 K.
7. Draw and explain the conductometric titration curve for the titration
between formic acid and NaOH.
6.8 ANSWERS
Self-Assessment Questions
1. The ionic mobility may be defined as the velocity with which an ion in a
solution would move under a potential gradient of 1 V m−1. It is denoted as
u and its SI unit is m2 V−1s−1.
2. The transference number is defined as the fraction of total current carried

by a given type of ion in solution. The transference numbers of cation and
anion are denoted as t+ and t− respectively. The transference numbers
and ionic mobilities are related as under
u− u−
t+ = and t− =
u+ + u− u+ + u−
where, u+ and u− respectively are the ionic mobilities of the cation and the
anion.
3. In this case copper sulphate is electrolysed using copper electrodes so
copper ions proportional to the total current passed in the solution (as
determined from the coulometer) would deposit on the cathode thereby
decreasing their concentration by same amount. However, copper ions
proportional to their transport number would move away from anode
compartment and move into the cathode compartment and increase their
concentration.
Let us first calculate the total amount of current passed:
The amount of silver deposited in the coulometer = 0.0405 g

We know that 107.88 g Ag ≡ 1 Faraday
1 0.0405
➔ 0.0405 g Ag = = 3.75  10− 4 F
107.88
As copper ion has a charge of 2 units, 3.75  10−4 F of current would

deposit
169
3.75  10−4
= = 1.877  10−4 moles of Cu2+ ion
2
i.e., 1.87  10−4 mol of copper sulphate will be lost from the cathodic
compartment.
It is given that the cathodic compartment after electrolysis has 0.44125 g
of Cu2+ ions; this is equivalent to
0.44125  159.6
= = 1.1090 g of CuSO 4
63.5
Mass of water in cathodic compartment = 36.4340 − 1.1090 = 35.3250 g
Initially, the solution was 0.2 molal i.e., 0.2  159.6 g of CuSO4 per kg of
water
The mass of CuSO4 initially in 35.3250 g of water was

0.2  159.6
=  35.3250 = 1.1276 g
1000
Loss in the mass of CuSO4 = 1.1276 −1.1090 g = 0.0186 g

0.0186 g
= = 0.0001165 mol
159.6 g mol −1
The expected loss of copper sulphate in the cathodic compartment due to

passage of current was 1.877  10−4 mol. However, the observed loss is
just 1.165  10−4 mol.
➔ (1.877−1.165)  10−4 mol = 7.12  10−5 mol of Cu2+ ions have migrated
into the cathodic compartment or have carried the current.
We know that transference number of cation is
Moles of electrolyt e lost from the anodic compartmen t
t+ =
Total number of moles of electrolyt e lost
0.712  10−4
t+ = = 0.379
1.877  10− 4
t − = 1 − t + = 1.0 − 0.379 = 0.621
Thus, the transport numbers of copper and sulphate ions have been found
to be 0.379 and 0.621 respectively
4. The methods generally employed for the experimental determination of

transference numbers are
• Hittorf’s method
• Moving boundary method
• Emf measurement method
5. In moving boundary method for the determination of transference number

of the ions of an electrolyte (called principal electrolyte) the additional
electrolyte that is used to create a boundary is called indicator electrolyte.
170 An indicator electrolyte must have anion or cation common with the
electrolyte being determined and the other ion should not move faster
than the ion whose transport number is to be determined.
6. We know that for determination of transference number by moving

boundary method,
10−3  l  a  c  F
t+ =
Q
We have been given the values as:
l = 2.1 cm a = 1.17 cm2 and c = 0.10 mol dm−3
Let us first find the value of Q (amount of charge passed) from the
coulometer data. We know that 1 F of charge would have deposited
107.88 g of silver. In other words
96485
107.88 g Ag = 96485 C  1 g Ag = C
107.88
96485  0.083
0.083 g Ag = = 74.23 C
107.88
Substituting the data in the expression, we get
10−3  2.1 cm  1.17 cm2  0.10 mol dm−3  96485 C mol −1

t+ = = 0.319 = 0.32
74.23 C
t − = 1 − 0.32 = 0.68
7. We are given:
c = 0.01 M, Λmc = 16.8 S cm 2 mol −1
First, we calculate the molar conductivity of acetic acid at infinite dilution

by using Kohlrausch’s law. According to the law, the molar conductivity for
acetic acid can be calculated as given below
Λm0 (CH3COOH) = 0m (H+ ) + 0m (CH3COO− ) = (349.8 + 40.9) S cm2 mol −1
0
ΛCH3 COOH
= 390.7 S cm2 mol −1
Further, we know that the percent ionisation of a weak electrolyte is given

as
Λmc
=  100%
Λm0
16.8 S cm2 mol −1

=  100% = 4.30%
390.7 S cm2 mol −1
8. If we dissolve a sparingly soluble salt of MX2 type in water the solubility

equilibrium can be represented as
MX 2 (S) + H2O (𝑙) ⇌ M2+ (aq) + 2X− (aq) 171

The corresponding expression for Ksp would be : K sp = [ M2 + ] [X − ]2

As the salt has extremely low solubility, we can assume that all the
dissolved salt is ionised and the measured molar conductivity will be same
as the molar conductivity at infinite dilution. We can therefore write
1000 
Molar conductivity = Λm = = S cm2 mol −1 = Λm0
s
Where, s is the molar solubility of the sparingly soluble salt,
Rearranging and simplifying,
1000 cm3 dm−3   (S cm-1 )
s=
Λm0 (S cm2 mol −1 )
The molar conductivity at infinite dilution can be obtained by using the

molar conductivities of the respective ions at infinite dilution by the
following expression.
Λm0 = v + 0+ + v −0−
For the salt, MX2 we can write,

Λm0 (MX 2 ) = 0m (M+ ) + 20m ( X− )
Substituting the value of solubility in the solubility product expression, we

get
3
 1000 
K sp = s(2s ) = 4s = 4
2 3
0
 (mol 3 dm− 9 )

 Λ m 
9. A schematic conductometric titration curve for the titration between oxalic

acid and NaOH is given below
There will be two equivalence points corresponding to the stepwise

neutralisation of diprotic oxalic acid.
Terminal Questions
1. The ionic mobility of an ion depends on the following factors:
• Charge on the ion
• Size of the ion
172 • Viscosity of the medium

An ion with a higher charge has higher ionic mobility because it would
experience a greater force due to electric field under which it is moving.
The force experienced is given as (F = zeE) where z is the charge on the
ion, e is the elementary charge and E is the electric field strength.
Secondly, a smaller ion has higher ionic mobility because it experiences
lesser friction with solvent molecules and other ions due to smaller
surface area. Thirdly, the ions slow down in a medium of higher viscosity
due to greater retardation force due to friction.
2. The exceptionally high ionic mobilities of hydrogen ions can be explained

in terms of Grotthus conduction mechanism. According to this mechanism
the proton in solution binds to a neighbouring water molecule and
momentarily converts it to a hydronium ion. This in turn transfers its proton
to another water molecule in neighbourhood which does the same to
another molecule and this process continues. As a result, a proton in any
region of the solution is effectively transported quickly to another part.
This mechanism is also known as proton hopping mechanism.
3. We know that the ionic conductivity 𝜆 is related to ionic mobility (𝑢) as

follows
 = zuF
Where, z is the charge on the ion and F is the Faraday’s constant.
The ionic mobilities can be calculated by rearranging the expression as,


u=
zF
Substituting the values.
3.87  10−3 S m2 mol −1

For Li+ ion: u = −1
= 4.011 10− 8 m2 V −1 s −1
1 96485 C mol
5.01 10 −3 S m2 mol −1
For Na+ ion: u = −1
= 5.193  10− 8 m2 V −1 s −1
1 96485 C mol
4. We know that the transport number of the cation is defined as

t+ =
First, we calculate the total number of moles of electrolytes lost by using

the amount of silver deposited on cathode.
The amount of silver deposited on cathode

0.2037 g
= = 0.000189 mol
107.88 gmol −1
Since in this case we are using silver electrodes, so 0.000189 moles of

silver will dissolve from the silver anode.
We are given the final amount of silver nitrate in the anode compartment
as 38.8 mg of silver nitrate and 18 g of water i.e., 173
0.0388 g
Final number of moles of silver nitrate = = 0.000228mol
169.87 g mol −1
Initial number of moles of silver nitrate in the anode compartment can be

obtained by calculating silver nitrate in 18 g of water
18 g water  0.0119 g AgNO 3 per g water

= = 0.000126 mol
169.87 g mol −1
The number of moles of silver nitrate transferred from anode compartment
= Initial no. of moles + Moles formed by dissolution of electrode −

final no. of moles
= 0.000126 + 0.000189 − 0.000228 = 0.000087
Substituting in the expression for transport number, we get
0.000087mol
t Ag+ = = 0.46
0.000189mol
We know that t + + t − = 1 so tNO− = 1 − 0.46 = 0.54

3
5. We know that the degree of ionisation (𝛼) of the weak electrolyte is given
as
Λmc
=
Λm0
Where, Λmc and Λm0 are the molar conductivities of the weak electrolyte at
a given concentration and at infinite dilution, respectively.
48.15 S cm2 mol −1

= = 0.123
390.6 S cm2 mol −1
6. We know that the solubility, conductivity, and molar conductivity at infinite

dilution are related as
1000 cm3 dm−3   (S cm−1 )

s=
Let us first calculate the conductivity of the salt only by correcting given
conductivity of solution for water as follows
 (salt) =  (solution) −  (water)
( AgCl) = (3.41 10−6 ) − (1.60  10−6 ) = 1.81 10−6 S cm−1
The molar conductivity for AgCl at infinite dilution is given as
174 = 138.2 S cm2 mol −1

Substituting the values of conductivity and molar conductivity at infinite
dilution in the expression for solubility (Eq. (6.38) we get
1000 cm3 dm−3   (S cm−1 )

s=
1000 cm3 dm−3  1.81 10 −6 S cm −1

s= 2 −1
= 1.31 10 − 5 mol dm− 3
138.2 S cm mol
Now for AgCl the expression for solubility product can be written as
K sp = [ Ag + ] [Cl− ) = s 2
Substituting the value of solubility, we get
K sp = (1.31 10 −5 )2 = 1.72  10 −10 mol 2 dm−6
7. Formic acid is a weak acid and its titration with a strong base like NaOH
will be similar to the one described for acetic acid in the text. A schematic
diagram for the conductometric titration between formic acid and NaOH is
given below.
Initially, the solution of formic acid would have a few hydrogen and
formate ions due to the poor ionisation of formic acid; the overall
conductivity is low. Initial addition of sodium hydroxide neutralises the fast
moving hydrogen ions and the conductivity decreases slightly. Further
addition of NaOH neutralises unionised formic acid and the conductivity
increases due to the formation of salt, sodium formate. Once all the formic
acid is neutralised i.e., at the equivalence point further addition of NaOH
increases conductivity sharply due to addition of sodium ions and
hydroxide ions (having high conductivity). The change in the slope
windicates equivalence point.
175
Unit 7 Electrochemistry-I
UNIT 7
Electrochemistry-I
Structure
7.1 Introduction Experimental Measurement of
EMF of Cell
7.6 Thermodynamics of Reversible
7.2 Electrochemical Cells
Cell
Galvanic Cells
Cell EMF and Spontaneity
Electrolytic cells
Cell EMF and Equilibrium Constant
7.3 Reversible and Irreversible
7.7 Nernst Equation
Cells
Applications of Nernst equation
7.4 Representing Electrochemical
Cells 7.8 Types of Electrodes
Cell Diagram and Cell Reaction 7.9 Summary
7.5 EMF of a Cell 7.10 Terminal Questions
Standard Reduction Potential 7.11 Answers
7.1 INTRODUCTION
In the previous two units you have learnt about different aspects of conduction
in electrolytic solutions. You would recall from Unit 5 that while discussing
about the mechanism of electrolytic conduction, we mentioned that when the
ions carrying current through the bulk of the electrolytic solution reach the
electrode, they undergo chemical reactions there. These reactions are
characteristic and depend on the nature of the electrolyte and the electrode. In
this and the next unit you would learn about electrochemical cells where we
would discuss the processes occurring at the electrodes in the cells and their
consequences.
In this unit dealing with first part of our discussion on electrochemistry we

would begin by introducing the domain of electrochemistry and discussing
electrochemical cells. Since most of the practical applications of
electrochemistry require electrochemical cells working reversibly so we would
clarify the meaning of reversible cells. This will be followed by discussion on
galvanic cells, their representation and writing cell reactions. Then we would
take up the concept of emf of a cell and its measurement. In this context we
would introduce the concepts of electrode potential; and standard electrode
176 potential.
We would then take up thermodynamic aspect of reversible cells. Herein, we
would take up the relationship between cell emf and thermodynamic
parameters like, Gibbs energy, equilibrium constant etc. We would also take
up Nernst equation and its applications before describing different types of
electrodes. In the next unit we would focus our discussion on the principles of
concentration cells, electrolytic cells, and applications of emf measurements.

❖ define electrochemistry and state it’s importance;
❖ differentiate between galvanic and electrolytic cells;
❖ differentiate between reversible and irreversible cells;
❖ describe a galvanic cell and explain its principle in terms of electrode

reactions;
❖ represent given galvanic cell in terms of cell diagram and write cell
reactions for it;
❖ explain the meaning and outline the significance of standard electrode

potential;
❖ define emf of a cell and calculate the same using standard electrode
potentials of the redox couples involved;
❖ describe the method for experimental measurement of cell emf;
❖ derive a relationship between cell emf and the Gibbs energy and predict
the spontaneity of cell reaction of a given galvanic cell;
❖ calculate the equilibrium constant of a redox reaction by using cell emf;
❖ write Nernst equations for half-cell reactions and cell reactions;
❖ outline the significance of Nernst equation and predict the spontaneity of

the cell reaction of a non-standard galvanic cell using the same;
❖ explain the principle of determination of pH of an aqueous solution using

emf measurement;
❖ list and describe different types of electrodes; and
❖ write the half-cell reactions and representations of different electrodes.
7.2 ELECTROCHEMICAL CELLS

As you are aware, electrochemistry is the branch of physical chemistry that
deals with the relationship between electricity, and chemical change in the
system. There are two possibilities where such a relationship exists; in one of
these, the spontaneous chemical reactions produce electricity and in the other,
we use electricity to bring about non-spontaneous chemical reactions. In 177
simple words, we can say that electrochemistry is the study of production of
electricity from energy released during spontaneous chemical reactions and
the use of electrical energy to make non-spontaneous reactions possible.
Further, you are also familiar with redox reactions-the chemical reactions that
involve transfer of electrons between two reactants participating in it. A cell in
which the progress of such an oxidation-reduction reaction is associated with
electric current is called an electrochemical cell. These are of two types. The
electrochemical cell in which the progress of a spontaneous chemical reaction
causes an electric current to flow is called a galvanic cell. On the other hand,
the electrochemical cell in which a current is passed by an external voltage, to
make an otherwise non-spontaneous chemical reaction to proceed is called an
electrolytic cell. An electrochemical cell typically consists of a solution of an
electrolyte and two electrodes at which oxidation and reduction processes
occur, respectively. The electrolyte usually is a solution of an acid, base or a
salt or a pure liquid. Here, in this unit we are going to take up the study of
galvanic cells. Let’s understand what are galvanic cells.
7.2.1 Galvanic Cells

In order to learn about galvanic cells, let us take up some simple experiments.
In the first experiment we take an aqueous solution of silver nitrate in a beaker
and dip a strip of copper in it. We would observe the following:
a) The part of copper strip dipped into the solution becomes thinner (some
copper metal is lost);
b) The colour of otherwise colourless solution becomes bluish;
c) A silvery layer is formed on the dipped copper strip

Expt.1: Copper strip d) The solution temperature increases slightly
in aqueous solution of
AgNO3 These observations can be explained in terms of the following changes
i) The copper atoms in the copper plate get oxidised to cupric ions releasing
two electrons, as per the following equation
Cu(s) → Cu2+(aq) + 2e− (Oxidation) …(7.1)
The blue colour of the solution is due to the formation of these cupric ions.
ii) The silver ions get reduced to silver metal by accepting the electrons
released by copper as per the following equation
2Ag+(aq) + 2e− → 2Ag(s) (Reduction) …(7.2)
The metallic silver so obtained is deposited on the copper plate.
The overall reaction can be given as the following redox reaction

Cu(s) + 2Ag+(aq) → Cu2+(aq) + 2Ag(s) …(7.3)
In simpler words, we can say that copper metal has a greater tendency to get
oxidised and displaces silver ions from the solution and there is a transfer of
electrons from copper atom to silver ions. Let’s take the second experiment to
be a familiar one; dipping a zinc rod in an aqueous solution (blue coloured) of
178 Copper (II) sulphate. In this case, we observe the following
a) The part of zinc rod dipped into the solution becomes thinner (some zinc
metal is lost);
b) The colour of blue solution fades and eventually becomes colourless;
c) Reddish-brown solid (elemental copper) deposits on the surface of zinc

rod
d) The solution temperature increases slightly
These observations can be explained in terms of the following changes
i) The zinc atoms in the zinc rod get oxidised to zinc ions by releasing two
electrons, as per the following equation
−
Zn(s) → Zn2+(aq) + 2e (Oxidation) …(7.4)
Expt.2: Zinc strip in
This accounts for the thinning of zinc rod aqueous solution of
CuSO4
ii) The copper ions in the solution get reduced to copper metal by accepting
the electrons released by zinc atoms as per the following equation
Cu2+(aq) + 2e− → Cu(s) (Reduction) …(7.5)
This is results in the formation of reddish-brown solid on the surface of

zinc rod
The overall reaction can be given as the following redox reaction
Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s) …(7.6)
In simpler words, we can say that zinc metal has a greater tendency to get
oxidised and displaces copper ions from the solution and there is a transfer of
electrons from zinc atom to copper ions. In the third experiment we dip a strip
Expt.3: Copper strip
of copper in an aqueous solution of Zinc (II) nitrate. In this case, we do not
in aqueous solution of
observe any reaction. Zn (NO3)2
Cu(s) + Zn2+(aq) → No reaction …(7.7)
What do we conclude from these experiments? We conclude that the

experiment 1 and 2 involve spontaneous reactions as represented by the
Eqs.(7.3) and (7.6) whereas, the reaction between copper metal and zinc ions
(experiment 3) is not spontaneous. You know from your earlier studies on
chemical energetics that a spontaneous reaction is accompanied by a
decrease in Gibbs energy. This Gibbs energy change leads to a change in the
temperature of the solution in experiment 1 and 2.
Now, the question comes up is ‘can we use the Gibbs energy change in
spontaneous reactions for doing some work?” and if yes, ‘how do we do
so?’The answer is yes and we can do so by not allowing a direct transfer of
electrons between the reactants. Practically speaking, this can be achieved by
separating the process of release of electrons and their consumption i.e.,
separating zinc metal from the copper sulphate solution in experiment 2. Such
a set up is called a Galvanic or a voltaic cell. Let us learn about the
construction and working of Galvanic cells by taking the example of Daniell
Cell in which the redox reaction given by Eq.(7.6) takes place. 179
Daniell Cell
In order to separate the process of release of electrons and their consumption,

in Daniell cell we take two different electrodes. In one of the electrodeswe take
an aqueous solution of zinc sulphate in a beaker and dip a zinc strip or rod in
it. For the second electrode we take a copper rod or strip and dip it in an
aqueous solution of copper sulphate taken in a beaker. Let us see what
happens in these electrodes. We begin with zinc electrode.
In case of zinc electrode, the strip of zinc is dipped in a dilute solution of zinc
sulphate. As zinc sulphate is a strong electrolyte, it is fully dissociated, and
initially the solution contains equal number of positive (Zn2+) and negative
Galvanic cells are (SO42-) ions and the solution as such is neutral. Similarly, the metal strip can
named after an Italian
be visualised as an array of positively charged kernels in the sea of electron
anatomist Luigi
and the overall metal is also electroneutral.
Galvani, who
demonstrated that Now, since zinc is an electropositive element, some of the zinc atoms from the
passage of electricity
electrode’s surface lose electrons to the electrode and enter the solution as
caused frog muscles
Zn2+ ions, i.e., the zinc atoms get oxidized. As a consequence, the charge
to contract and two
different metals in balance in the metal is disturbed and the metal has a small excess of negative
contact with the charge. On the other hand, due to the release of zinc ions from metal to the
muscle tissue solution there is a small excess of positive charge in the solution. In time,
produce an electric some zinc ions may get attracted back to the negative metal and get deposited
current. on it by taking electrons from there, i.e., the zinc ions get reduced. At a certain
stage, the following redox equilibrium is established between the zinc strip and
the zinc ions.
Zn(s) ⇌ Zn2+(aq) + 2e− …(7.8)
Eventually, a potential develops between the negatively charged electrode and

the excess positive charge in the solution near the electrode. A system
The voltaic cell
containing a metal strip or rod dipped in a solution of its ions is called half-cell
involving zinc and
copper electrodes is (or electrode) and the potential developed is called half-cell potential (or
called a Daniell cell electrode potential). A similar process occurs in case where a copper strip is
after the English dipped in a solution of copper sulphate.
chemist John Daniell,
who developed it in Cu(s) ⇌ Cu2+(aq) + 2e− …(7.9)
1836.
Now, if we connect these two electrodes by a metal wire the electron would
flow from zinc electrode to copper electrode. We can say so on the basis of
experiment 2 and 3 described above. You would recall that in experiment 2
zinc could displace copper ions from solution but in experiment 3 it’s reverse
was not true. This implies that the potential of zinc to get oxidized is more than
that of copper. Alternatively, we can visualise that the voltage, or potential
difference, between the zinc rod and the zinc ions around it is more than that
between the copper rod and copper ions. This difference of voltages (or
potential differences) is the driving force for the transfer of electrons. It is like
the flow of water from a higher level to a lower level.
Further, this flow of electrons from zinc to copper would cause deposition of
copper on the copper electrode due to reduction of copper ions from the
solution. These conclusions are supported by the experimental observation
that in Daniell cell the mass of zinc electrode decreases whereas that of
180 copper electrode increases.
The reactions at the two electrodes would be:
Zn(s) → Zn2+(aq) + 2e− (Oxidation) …(7.4)

Cu2+(aq) + 2e− → Cu(s) (Reduction) …(7.5)
The overall reaction occurring in the cell can be obtained by adding Eq. (7.4)
and Eq. (7.5) to give
Zn(s) + Cu2+ (aq) → Zn2+ (aq) + Cu(s) …(7.6)
Thus, the chemical change in the cell is basically an electron-transfer reaction.
As a result of the flow of electrons from zinc to copper electrode and the
accompanied reactions there will be an excess of positive charge around zinc
(due to excess Zn2+ ions) and excess of negative charge around copper
electrode (due to excess SO42− ions) as Cu2+ ions here get reduced.
Therefore, the process would stop very soon. For this process to continue we
need to connect the electrolytes in two half cells i.e., complete the electrical
circuit between the two solutions. In other words, the charge carried by the
electrons in the external circuit must be followed by a transport of ions
between the two half cells. That is, we must provide a way for ions to move
from one half cell to the other.
This is achieved by using a salt bridge to link the two electrolytic solutions.
The salt bridge is basically an inverted U-shaped tube containing a saturated
solution of an inert electrolyte like KCl, KNO3 or NaNO3 etc., whose ions are
neither involved in the net chemical change nor do these interact with the
electrodes. This solution is mixed with a gelatinous material, such as agar-
agar, so that it does not flow into the electrode compartments. Other way to do
so is to place a sintered disc on each end of the tube.
Once the two solutions are connected through the salt bridge, the excess
positive charge around the zinc electrode is neutralised by the transfer of
negative ions from the salt bridge and to a small extent by migration of zinc
ions to the salt bridge. Similarly, the excess negative charge around the
copper electrode is neutralized mainly by the transfer of positive ions from the
salt bridge and to a small extent by migration of sulphate ions to the salt
bridge. Due to the neutralisation of the charges around the electrodes, the
oxidation of zinc from the zinc electrode and reduction of copper ions on the
copper electrode resumes. The process of transfer of electrons from zinc to
copper electrode in the external circuit and transfer of ions across the
electrolytes resumes. A schematic diagram of Daniell cell constructed by using
salt bridge to connect the two electrolytes is given in Fig. (7.1)
Fig. 7.1: A schematic diagram of Daniell cell. 181

The function of salt bridge can be given as under:
a. It completes the cell circuit by connecting the electrolyte solutions of two

half cells.
b. It helps in maintaining the electrical neutrality of the solutions in the two
half cells.
c. It does not allow the transfer or diffusion of the electrolyte solution from
one half cell to the other.
d. It prevents the liquid-liquid junction potential i.e., the potential difference
that would develop between two electrolyte solutions if the two are
allowed to be in contact with each other. (you would learn about liquid
junction potential in the next unit.)
The half-cell in which the oxidation reaction takes place is called the anode,
and the half-cell involving the reduction reaction is called the cathode. The
two half-cells put together constitute a voltaic cell. Now, if we attach some
electrical device such as a lightbulb to the wire, connecting two electrodes we
can operate the device (the bulb glows). In other words, by separating the half-
reactions, we can extract work from the spontaneous electrochemical reaction.
Having learnt about the working of a galvanic cell using the example of Daniell
cell let’s learn about writing the cell reaction for a galvanic cell.
Example 7.1: Write down the cell reaction for the galvanic cell on the basis of
the observation that a strip of copper metal when placed in an
aqueous solution of silver nitrate, displaces silver ions from the
solution. However, its reverse is not true.
Solution: The given observation means that copper is more electropositive
than silver; i.e., it has a greater tendency to get oxidised; i.e., the
following reaction takes place at the anode
Cu(s) → Cu2+(aq) + 2e− (Oxidation)
We know that an oxidation reaction must be accompanied by a reduction
reaction; i.e., in the given system the silver ions get reduced to silver atoms.
Since each copper atom loses two electrons to form copper ion and each
silver ion requires just one electron to produce silver atom; therefore, for every
copper ion formed two silver atoms are deposited on the cathode as per the
following reaction
2Ag+(aq) + 2e− → 2Ag(s) (Reduction)
It is important to note Now, if we combine, copper and silver electrodes, they will form a galvanic cell
that while combining in which copper electrode would act as an anode whereas silver electrode will
the half-cell equations act as a cathode. Further, there will be a transfer of electrons from copper
to produce the overall electrode to silver electrode when the current is drawn from the cell. The
cell equation, we overall cell reaction can be obtained by adding the reactions occurring at
must ensure that the
anode (oxidation) and cathode (reduction) as follows:
number of electrons
involved in reduction At anode: Cu(s) → Cu2+(aq) + 2e− (Oxidation)
reaction are equal to
the number involved At cathode: 2Ag+(aq) + 2e− → 2Ag(s) (Reduction)
in oxidation reaction.
Cell reaction: Cu(s) + 2Ag+(aq) → Cu2+(aq) + 2Ag(s)
182
On the basis of the above example, we can outline the procedure for writing
the cell reaction for a galvanic cell.
Step1: Write the hall-cell reaction taking place at the anode i.e., the oxidation
reaction
Step 2: Write the half-cell reaction taking place at the cathode i.e., the
reduction reaction
Step 3: Combine the above two half-cell reactions ensuring that the number of
electrons released at the anode is equal to the number of electrons
used at the cathode.
Having learnt about Galvanic or Voltaic cells in which we use the spontaneous
redox reactions to get useful electrical work let us learn about the cells in
which we use external potential to cause a non-spontaneous reaction.
7.2.2 Electrolytic Cells

As stated above, the electrochemical cells in which non-spontaneous
reactions are made to occur by causing a flow of electricity (electric current)
through the cell by using an outside source, such as a battery or a generator
are called electrolytic cells. In an electrolytic cell two electrodes are dipped into
a solution of an electrolyte taken in a container. These electrodes are then
connected to an external source of electricity. As a consequence, the ions in
the electrolyte move towards the oppositely charged electrode and undergo
chemical reactions on the electrodes. The movement of ions is an electric
current. The whole process is called electrolysis. A schematic diagram of an
electrolytic cell is given in Fig. (7.2).
Fig. 7.2: A schematic diagram of an electrolytic cell.
As in case of galvanic cells, the flow of current through the electrolyte is due to
the movement of ions to oppositely charged electrodes whereas in the
external circuit it is due to flow of electrons. We would discuss about
electrolytic cells in details in the next unit. For now, let us learn about the
reversible and irreversible cells. However, before that answer the following
simple question to assess your understanding of electrochemical cells.
SAQ 1
What are galvanic cells? It is observed that a strip of aluminum kept in a
solution of silver nitrate displaces silver ions from solution. Formulate the cell-
equation for a galvanic cell prepared by using aluminum and silver electrodes.
183
7.3 REVERSIBLE AND IRREVERSIBLE CELLS

As stated above, in galvanic cells the Gibbs energy change of the
spontaneous redox reaction causes the development of potential difference
across the electrodes and this can be used to get useful work. We can relate
other thermodynamic parameters with the potential difference and obtain their
values from electrochemical measurements. However, for this to be possible
the electrochemical cell must be reversible.
A reversible cell may be defined as the one in which the reactions are always
in state of equilibrium and only infinitesimally small currents are drawn from it.
A reversible cell must satisfy the following conditions.
i) If we connect an external source of emf to the cell such that the driving
force (applied voltage) and the opposing force (the cell potential
difference) are equal no reaction should occur in the cell
ii) If the applied voltage is infinitesimally smaller than the cell voltage, then
the cell reaction would occur to an infinitesimally small extent and
infinitesimally small current would flow from the cell to external source.
iii) If the applied voltage is infinitesimally greater than the cell voltage, then
the cell reaction would occur to an infinitesimally extent in the reverse
direction and infinitesimally small current would flow from the external
source to the cell
A cell not satisfying the above requirements is called an irreversible cell. Let
us take an example each of reversible and irreversible cells.
Daniell cell discussed above is an example of a reversible cell. If we connect

an external source having slightly lower voltage than the cell, then the
In a typical galvanic following reaction would occur in the cell and a small amount of current would
cell, the half-cells flow from the cell to the external source.
consist of a metallic
electrode dipped into Zn(s) + Cu2+ (aq) → Zn2+ (aq) + Cu(s) …(7.6)
corresponding salt
solution. The metallic However, if the connected external source has slightly greater voltage than the
electrodes are cell, then the reaction occurring in the cell would get reversed and a small
connected externally amount of current would flow from the external source to the cell.
by a metallic wire and
electrolytes of the two Zn2+ (aq) + Cu(s) → Zn(s) + Cu2+ (aq) …(7.10)
half-cells are
connected internally On the other hand, if the applied external voltage is exactly equal to the cell
through a salt bridge voltage, there will be no reaction in the cell.
Let us now consider a cell containing zinc and silver electrodes dipped in a
solution of sulphuric acid taken in a container. On connecting the two
electrodes by a wire it is observed that zinc dissolves with the evolution of
hydrogen gas and zinc sulphate is formed in the solution. The change can be
represented as the following reaction:
Zn(s) + H2SO4 → ZnSO4 (aq) + H2(g) …(7.11)
On the other hand, if we connect the cell with an external source having
184 potential slightly greater than of the cell, we find that silver dissolves and
hydrogen is evolved at the zinc electrode. The change can be represented as
the following reaction:
2Ag(s) + H2SO4 → Ag2SO4 + H2(g) …(7.12)
Thus, we find that in this case, the condition of reversibility i.e., on applying an
external voltage greater than the cell voltage, the reaction should reverse is
not being followed. Therefore, it is an example of irreversible cell. In such a
case, we cannot relate the cell emf with thermodynamic properties.
7.4 REPRESENTING GALVANIC CELLS

In our discussion above, we used the example of Daniell cell to describe the
formation and the functioning of a galvanic cell. In principle, we can create any
number of galvanic cells by using combinations of two different metal
electrodes. However, in order to learn about or describe different galvanic cells
we do not need to draw sketches like the one given in Fig. (7.1); we use a
symbolic representation for these. Such a representation is called a cell
diagram or cell notation. There are certain rules (conventions) that need to
be followed while writing the cell diagram for a given galvanic cell. Let us learn
about these rules by using the example of Daniell cell as follows:
i) The anode, the electrode at which oxidation occurs, is placed at the left
side of the diagram and the cathode, the electrode at which reduction
occurs, is placed at the right side of the diagram i.e.,
Zn(s)| Zn 2 + || Cu2 + | Cu(s) …(7.13) In case of cells with

transference;
Here, a single vertical line indicates the boundary separating species in involving the
different phases in a given electrode (half-cell). The double vertical line development of liquid
indicates the salt bridge. [Sometimes, a single broken (dashed) vertical junction potential a
line is used to represent a porous boundary, or some other means of broken vertical line is
preventing the electrolytes from mixing while allowing ion to flow.] used in place of two
vertical lines to
ii) The concentrations or activities of aqueous solutions are written in indicate the porous
parentheses after the symbol of the ions in the cell notation boundary.
Zn(s) | Zn2+ (aq,1M) || Cu2+ (aq,1M) | Cu(s) …(7.14)
iii) Sometimes, the electrolyte used in the salt bridge is also indicated. In such
a case the cell diagram for Daniell cell becomes,
Zn(s) | Zn2+ (aq,1M) | KCl(satd.) | Cu2+ (aq,1M) | Cu(s) …(7.15)
It is important to note that that the spectator ions, (the counter ions of the
electrolytes) that are present in the system but do not participate in the cell
reaction, are not shown in the cell diagram.
7.4.1 Cell Diagram and Cell Reaction

The representation of a galvanic cell in terms of cell diagram is quite
convenient way of expressing the cell. It is but natural that the cell diagram
and the reaction taking place in the cell are related. In principle, we should be
able to write the cell notation from the cell reaction and also, we should be 185
able to work out the cell reaction from the cell notation. Let us first learn how to
You may note here write cell diagram from the cell reaction. You know that a cell reaction is
that left and right here basically a redox reaction; and is a combination of two half-cell reactions. In
refer to the way the the process of writing cell diagram from cell reaction the first step is to identify
electrode is and write the two half-cell reactions. Once that is done then the process
represented in the cell
becomes quite straight forward. Let us take an example to understand it.
diagram. It has
nothing to do with the
Example 7.2: Write the cell diagram for a galvanic cell in which the following
physical location of
the two electrodes in
reaction takes place.
the actual galvanic
Cell reaction: Zn(s) + 2Ag+(aq) → Zn2+(aq) + 2Ag(s)
cell.
Assume that potassium nitrate is used as electrolyte in the salt bridge and the
concentrations of zinc ions and silver ions are c1 and c2 respectively.
Solution: As stated above, the first step in the process of writing cell diagram
from cell reaction is to separate the two half-cell reactions. This
basically means that we need to identify the species undergoing
oxidation and reduction, respectively.
Here, we see that the metallic zinc is getting oxidised and the silver ions are
getting reduced to silver metal. So, we can write the oxidation and reduction
half-cell reactions as
Oxidation: Zn(s) → Zn2+(aq) + 2e−
Reduction: 2Ag+(aq) + 2e− → 2Ag(s)
We place the anode at the left side and the cathode, at the right side of the
diagram by separating different phases of the two half-cells by a single vertical
line and by representing the salt bridge by a double vertical line as follows.
Zn(s) | Zn2+ (aq) || Ag+ (aq) | Ag(s)
Note that the physical states of different species are indicated in the
parenthesis. As the concentrations of the ions are given, we include them as
Zn(s) | Zn2+ (aq, c1) || Ag+ (aq, c2 ) | Ag(s)
Further, as the electrolyte used in the salt bridge is also given, we include that
also in the cell notation as follows
Zn(s) | Zn2+ (aq, c1) | KNO 3 (satd.) | Ag+ (aq, c2 ) | Ag(s)
This is the required cell diagram for the given galvanic cell
Having learnt to write cell diagram from the cell reaction let us now learn to
write cell reaction on the basis of the cell diagram. We will again take an
example to do so.
Example 7.3: Write the balanced cell reaction for the galvanic cell represented
by the following cell diagram.
Sn(s) | Sn2+ (aq) || Ag+ (aq) | Ag(s)

186
Solution: As we know that the balanced cell reaction for a galvanic cell can be
obtained by adding the oxidation and reduction reactions in such a
way that total number of electrons lost and gained are equal.
Further, we know that in a cell diagram the electrode on which the oxidation
occurs is given on the left and the electrode at which reduction takes place is
given on the right. Therefore, in this case tin is undergoing oxidation whereas
silver ions are getting reduced. The corresponding equations can be written as
Oxidation: Sn(s) → Sn2+(aq) + 2e−
Reduction: Ag+(aq) + e− → Ag(s)
We find that tin atom gives two electrons while getting oxidised and a silver ion
needs just one electron to be reduced. So, to balance the electrons we
multiply the reduction equation by 2 to get,
2Ag+(aq) + 2e− → 2Ag(s)
We can get the cell reaction by adding the oxidation and reduction equations
as follows
Oxidation: Sn(s) → Sn2+(aq) + 2e−
Reduction: 2Ag+(aq) + 2e− → 2Ag(s)
Cell reaction: Sn(s) + 2Ag+(aq) → Sn2+(aq) + 2Ag(s)
Having learnt about galvanic cells, their working and representation let us now
learn about the emf of the cell. However, before that solve the following simple
question to assess your understanding.
SAQ 2
What is a cell diagram? Write the cell diagram for a galvanic cell in which the
following reaction takes place.
Fe(s) + Cd2+(aq) → Fe2+(aq) + Cd(s)
7.5 EMF OF A CELL

As discussed above, in galvanic cells there is a transfer of electrons from the
negative electrode (anode)to the positive electrode (cathode). This transfer of
electrons causes a current to flow from the electrode at higher potential to the
one at lower potential. This difference between the electrode potentials of the
electrodes when no current is drawn through the cell is known as the cell
electromotive force (emf) and is expressed in volts. In terms of the cell
notation in which the anode is written on the left and the cathode on the right
we can write, the standard cell emf as
0
Ecell = ER0 − EL0 …(7.16)
Where, E R0 and EL0 are the standard electrode potentials of the cathode and
the anode, respectively. In order to understand and determine emf of a cell we 187
need to first understand the meaning and significance of electrode potential
also conventionally expressed as reduction potential
7.5.1 Standard Electrode Potential

Let us recall from above, that when a metal (e.g., Zn or Cu) is placed in an
aqueous solution of its salt, some kind of charge separation develops between
the metal and nearby solution. The equilibrium processes can be represented
by the equations like,
Zn(s) ⇌ Zn2+(aq) + 2e− …(7.8)
Cu(s) ⇌ Cu2+(aq) + 2e− …(7.9)
The charge separation leads to development of a potential difference and this

is called electrode potential or half-cell potential. When all the species
involved in a half-cell are at unit concentration (in case a gas appears in the
electrode reaction, then it is to be at a pressure of 105 Pa), then the electrode
potential is known as standard electrode potential.
Determination of Standard Reduction Potentials
The potential of an individual electrode or half-cell cannot be measured. If we

try to measure the half-cell potential using a voltmeter, we will place one of the
test leads on the metal and the other in the adjoining solution. The moment we
place the metallic test lead in the solution a new half-cell comes into the
existence. As a consequence, the measured potential will not be that of the
half-cell being measured. However, we can measure the difference between
the two half-cell potentials that gives the emf of the cell. This can be measured
with the help of a potentiometer.
For Daniell cell, the cell emf is found to be 1.11 V. This is the difference
between the potential of the zinc half-cell (anode) and copper half-cell
(cathode). The question comes is that how do we find out the potential of
individual half cells? As stated above, we cannot directly measure the potential
of a half-cell, so we need to combine the half cell with some electrode (or half-
cell) for which the potential is zero. In other words, we need to have a
reference, like we take the temperature at the freezing point of water to be
zero-degree Celsius.
The standard hydrogen electrode (SHE) is taken to be such a reference

whose potential is arbitrarily taken to be equal to zero volt at all temperatures.
The SHE consists of a platinum electrode (coated with platinum black) is
partially dipped in a 1M HCl solution and pure hydrogen gas is bubbled
through it. The pressure of hydrogen gas is maintained at 105 Pa. Now, to
measure the electrode potential of the given half-cell, it is combined with the
Schematic diagram of SHE to form a galvanic cell. It’s emf is then measured with the help of a
standard hydrogen potentiometer. The value so obtained gives the potential of the given half-cell.
electrode In the hydrogen electrode either the protons are reduced, or hydrogen
molecules are oxidized at the Pt surface according to the following equation:
2H+ (aq) + 2e− ⇌ H2 (g) …(7.17)

As a matter of convention, the standard hydrogen electrode is always taken as
188
the electrode on the left of the cell diagram (anode) and the electrode under
consideration on the right (cathode). In other words, there is oxidation at the
hydrogen electrode and reduction at the half-cell being measured. The cell
diagram for the combination of SHE and zinc electrode would then be,
Pt,H2 | H+ (c = 1) | Zn 2 + (c = 1) | Zn …(7.18)
For such a combination of zinc electrode, and SHE the half-cell reactions can
be written as The measured
potential of the cell
Anode: H2 (g) → 2H+ (aq) + 2e− …(7.19) between a redox
couple (under
Cathode: Zn2+ (aq) + 2e− → Zn(s) …(7.4) standard conditions;
solutes at 1 M
Adding the two equations we get the overall cell reaction as concentration, gases
at 101.3 kPa) and
Zn2+ (aq) + H2 (g) → Zn(s) + H+ (aq) …(7.20)
standard hydrogen
electrode is called the
The measured potential of the cell containing zinc electrode and hydrogen
standard reduction
electrode is found to be 0.77 V. However, it is observed that the zinc electrode potential or standard
starts to dissolve to give Zn2+ and the concentration of H+ ions in the hydrogen electrode potential.
electrode decreases (You may recall from your earlier studies that if we place
a piece of zinc metal in an acid, it displaces hydrogen ions and H2 gas is
evolved). This suggests that the zinc electrode is acting as anode whereas
A half-cell that takes
hydrogen electrode acts as cathode. In other words, we can say that the
electrons from the
reaction as given in Eq. (7.20) is not spontaneous. The spontaneous cell standard hydrogen
reaction is as follows cell is assigned a
positive value of E0,
Zn(s) + 2H+ (aq) → Zn2+ (aq) + H2 (g) …(7.21) and one that donates
electrons to the
And the cell diagram for this galvanic cell can be given as follows:
hydrogen electrode, a
Zn(s) | Zn2+ (aq, c = 1) | H+ (aq, c = 1) | H2, Pt …(7.22) negative value.
As we have reversed the reaction, the sign of the potential would also be
reversed, i.e.,
Zn(s) + 2H+ (aq) → Zn2+ (aq) + H2 (g) E 0 = −0.77 V …(7.23)
It is important to note here that though we have reversed the sign, the
absolute value of the potential difference as measured would still be 0.77. The
half-cell reactions would be
Anode: Zn(s) → Zn2+ (aq) + 2e− E 0 = −0.77 V …(7.4)
Cathode: 2H+ (aq) + 2e− → H2 (g) E 0 = 0.00 V …(7.24)
As mentioned before, the standard cell emf is always taken as

0
Ecell = ER0 − EL0 …(7.16)

0
Ecell = 000 − (−0.77) = 0.77V …(7.25)
Now, if we take a combination of copper electrode (under standard conditions)

with SHE and measure the cell potential we get a value of 0.34 V. Here, Cu2+
ions would get reduced to copper metal (i.e., copper electrode would act as 189
cathode) whereas hydrogen gas would get oxidised to hydrogen ions
(i.e., hydrogen electrode would act as anode) i.e., the following half-cell
reactions would occur.
You may note here
Anode: H2 (g) → 2H+ (aq) + 2e− E 0 = 0.00 V …(7.19)
that the half-reactions
are written to show
Cathode: Cu2+ (aq) → Cu(s) E 0 = 0.34V …(7.5)
the oxidation and
reductions taking
The overall cell reaction and the cell notation would be as follows
place at the anode
and cathode, Cu2+ (aq) + H2 (g) → Cu(s) + 2H+ (aq) …(7.26)
respectively. The
overall cell reaction is Pt, H2 (g) | H+ (aq,a = 1) || Cu2+ (aq. a = 1) | Cu(s) …(7.27)
obtained as the sum
of the two half- The corresponding standard cell emf would be
reactions. However,
0
the cell potential is Ecell = ER0 − EL0 …(7.16)
the difference
between the reduction Substituting the values, we get
potentials of the two
0
redox couples. Ecell = 0.34 − (0.00) = 0.34 V …(7.28)
Different electrodes or redox couples are arranged in terms of decreasing

value of their standard electrode potentials as given in Table 7.1. This
arrangement is referred to as electrochemical series. A negative value of the
electrode potential means that the redox couple is a stronger reducing agent
than the H+/H2 couple whereas a positive value conveys that the redox couple
is a weaker reducing agent than the H+/H2 couple. In other words, the redox
couples below hydrogen in the series would reduce hydrogen ions to hydrogen
gas i.e., they will displace hydrogen ions from acid solutions. On the other
hand, the redox couples higher than hydrogen in the series will not be able to
displace hydrogen ions from an acid solution.
You may note that the electrodes or the half-cell reactions are arranged in
order of their decreasing E 0 values and can be used to predict the relative
strengths of various oxidants and reductants. In general, we can say that a
species on the left side of a half reaction (i.e., the oxidised form) will
spontaneously oxidise any species on the right side of another half-reaction
that lies above it in the table. Similarly, any species on the right side of a half-
reaction (i.e., the reduced form) will spontaneously reduce any species on the
left side of another half-reaction that lies below it in the table.
In the event of an electrochemical cell constructed by the combination of any

two electrodes; the electrode with a higher value of electrode potential, E 0
would act as cathode and the one with a lower value would act as anode. If we
make a galvanic cell by combining zinc electrode and copper electrode (i.e.,
make Daniell cell); there would be oxidation at the zinc electrode (anode,
lower E 0 ) and reduction at the copper electrode (cathode, higher E 0 ). The
cell would be represented as
Zn(s) | Zn2+ (c = 1) || Cu2 (c = 1) | Cu … (7.6)
The standard cell emf for the cell can be obtained by using Eq. (7.16).
0
190
Ecell = 0.34 − (−0.77) = 1.11V …(7.29)
0
Table 7.1: Standard electrode potentials (E ) for some redox half-cell
reactions at 298 K
Reduction half-reactions E0, Volts
Oxidising agent Reducing agent
F2 (g) + 2e− ⇌ 2F − (aq) +2.65
S2O82− (aq) + 2e− ⇌ 2SO24− (aq) +2.01
Ce 4 + (aq) + e − ⇌ Ce 3+ (aq) +1.44
O2 + H+ (aq) + 4e− ⇌ 2H2O(I) +1.23
Br2 (g) + 2e− ⇌ 2Br(aq) +1.07
Ag + (aq) + e − ⇌ Ag(s) +0.80
Fe3 + (aq) + e − ⇌ Fe2+ (aq) +0.77
Cu 2 + (aq) + 2e − ⇌ Cu(s) +0.34
Sn4 + (aq) + 2e − ⇌ Sn2+ (aq) +0.15
2H+ (aq) + 2e − ⇌ H2 (g) 0.00
Pb2 + (aq) + 2e − ⇌ Pb(s) −0.13
Sn2 + (aq) + 2e − ⇌ Sn(s) −0.14
Ni2 + (aq) + 2e − ⇌ Ni(s) −0.25
Cd2 + (aq) + 2e − ⇌ Cd(s) −0.40
Cr 3 + (aq) + 3e − ⇌ Cr(s) −0.42
Cr 3 + (aq) + e − ⇌ Cr 2+ (aq) −0.424
Zn 2 + (aq) + 2e − ⇌ Zn(s) −0.77
Al3 + (aq) + 3e − ⇌ Al(s) −1.66
Mg2+ (aq) + 2e− ⇌ Mg(s) −2.38
Be2 + (aq) + 2e − ⇌ Be(s) −1.99
K + (aq) + e − ⇌ K(s) −2.92
Li + (aq) + e − ⇌ Li(s) −3.04
Having learnt about the meaning and significance of cell emf, let us now learn
how do we actually measure the cell emf. However, before that answer the
following simple question to assess your understanding. 191
SAQ 3
The cell reaction for a galvanic cell is given below
Sn(s) + 2Ag+ (aq) → Sn2+ (aq) + 2Ag(s)
a) Write the half-cell reactions at the anode and the cathode
b) Calculate the value of cell emf under standard conditions
7.5.2 Experimental Measurement of EMF

The emf of a cell is usually measured with a potentiometer. The ends of a
uniform wire (XY) of high resistance is connected to a cell (C) of large emf.
Then we connect one electrode of the test cell, T (whose emf has to be
measured) to one end (X) of the wire and the second electrode is connected to
a sliding contact through a galvanometer to detect the flow of current as
shown in the Fig. (7.3).
Fig. 7.3: A schematic diagram of potentiometer setup for measuring cell emf.
In the event of measurement of emf of the cell T, the sliding contact connected
to the second terminal of the galvanometer is moved along the wire XY till we
reach a point, Z where the galvanometer shows zero current flow. At this
stage, the potential from cell C across the segment XZ is exactly balanced by
the emf of cell T.
Then we take another cell A, of accurately known emf EA and replace cell T
with cell A and once again the point (now Z’) where the galvanometer shows
zero current flow is located. Under these conditions we can write,
ET XZ
= …(7.30)
E A XZ '
Using the values of XZ and XZ’ along with the known emf of the cell, A we can
determine the emf of the given cell T.
7.6 THERMODYNAMICS OF REVERSIBLE CELLS

The measured values of the emf of reversible cells can provide us useful
thermodynamic parameters of the cell reaction occurring in them. This linkage
between the cell emf and thermodynamic parameters like, Gibbs energy
change (and hence spontaneity) and equilibrium constant are very significant
from the point of view of applications of emf measurements. Let us explore
192 these linkages.
7.6.1 Cell EMF and Spontaneity
You have learnt that in galvanic cells the Gibbs energy of the spontaneous
redox reaction is extracted as work. This work is electrical in nature and is due
to the movement of ions. Conventional current moves from a point of higher
potential to a point of lower potential. Electrons move in opposite direction.
This work done due to the moving charges depends on the difference in the
electrode potentials (Ecell), the number (n) of moles of electrons being
transferred, and the charge per mole of the electrons (F). We can write,
w elec = −nFEcell …(7.31)
The negative sign in this relation indicates that the work is done by the system.
Now since this work is equal to the change in Gibbs energy of reaction i.e.,
we can write,
w elec = Δr G = −nFEcell …(7.32)
Thus, Δr G = −nFEcell …(7.33)
It is an important relation that connects the Gibbs energy change with the cell
emf. Since, n, and F (Faraday’s constant), both are positive, we can conclude
(from Eq. (7.33)) that a galvanic cell for which E cell is positive, the cell reaction
would be spontaneous (as rG will be negative). For the cell under standard
conditions we can write,
r G0 = −nFEcell
0
…(7.34)
0
We can therefore say that if the value of Ecell for a cell is positive, then the
reaction written as discussed above will occur spontaneously. On the other
0
hand, if the value of Ecell is negative, it means that the reaction for the cell (as
constructed) is not spontaneous, and under standard conditions it will not
occur as written. It would be spontaneous in the opposite direction. However,
the reaction as written can be made to occur with a sufficient input of electrical
energy, i.e., we make it happen electrolytically. Let us take an example to see
how we can use electrochemical series to predict whether a given redox
reaction would be spontaneous or not.
Example 7.4: Predict, using data from Table 7.1, whether the following redox
reaction would be spontaneous or not under standard
conditions.
3Ni(s) + 2Al3+ (aq) → 3Ni2+ (aq) + 2Al(s)
Solution: The first step is to identify the species getting oxidised and reduced
respectively and to write two half reactions. We find here that nickel
is getting oxidised whereas aluminum ions are getting reduced. The
corresponding half-cell reactions would be
Oxidation: Ni(s) → Ni2+(aq) + 2e− E 0 = −0.25 V
Reduction: Al3+(aq) + 3e− → Al(s) E 0 = −1.66 V 193

The reduction potentials for Ni / Ni and Al / Al3+ redox couples, as given in
2+
Table 7.1, are −0.25 and −1.66 respectively

We find that nickel atom gives two electrons while getting oxidised and an
You may note that we
have suitably aluminum ion needs three electrons to be reduced. So, to balance the
multiplied the electrons we multiply the oxidation reaction by 3 and the reduction reaction by
oxidation and 2 to get,
reduction reactions to
Oxidation: 3Ni(s) → 3Ni2+(aq) + 6e− E 0 = −0.25 V
balance the electrons,
the corresponding Reduction: 2Al3+(aq) + 6e− → 2Al(s) E 0 = −1.66 V
reduction potentials
are not multiplied. We know that
0
Ecell = ER0 − EL0

0
Ecell = −1.66 − (−0.25) = −1.41V
As the cell emf is found to be negative it means that the reaction as written will
not be spontaneous.
As we have seen above that the Gibbs energy change for a reaction and the
0
Ecell for a galvanic cell are related so we can calculate the Gibbs energy
change for a redox reaction by measuring the standard cell emf of the galvanic
cell based on the reaction. Let us learn it with the help of an example,
Example 7.5: Calculate the Gibbs energy change for the reaction taking place
in the galvanic cell formed by combining copper electrode with
hydrogen electrode.
Solution: We start with writing the cell notation for the given galvanic cell.
The half-cell reactions, as discussed before, can be written as
Anode: H2 (g) → 2H+ (aq) + 2e− E 0 = 0.00V
Cathode: Cu2+ (aq) + 2e− → Cu(s) E 0 = 0.34V
The overall cell reaction and the cell notation would be

H2 (g) + Cu2+ (aq) → Cu(s) + 2H+ (aq)
Pt, H2 (g) | H+ (aq,c = 1) || Cu2+ (aq,c = 1) | Cu(s)
The corresponding standard cell emf would be

0
Ecell = ER0 − EL0

0
Ecell = 0.34 − (0.00) = 0.34 V
As per Eq. (7.34) the standard Gibb’s energy change is given as

0
The value of n=2 here, as two electrons are getting transferred from copper to
194 hydrogen ions in the cell reaction.
r G0 = −2  96485 C mol −1  0.34 V
r G0 = −65.61kJmol −1
You may note here that for the given cell we could write the half-cell reactions
as follows also
1
Anode: H2 (g) → H+ (aq) + e− E 0 = 0.00 V
2
1 2+ 1
Cathode: Cu (aq) + e− → Cu(s) E 0 = 0.34 V
2 2
In such a case the value of n=1 and the calculated value of Gibbs energy
change would be
r G0 = −1 96485 C mol −1  0.34 V
r G0 = −328 kJmol −1
This value of Gibbs energy change would be for one mole of the following cell
reaction.
1 1 1
H2 (g) + Cu2+ (aq) → H+ (aq) + Cu(s)
2 2 2
Whereas the value (= −65.6 kJ mol−1) we calculated above was for one mole
of the following reaction
H2 (g) + Cu2 + (aq) → 2H+ (aq) + Cu(s)
You may take a note of the fact that the Gibbs energy we get from the
measurement of the cell emf would depend on the number of electrons
participating in the reaction. This in turn, would depend on the way we write
the electrode reactions.
7.6.2 Cell EMF and Equilibrium Constant

We have just related the cell emf with the Gibbs energy of the redox reaction
occurring in a galvanic cell in terms of the following equation,
0
…(7.34)
You would recall from your earlier studies on chemical energetics that the
Gibbs energy change and the equilibrium constant of a reaction are related as
r G0 = −RT ln K …(7.35)
We can use these two expressions to relate the cell emf and the equilibrium
constant as follows
0
− RT ln K = −nFEcell …(7.36) 195
Rearranging, we get
nF 0 0 RT
ln K = Ecell or Ecell = ln K …(7.37)
RT nF
This is an important relation that facilitates the determination of equilibrium

constant of a redox reaction by measuring the emf of the corresponding
galvanic cell. Let us take an example to understand this application of emf
measurement.
Example 7.6: Calculate the equilibrium constant for the cell reaction for
Daniell cell working under standard conditions.
Solution: The Daniell cell under standard conditions can be represented as
Zn(s) | Zn2+ (c = 1) || Cu2+ (c = 1) | Cu
The corresponding half-cell reactions are

Anode: Zn(s) ⇌ Zn2+ (aq) + 2e− E 0 = −0.77
Cathode: Cu2+ (aq) + 2e− ⇌ Cu(s) E 0 = 0.34
The standard cell emf for the cell can be obtained by using Eq. (7.16).
0
Ecell = 0.34 − (0.77) = 1.11V
We know from Eq. (7.33) that
nF 0
ln K = Ecell
RT
2  96485 C mol −1
ln K =  1.11V
8.314 JK −1mol −1  298.15 K
Solving, we get
K = 1037.52 = 3.3  1037
Thus, the equilibrium constant for the reaction occurring in Daniell cell under
standard conditions would be, 3.3  1037
You have learnt that the value of standard cell emf for a voltaic cell can
provide useful thermodynamic data like, the Gibbs energy change and
equilibrium constant. However, what if the cell is not operating under standard
conditions? We need to use Nernst equation under these conditions. Let us
learn about the Nernst equation-an important equation in electrochemistry.
However, before that solve the following simple questions to gauge your
understanding.
SAQ 4
The cell reaction for a galvanic cell is given below
2Al(s) + 3Sn2+ (aq) → 2Al3+ (aq) + 3Sn(s)
b) Predict whether the given cell reaction be spontaneous; use data from
Table 7.1.
196
SAQ 5
Calculate the equilibrium constant for the reaction occurring in the following
voltaic cell. (Use data from Table 7.1).
Fe(s) | Fe2+ (aq,c = 1) || Cd2+ (aq,c = 1) | Cd(s)
7.7 NERNST EQUATION AND ITS APPLICATIONS

The discussion above has been on the standard electrode potential i.e., the
standard reduction potential of a redox couple when all the species are at
standard conditions (1 M concentrations / 1 bar pressure). However, in real
systems, the conditions may not be standard, therefore, the electrode
potential/ cell emf would be different. In such cases the actual potential of the
redox couple would depend on the standard electrode potential and the actual
concentrations of the species involved. The relationship between the actual
electrode potential and standard electrode potential for a given redox couple
was formulated by Walther Nernst. It is expressed in terms of an equation
called Nernst equation which can be derived on the basis of the relationship
between the Gibbs energy change and the cell emf as given in Eq. (7.33) and
Eq. (7.34). We can rewrite the equations as
 r G = −nFEcell …(7.33)
0
…(7.34)
Further, you would recall from the course BCHCT-133 that the Gibbs energy
change under standard and non-standard conditions are related as
r G = r G0 + RT ln Q …(7.38)
Where, Q is the reaction quotient; R is gas constant and T is the absolute

temperature. Substituting expressions for Gibbs energy changes we get,
0 0
− nFEcell = −nFEcell + RT ln Q …(7.39)
Dividing the expression by −nF on both sides we get
0 RT
E cell = E cell − ln Q …(7.40)
nF
This is the Nernst equation. Here, R is the gas constant, T is the absolute
temperature, n is the number of electrons participating in the reaction, and F is
the Faraday’s constant. Substituting these values and converting natural
logarithm to the one to the base 10 we get
0 8.314 JK −1 mol −1 298.15 K

Ecell = Ecell −  2.303 log Q …(7.41)
n  96485 C mo l −1
Simplifying, we get
0 0.0592
Ecell = Ecell − log Q …(7.42)
n 197
Nernst Equation for Electrode (half-cell) Reactions
Let us consider the following electrode reaction,
Mn+ (aq) + ne − → M(s) …(7.43)
The electrode potential of the electrode at any concentration measured with

respect to standard hydrogen electrode will be given by the following equation
0.0592 [M]
EMn + /M = EM0 n + / M − log n+
…(7.44)
n [M ]
The logarithm term is the ratio of the concentrations of the reduced and
oxidised forms of the species. As the concentration (rather activities) for pure
solids and liquids are taken as 1, the equation becomes,
0.0592 1
EMn + /M = EM0 n + / M − log n+
…(7.45)
n [M ]
As an example, for copper electrode, the Nernst equation at 298 K would be

0.0592 1
0
ECu2+ / Cu = ECu2+ − log 2+
…(7.46)
/ Cu 2 [Cu (aq)]
7.7.1 Applications of Nernst Equation

The Nernst equation finds extensive applications in analytical chemistry and
life processes. Electrochemical cells are extensively used for calculating the
pH of solutions, solubility product, equilibrium constant and other
thermodynamic properties. In all these applications of electrochemical cells the
Nernst equation has a role to play. We will take up following simple common
applications
• Determination of equilibrium constant
• Determination of cell emf under non-standard conditions
• Predicting spontaneity of a cell reactions under non-standard conditions
• Determination of pH value of a solution
• Determination of Ksp of a sparingly soluble salt
Let us take up these applications with the help of examples.
Determination of equilibrium constant
Once again, you may recall from your earlier study about chemical equilibrium
that at equilibrium, Q =K and rG = 0 which means that Ecell = 0.
Substituting in Eq. (7.40), we get
0 RT nF 0
0 = Ecell − ln K ➔ ln K = Ecell …(7.47)
nF RT
Which is the same expression we got before, Eq. (7.37). In other words, we
can determine the equilibrium constant from cell emf measurement. In
example 7.6 you have seen how this equation can be used to determine the
198 equilibrium constant of a redox reaction.
Determination of cell emf under non-standard conditions
If a galvanic cell is working under standard conditions, then its emf can be
easily obtained by using the standard electrode potentials of the redox couples
involved. The Nernst equation allows to do the same when the cell is working
under non-standard conditions say the concentrations (activities) of the ions
are different from unity.
Let us understand it with the help of an example.
Example 7.7: Calculate the emf of the galvanic cell given by the following cell
0 0
diagram. (Given: ENi2+
/Ni
= −0.25 and EPb 2+
/Pb
= −0.13)
Ni(s) | Ni 2+ (aq,c = 0.03 M) || Pb2+ (aq,c = 0.30) | Pb(s)
Solution: We know that according to the Nernst equation,

0 0.0592
Ecell = Ecell − n
log Q
0
Therefore, to calculate the value of E cell we need to know Ecell and Q. To
0
calculate the value of Ecell we would proceed as in Example 7.4. We note here
that nickel is getting oxidised whereas lead ions are getting reduced. The
corresponding half-cell reactions would be
Oxidation: Ni(s) → Ni 2+ (aq) + 2e − E 0 = −0.25 V
Reduction: Pb 2+ (aq) + 2e − → Pb(s) E 0 = −0.13 V
The cell reaction would be
Ni(s) + Pb 2+ (aq) → Ni 2+ ( aq) + Pb(s)
We know that
0 0 0
Ecell = ERight − ELef t

0
Ecell = −0.13 − ( −0.25) = 0.12 V
You would recall from your earlier study on chemical equilibrium that the
reaction quotient,Q for a reaction has the same expression as that of
equilibrium constant but the concentrations are not at equilibrium. So for the
cell reaction given above, we can write
[Ni 2 + ]
Q=
[Pb 2 + ]
Note here that in this expression we have not included the concentrations of
solid lead and nickle as these are taken as 1. Substituting the standard cell
emf, value of Q and the number of electrons (n) in the nernst equation we get
[Ni2 + ]
Ecell = 0.12 − 0.0592 log =
2 [Pb2 + ] 199
Substituting the given concentrations of ions, we get
Ecell = 0.12 − 0.0592

2
log 00..03
30
Simplifying, we get
Ecell = 0.1496 V
As the cell emf is found to be positive it means that the reaction as written will
be spontaneous under given conditions.
Predicting spontaneity of a cell reactions under non-standard conditions
You have learnt above that the cell emf is directly related to the Gibbs energy
change and the expressions for the cells under standard and non-standard
conditions are as given below
0
…(7.33)
 r G = −nFEcell …(7.34)
You have learnt about the determination of E cell for a voltaic cell under
nonstandard conditions in example 7.7. Once its value is known it can be used
to get the Gibbs energy change for the reaction. The algebraic sign of either
the cell emf or of Gibbs energy change can be used to predict the spontaneity
of a cell reaction under non-standard conditions.
Determination of pH value of a solution
You know that the pH value is a measure of the concentration of hydrogen

ions in an aqueous solution. In other words, if we can measure the
concentration of hydrogen ions in a solution, we can in principle determine its
pH value. Now the question is can we use the emf measurement to find the pH
of a solution? The answer is yes. We can do so by making the given solution a
hydrogen electrode by dipping a platinum electrode in it and bubbling
hydrogen gas around it at a pressure of 1 bar. This hydrogen electrode can be
combined with another electrode to form a galvanic cell. As the concentration
of hydrogen ions in the given solution is different from standard conditions, the
cell so formed will be under non-standard conditions. The measured emf of
such a cell can then be used to determine the concentration of hydrogen ions
and hence the pH of the solution. Let us understand it with the help of an
example.
Example 7.8: The aqueous solution of an acid is provided with a platinum

electrode around which hydrogen gas is bubbled at a pressure
of 1 bar. The hydrogen electrode so obtained is combined with a
standard zinc electrode to construct a galvanic cell. If the emf of
the cell at 298 K is found to be 0.39 V, find the pH of the
0
solution. (Given: EZn 2 + / Zn = −0.77 V )
Solution: The cell can be represented as
Zn(s) | Zn2+ (aq,c = 1) || H+ (aq,c = ?) | H2 (g),Pt E = 0.39 V

200
The corresponding cell reaction would be
Zn(s) + 2H+ (aq) → Zn2+ (aq) + H2 (g)
The standard cell emf would be

0
Ecell = 0.00 − (−0.77) = +0.77 V
The Nernst equation for the cell can be written on the basis of cell reaction as
[ Zn2 + ] pH
0
Ecell = Ecell − 0.0592 log 2
n [Zn][H+ ] 2
As the concentration of pure solids is taken as 1 and p H2 = 1 bar we can write,
2+
0
Ecell = Ecell − 0.0592 log [ Zn+ ]
n [H ] 2
Since we have standard zinc electrode, [Zn 2 + ] = 1M, substituting the values,
[ 1]
0.39 = 0.77 − 0.0592 log
2 [H+ ] 2
Rearranging we write,
[ 1]
− 0.38 = − 0.0592 log =
0.0592
log [ H + ] 2
2 [H+ ] 2 2
− 0.38 = 0.0592 log [ H+ ]  0.38 = −0.0592 log [ H+ ]

0.38
 0.38 = 0.0592 pH  pH = 0.0592
= 6.42
Thus, the pH of given solution is calculated to be 6.42
Determination of Ksp of a sparingly soluble salt
You have learnt about the solubility and solubility product of sparingly soluble
salts in BCHCT-133 course. You would recall that these salts have extremely
low solubility. The dissolved part of the sparingly soluble salt in its solution can
be considered to be fully dissociated. The product of the molar concentrations
of the constituent ions in solution, each raised to the power of its stoichiometric
coefficient in the solubility equilibrium is called solubility product. The emf
measurement can be used to determine the solubility product of a sparingly
soluble salt. The principle of such a determination is similar to that of the
determination of pH of an aqueous solution explained above. Let’s understand
it with the help of an example.
Example 7.9: A silver-silver ion electrode formed by dipping a silver rod in a

saturated solution of AgCl showed a potential of 0.50 V when
combined with a standard hydrogen electrode. Calculate the
0
solubility product of AgCl. (Given: EAg+ / Ag = 0.80 V)
Solution: We know that for AgCl, Ksp = [Ag+] [Cl−]
Also, we know that the concentration of silver ions and chloride ions will be
equal. If the solubility of the salt is ‘s’, then the concentrations of silver and
chloride ions would be s mol dm−3 each. 201
We can write
K sp = s 2 mol 2 dm −6
Thus, if we know the concentration of silver ions in the solution, we can find
the solubility product. The concentration of the silver ions can be obtained
from the emf of given cell. The cell can be represented as
Pt, H2 (g) | H+ (aq,c = 1) || Ag+ (aq,c = ?) | Ag(s) E = 0.50 V
The standard cell emf would be

0
E cell = 0.80 V − ( 0.00 V ) = +0.80 V
The cell reaction would be
Ag+ (aq) + 1/2H2 (g) → Ag(s) + H+ (aq)
We can write the Nernst equation as
[ Ag ] [ H+ ]
0
Ecell = Ecell = − 0.0592 log
n [ Ag + ] p1/ 2
H2
As the concentration of pure solids is taken as 1, and for standard hydrogen

electrode the concentration of hydrogen ions is 1M and the pressure of
hydrogen gas is pH 2 = 1bar we can write,
0
Ecell = Ecell = − 0.0592 log 1
n [ Ag+ ]
0.50 = 0.80 − 0.0592 log 1

n [ Ag+ ]
Simplifying, we get
−0.30
log [ Ag + ] = 0.0592
− 5.07  [ Ag + ] = 8.5  10 −6 mol dm−3
Substituting in the solubility product expression, we get
 K sp = (8.5  10−6 )2 = 7.225  10−11 mol 2 dm−6
Thus, the solubility product of silver chloride is calculated to be
= 7.225  10−11 mol 2 dm−6
Having learnt about the Nernst equation and its applications, let’s now take up
different types of electrodes used in electrochemical cells. However, before
that solve the following simple questions to assess your understanding.
SAQ 6
Will the following reaction as written, be spontaneous if the concentrations of
Fe2+and Cd2+ ions are 1.00 M and 0.20 M respectively? ( Use Table 7.1)
Cd(s) + Fe2+(aq) → Cd2+(aq) + Fe(s)

202
SAQ 7
The emf of a voltaic cell containing copper and silver electrodes is found to be
0.40 V. If the concentration of silver ions is 0.70 M, calculate the concentration
of copper ions. ( Use Table 7.1)
7.8 TYPES OF ELECTRODES

A large number of different types of electrodes are employed in the
electrochemical cells. These are classified as
• Gas electrodes
• Metal-metal ion electrodes
• Metal-sparingly soluble salt electrode
• Redox electrodes
• Amalgam electrodes
• Membrane electrodes
Let’s learn about these types of electrodes with their representative examples.
Gas electrodes: These consist of a gas bubbled around an inert metal rod /
strip like platinized platinum dipped in a solution containing ions to which the
gas is reversible. Over a period of time, the gas gets adsorbed on the inert
metal and an equilibrium is established between the gas and its own ions in
the solution. Standard hydrogen electrode, about which you have learnt above
is an important example of this class. The reduction half-cell reaction for
hydrogen electrode and its representation is given as
H+ (aq) + e− ⇌
1
H ( g)
2 2
…(7.48)
Pt, H2 (g)| H+ (aq, c = 1)| …(7.49)
The potential of the gas electrode depends on the pressure of the gas, and the
concentration of the ions in solution. For hydrogen gas electrode, the Nernst
equation can be written as
p1/2
0 0.0592 H
E =E − 1
log c 2 …(7.50)
H+
Since for standard hydrogen electrode, E0 is taken as zero, we can write

p 1/2 c +
0.0592 H
E=− log c 2  E = 0.0592 log H
…(7.51)
1
H+ p 1/2
H2
Other commonly used gas electrodes, their representation and half-cell

reactions are given below.
Gas electrode Half-cell reaction Representation

Oxygen 1
O ( g) + H 2 O + 2e − ⇌ 2OH- ( aq) Pt,O2 (g)1bar | OH− (aq, c = 1)|
2 2
electrode
Chlorine 1
Cl2 (g) + 2e − ⇌ Cl− (aq) Pt, O2 (g)1bar | Cl− (aq, c = 1) |
2
electrode 203
Metal-metal ion electrode
It is the one of the most commonly used categories of electrodes. A metal-

metal ion electrode typically consists of a metal strip /rod in contact with a
solution of its own ions to which the electrode is reversible. The half-cell
reaction for such an electrode can be given as
Mn+ (aq) + ne − → M(s) …(7.43)
A standard metal-metal ion electrode is represented as
Mn+ (s) | Mn+ ( aq, c = 1) | …(7.52)
The potential of metal-metal ion electrode depends on the concentration of the

metal ions in the solution and the temperature. The Nernst equation for the
electrode can be given as
E Mn+ / M = E M0 n+ /M − 0.0592 log 1

…(7.53)
n [Mn + ]
Zn | Zn2+; Cu | Cu2+; Pb | Pb2+and Ag | Ag+; are common examples of metal-

metal ion electrodes.
Amalgam electrode
In case of certain metals it is not possible to use pure metal as it can react with
water, e.g., potassium. In such cases, an amalgam of the metal is used and
the electrodes are called amalgam electrodes. Electrical contact is made by
a platinum wire dipped into the amalgam pool. For example, the potassium
amalgam electrode can be represented as
Pt (s) | K (Hg) | K + (aq) | …(7.54)
The potential of amalgam electrodes depend on the concentration (activity) of

the metal in the amalgam. The potential of amalgam electrode can be given as
0.0592 [ M( Hg )]
E Mn+ /M = E M0 n+ /M − log …(7.55)
n [ Mn + ]
The amalgam electrodes have an added advantage as these attain equilibrium

relatively easily as compared to pure metal electrodes.
Metal –sparingly soluble salt electrode: such an electrode consists of a

metal in contact with one of its sparingly soluble salts and a salt solution
containing negative ion common with the salt. The electrode reaction involves
a reversible reaction between the metal and the negative ion to form sparingly
soluble salt accompanied by the liberation of electrons. Calomel electrode and
silver-silver chloride electrodes are common examples of this type of
electrodes.
The calomel electrode consists of mercury (Hg) in contact with its insoluble
salt, mercurous chloride (Hg2Cl2) and a solution of KCl. The electrode is
represented as
204 Hg( l ) | Hg 2Cl2 (s)| Cl− (aq, c = 1) | …(7.56)

The calomel electrode is reversible to chloride ions and its potential depends
on the concentration of chloride ions. However, if we take a saturated solution
of KCl then it’s half-cell potential becomes constant (0.2682 V) and the
electrode is called Saturated Calomel Electrode (SCE). As a consequence, it
is commonly used as a reference electrode. The SCE is represented as
Hg( l ) | Hg 2Cl2 (s)| Cl− (aq, satd.) | …(7.57)
When used as a cathode in a galvanic cell, the mercurous chloride is reduced

to mercury as per the following equation
Hg 2Cl2 (s) + 2e− → Hg (l ) + 2Cl− …(7.58)
As it is inconvenient to use standard hydrogen electrode, the saturated

calomel electrode is commonly employed as a reference electrode in
electrochemical work. Once it has been calibrated against the SHE, it can be
used to determine the standard electrode potentials of many other electrodes
Redox electrodes
This type of electrodes consists of an inert metal like platinum in contact with
an aqueous solution of the ions of an element in different oxidation state. The
metal electrode does not react with the species in solution, it merely acts as a
carrier of electrons. A system in which a platinum electrode is dipped in an
aqueous solution containing ferrous and ferric ions is one of the most
commonly used redox electrode.
The half-cell reaction, and electrode representation for it can be given as
Fe3 + (aq) + e− → Fe2+ (aq) …(7.59)
Pt(s) | Fe3 + (aq,c = c1); Fe2+ (aq,c = c2 ) | …(7.60)
The potential of such an electrode depends on the ratio of the concentrations

of the metal ions in the two different oxidation states. For the Ferric/ferrous ion
electrode, we can write
0 0.0592 [Fe2 + ]
EFe3 + /Fe2 + = EFe3+
/Fe2 +
− log …(7.61)
1 [Fe3 + ]
Membrane electrodes
In this type of electrode two solutions having different concentrations of the

same salt are separated by a membrane that is selectively permeable to one
of the ions of the salt. This ion would tend to diffuse through the membrane
whereas the other ion will not be able to do so. As a consequence, a potential
develops across the membrane. A glass electrode used for the measurement
of pH of aqueous solutions is one of the most common examples of this class.
You would learn in detail about glass electrode in the next unit when we would
take up pH determination as an application of emf measurements.
Let us now sum up what we have discussed in this unit. However, before that
solve the following simple question to assess your understanding. 205
SAQ 8
A redox electrode contains aqueous solution of Sn4+ and Sn2+ ions in which a
platinum rod is dipped.
a) Write the electrode reaction
b) Give the half-cell representation
c) Using data from Table 7.1 calculate the potential of the electrode if the
concentrations of stannous and stannic ions are 0.50M and 0.25 M
respectively.
7.9 SUMMARY
In this first unit on electrochemistry, we started by introducing the domain of
electrochemistry as the one that deals with the study of production of
electricity from energy released during spontaneous chemical reactions and
also the use of electrical energy to make non-spontaneous reactions possible.
Thereafter, we took up electrochemical cells wherein we talked about Galvanic
and electrolytic cells. Since our main focus in this unit was on galvanic cells
we explained different aspects of galvanic cells by taking Daniell cell as a
representative example. This was followed by differentiating between
reversible and irreversible cells.
The next topic we took up was the representation of galvanic cells wherein we
talked about writing cell-notation or cell diagram for a given galvanic cell, and
its relationship with the cell reaction. This was followed by the concept of emf
of the cell and its measurement. In this context we introduced the concepts of
electrode potential; standard electrode potential and cell emf etc. Thereafter,
we explained the relationship between cell emf and thermodynamic
parameters like, Gibbs energy, equilibrium constant etc. We also discussed
about the Nernst equation and its applications. Towards the end of the unit we
described different types of electrodes used and also explained the reactions
taking place in them along with their advantages.

1. Write the cell diagram for a galvanic cell in which the following reaction
takes place.
Cell reaction: Zn(s) + 2Ag+(aq) → Zn2+(aq) + 2Ag(s)
Assume that potassium nitrate is used as electrolyte in the salt bridge and
the concentrations of zinc ions and silver ions are c1 and c2, respectively.
2. Calculate the emf of a Daniell cell in which the concentration of zinc ions in
zinc electrode and copper ions in copper electrode are 0.050 and 0.025 M
respectively.
3. The cell reaction for a galvanic cell is given below
Ni(s) + 2Ag+ (aq) →Ni2+ (aq) + 2Ag(s)
206 a) Write the half-cell reactions at the anode and the cathode
b) Calculate the value of standard cell emf
c) Predict whether the cell reaction given above is spontaneous or not
4. The standard electrode potential of zinc electrode is −0.77V. Calculate the

potential of zinc electrode containing 2M aqueous solution at 300K
5. The cell reaction for a galvanic cell is given below
Cd(s) + Pb2+(aq) →Cd2+(aq) + Pb(s)
b) Calculate the value of cell emf under standard conditions
c) Calculate the cell emf if the concentrations of cadmium and zinc ions
are 0.02 M and 0.2 M respectively.
7.11 ANSWERS
Self Assessement Questions
1. Galvanic cells are the electrochemical cells in which the Gibbs energy
change of the redox reaction is utilised to perform electrical work.
As the silver ions are getting displaced this means that these ions are
getting reduced. Further, since the reduction must be accompanied by
oxidation, the aluminium metal would get oxidised to give aluminum ions.
Therefore, if a galvanic cell is formed by using aluminum and silver
electrodes, the aluminium electrode would act as anode whereas silver
electrode would act as cathode. The cell reaction can be given as
3Ag + (aq) + Al(s) → 3Ag(s) + Al 3 +
2. A cell-diagram is a shorthand notation (a symbolic representation) of an

electrochemical cell. The cell-diagram of the galvanic cell in which the
given reaction takes place will be
Fe(s)| Fe2 (aq)|| Cd2+ (aq)| Cd(s)
3. In the given reaction tin is getting oxidised and silver ions are getting
reduced. The half-cell reactions at the anode and cathode would be
Anode: Sn(s) → Sn2+ (aq) + 2e− E 0 = −0.14 V
Cathode: 2Ag+ (aq) + 2e− → 2Ag(s) E 0 = 0.80 V
(You may note here that we have multiplied the cathodic equation by 2 to
balance electrons but we have not multiplied the half-cell potential)
0 0 0
We know that Ecell = Ecathode − Eanode
Substituting the values from Table 7.1, we get

0
Ecell = 0.80 − ( −0.14) = 0.94 V
207
4. In the given reaction aluminum is getting oxidised and tin ions are getting
reduced. The half-cell reactions at the anode and cathode would be
Anode: 2Al(s) → 2Al3 (aq) + 6e− E 0 = −0.166 V
Cathode: 3Sn2+ (aq) + 6e− → 3Sn(s) E 0 = −0.14 V
(You may note here that we have multiplied the cathodic reaction by 3 and
the anodic reaction by 2 to balance electrons but we have not multiplied
the half-cell potential)
0 0 0
We know that Ecell = Ecathode − Eanode

0
Ecell = −0.14 − (−1.66) = 1.80 V
Since the standard cell emf is found to be positive, the cell reaction is
spontaneous.
5. The half-cell reactions for the given voltaic cell can be given as
Anode: Fe(s) → Fe2+ (aq) + 2e− E 0 = −0.41V
Cathode: Cd 2 + (aq) + 2e − → Cd ( s ) E 0 = −0.40 V
The standard cell emf for the cell can be obtained by using the following
equation
0 0 0
Ecell = Ecathode − Eanode

0
Ecell = −0.40 − (−0.41) = 0.01V
We know that,
nF 0
ln K = Ecell
RT
2  96485 C mol −1
ln K =  0.01V
8.314 JK −1mol −1  298.15 K
Solving, we get K = 100.338 = 2.17
Thus, the equilibrium constant for the reaction occurring in the given
voltaic cell under standard conditions would be, K = 2.17
6. As the given voltaic cell is not under standard conditions, we would need
to use Nernst equation to calculate cell emf.
We know that according to Nernst equation
0 0.0592
Ecell = Ecell − log Q
n
0
First, we calculate Ecell
208 For the given cell, the half-cell reactions can be written as
2+ 2+ − 0
Anode: Cd (s) → Cd (aq) + 2e E = −0.40 V
Cathode: Fe(aq) + 2e− → Fe(s) E 0 = −0.41V
0
The value of Ecell would be
0
Ecell = 0.40 − (−0.41) = 0.01V
For the given cell reaction, the reaction quotient, Q would be
[Cd2 + ] 0.2
Q= = = 0 .2
[Fe2 + ] 1.0
Substituting the standard cell emf, value of Q and the number of electrons
(n) in the nernst equation we get
0.0592
Ecell = 0.01 − log 0.2
2
0
Simplifying, we get Ecell = 0.03
As the cell emf is found to be positive it means that the reaction as written
will be spontaneous under given conditions.
7. From Table 7.1 we observe that the standard electrode potential of silver
electrode (0.80 V) is more positive than that of copper electrode (0.34 V).
This implies that there will be reduction at the silver electrode (cathode)
and oxidation at copper electrode (anode). We can write the half-cell
reactions as
Anode: Cu(s) → Cu2+ (aq) + 2e− E 0 = 0.34 V
Cathode: 2Ag+ (aq) + 2e− → 2Ag(s) E 0 = −0.80 V
0
The value of Ecell would be
0
Ecell = 0.80 − (0.34) = 0.46 V
As the cell is not under standard conditions, we use Nernst equation, i.e.,
0
Ecell = Ecell − 0.0592
n
log Q
Substituting the given value of cell emf along with the computed standard
cell emf, we get
[ Cu 2 + ]
0.40 = 0.46 − 0.0592 log
2 [Ag + ] 2
Substituting the concentration of silver ions and simplifying we get
[Cu2+ ]
 2.027 = log
0.0049
Solving, we get [Cu2 + ] = 0.52 M 209

8. The electrode reaction can be written as
Sn4 + (aq) + 2e− → Sn2 (aq)
The corresponding half-cell can be represented as
Pt(s),Sn4 + (aq),Sn2+ (aq) |
From Table 7.1 we can see that the standard electrode potential is
+0.15 V
The half-cell potential under given conditions can be obtained by using

Nernst equation,
0.0592 [Sn 2 + ]
E = E0 − log
n [Sn 4 + ]

0.0592 0.50
E = 0.15 − log
2 0.25
Simplifying, we get, E = 0.141 V
Terminal Questions
1. The cell diagram for the given galvanic cell would be
Zn(s) | Zn2+ (aq, c = c1) | KNO 3 (satd.)| Ag+ (aq, c = c2 ) | Ag(s)
2. The cell diagram for the Daniell cell under standard conditions can be
written as
Zn(s) | Zn2+ (aq, c = 1) || Cu2+ (aq, c = 1) | Cu(s)

0
The standard cell emf, E cell can be obtained as
0
Ecell = 0.34 − (−0.77) = 1.11V
The cell potential of the Daniell cell under given conditions can be
obtained by using Nernst equation
0.0592 [Zn2 + ]
E = 1.11 − log
2 [Cu2 + ]
Substituting the given concentrations, we get

0.0592 [0.050]
E = 1.11− log
2 [0.025]
Solving, we get E = 1.101 V
3. For the given galvanic cell
a) The half-cell reactions can be written as
Anode: Ni(s) → Ni 2 + (aq) + 2e−
210 Cathode: 2Ag+ (aq) + 2e− → 2Ag(s)

b) The standard cell emf can be obtained as

0 0 0

0
Ecell = 0.80 − ( −0.25) = 1.05 V
c) As the value of the cell potential is positive, the reaction as written is

spontaneous.
4. We know that the potential of an electrode under non-standard conditions

can be obtained by using Nernst equation, viz.,
RT
E = E0 − ln Q
nF
For zinc electrode, the half-cell reaction is
Zn2+ (aq) + 2e− → Zn(s) E 0 = −0.77 V
Substituting in the Nernst equation, we write
8.31JK −1 mol −1  300 K 1

E = −0.77 − −1
2.303 log
2  96485 C mol [ Zn 2 + ]
1
E = −0.77 − 0.02977 log
[Zn2+ ]
Substituting the value of concentration of zinc ions, we get
1
E = −0.77 − 0.02977 log = −0.761V
2
5. For the given galvanic cell
a) The half-cell reactions can be written as
Anode: Cd (s) → Cd2+ (aq) + 2e−
Cathode: Pb2+ (aq) 2e− → Pb (s)
b) The standard cell emf can be obtained as

0 0 0

0
Ecell = −0.13 − (−0.40) = 0.27 V
c) As the cell is not under standard conditions, we use Nernst equation

to obtain cell emf. i.e.,
0
Ecell = Ecell − 0.0592
n
log Q
211
For the given cell, the equation becomes
[ Cd2 + ]
0
E cell = E cell − 0.0592 log
2 [Pb 2 + ]
Ecell = 0.27 − 0.0592

2
log 00..20
02
= 0.30 V
212
Unit 8 Electrochemistry-II
UNIT 8
Electrochemistry-II
Structure
8.1 Introduction 8.4 Electrolytic Cells
Expected Learning Outcomes Electrolysis in Different Systems
8.2 Concentration Cells Faraday’s Laws of Electrolysis
Concentration Cells without 8.5 Applications of Electrolysis
Transference
8.6 Summary
Concentration Cells with
Transference
8.8 Answers
8.3 Applications of EMF
Measurements
Determination of pH of aqueous
solutions
Potentiometric Titrations
8.1 INTRODUCTION
In the previous unit you have learnt about galvanic cells in terms of their
formation, principle of working, cell reactions and cell emf etc. You have also
learnt about the thermodynamic applications of emf measurements besides
different types of electrodes. In this unit, to begin with we would continue with
galvanic cells and take up concentration cells, a type of galvanic cells that are
obtained by combining two electrodes (or half cells) that differ only in
concentration of electrolytes or the electrode material. We would take up their
classification and discuss different types of concentration cells in terms of the
electrode reactions, cell reactions and mechanism of their action. In this
context we would also bring in the concept of liquid junction potential and its
significance.
Thereafter, we would take up two important experimental applications of emf

measurements. Herein, we would take up measurement of pH of aqueous
solutions and potentiometric titrations. This would be followed by discussion
on the other type of electrochemical cells, viz., faradaic, or electrolytic cells.
We would differentiate between the voltaic and electrolytic cells and discuss
about the phenomenon of electrolysis. In this context you would study the
electrolysis of different types of systems that include molten salts and aqueous 213
solutions. Thereafter, we would take up the quantitative aspect of electrolysis

and discuss about the Faraday’s laws of electrolysis and their significance.
In the next unit we would take up the study of carboxylic acids.

❖ define and classify concentration cells giving examples of different types;
❖ write the cell reactions and Nernst equations for different types of
concentration cells;
❖ differentiate between electrode concentration cells and electrolyte

concentration cells giving examples;
❖ differentiate between concentration cells with and without transference

giving examples;
❖ define liquid junction potential and describe its development;
❖ derive expressions for the emf of concentration cells with and without
transference;
❖ explain different methods of pH determination using emf measurement;
❖ describe the construction of glass electrode and explain the principle of

its working;
❖ define potentiometric titration and draw a schematic graph of a redox

potentiometric titration;
❖ discuss the differences between voltaic and electrolytic cells;
In principle, if two ❖ define electrolysis and explain the electrolysis of molten salts and
identical electrodes aqueous solutions; and
are immersed in the
same solution, the ❖ state Faraday’s laws of electrolysis and give their significance.
cell potential will be
zero. However, if 8.2 CONCENTRATION CELLS
either the electrodes
have different You would recall from the previous unit that the galvanic cells we considered
composition or they
had two different electrodes having different half-cell reactions. Such cells are
are immersed in
solutions of different commonly referred to as chemical cells as these produce electrical energy
concentrations, a cell from chemical changes. In another type of galvanic cells, we use two identical
potential will develop electrodes having the same half-cell reactions; however, these differ in terms
of concentration of electrolytes or the composition of electrode material. Such
galvanic cells are called concentration cells. In such cells, there is no overall
chemical reaction; the change in emf is due to the change in the concentration
of the electrolyte or the electrodes. The concentration cells can be divided into
two groups depending on whether they differ in the electrode material or the
concentration of the electrolyte. The two types are:
• Electrode concentration cells
214 • Electrolyte concentration cells

Let us learn about these in somewhat details.
8.2.1 Electrode Concentration Cells

As the name suggests, in such concentration cells the composition of
electrode material is different. For example, if we take two hydrogen
electrodes in which the hydrogen gas at different pressures is bubbled around
the platinum electrode and dip them in an aqueous solution containing 1 M
hydrogen ions. This will form a electrode concentration cell and can be
represented by the following cell-diagram
Pt(s);H2 (g, p2 ) | H+ (aq,1M) | H2 (g, p1); Pt(s) p2  p1 …(8.1)
You may note here that the electrode in which the pressure of hydrogen gas is
more, would form the anode (i.e., oxidation would take place at this electrode).
The two half-cell reactions would be
1
Anode: H2 (g, p2 ) → H+ (aq,1M) + e− …(8.2)
2
Cathode: 1 …(8.3)
H+ (aq,1M) + e − → H2 (g, p1 )
2
The overall cell-reaction (obtained by adding Eq. 8.2 and Eq. 8.3) would be
1 1
H2 (g, p2 ) → H2 (g, p1) …(8.4)
2 2
The Eq. (8.4) implies that the cell reaction involves a transfer of hydrogen gas
from higher pressure to lower pressure. The cell emf can be expressed in
terms of the following Nernst equation
0 RT p
Ecell = Ecell − 2.303 log 1 …(8.5)
F p2
0
It is important to note that the standard cell emf, Ecell of any concentration cell
would be zero. This is so because the electrodes are identical, and their
standard electrode potentials would be equal, and their difference would be
zero.
0
Ecell = EH0 + / H − EH0 + / H = 0 …(8.6)
2 2
So, we can write,
RT p RT p
Ecell = − 2.303 log 1 = 2.303 log 2 …(8.7)
F p2 F p1
Since p2 is greater than p1, the value of Ecell will be positive and the net cell
reaction would be spontaneous and proceed till the two pressures become
equal. This is why it was stated that the hydrogen electrode with greater
pressure of hydrogen would form anode. If we had taken the electrode with
lower pressure as anode, then the cell reaction would not have been
spontaneous. You may note here that the Ecell in this case depends only on
the pressure of hydrogen gas in the two electrodes and is independent of the
concentration (or activity) of hydrogen ions. 215
Two amalgam electrodes having different electrode compositions (activities)

in contact with the solution of an electrolyte having the ion of the metal in the
amalgam can also combine to form concentration cells. For examples, two
sodium amalgam electrodes having varying concentrations (molalities) of
sodium metal are dipped in a solution of sodium chloride to form an electrode
concentration cell.
The cell diagram and the cell reaction for the electrode concentration cell so
obtained can be given as
You may note here Na( c = m 2 in Hg) | NaCl(aq, c = c 1 ) | Na( c = m1 in Hg) m 2  m1 …(8.8)
that in case of
amalgam Here again, the electrode with higher concentration of sodium metal in the
concentration cells amalgam would form the anode.
we have used
molality as the unit for Anode: Na( c = m2 in Hg) → Na + (aq) + e− …(8.9)
concentration. This is
only for convenience. Cathode: Na + (aq) + e− → Na( c = m1 in Hg) …(8.10)
We could use
molarity also as used The overall cell-reaction would be
in other cases.
Na( c = m2 in Hg) → Na( c = m1 in Hg) …(8.11)
Again, the cell reaction involves a transfer of sodium from the amalgam having
higher concentration of sodium to the one having lower concentration. The cell
emf can be expressed in terms of the following Nernst equation
0 RT m
Ecell = Ecell − 2.303 log 1 …(8.12)
F m2
0
As Ecell will be zero, we can write that
RT m RT m
Ecell = − 2.303 log 1 = 2.303 log 2 …(8.13)
F m2 F m1
Since m2 > m1, the Ecell will be positive, and the net cell reaction would be
spontaneous and proceed till the concentrations of sodium in the two
electrodes become equal. You may also note that the Ecell depends only on
the concentration of sodium in the amalgam electrodes and is independent of
the concentration of sodium ions. Let us take an example to learn about the
use of electrode concentration cell.
Example 8.1: The label of a sample of sodium amalgam having small amount
of sodium was lost. In order to determine its composition, it was
combined with another sample of sodium amalgam in which the
concentration of sodium was 9.26 m. The two electrodes were
dipped into a sample of 0.2 M sodium ions and the cell emf was
found to be 0.03V at 298 K. Determine the composition of the
sample of sodium amalgam with lost label.
Solution: As the given sample of sodium amalgam is supposed to have a

small amount of sodium, this would act as cathode in the electrode
concentration cell formed with another sample of sodium amalgam
216 having a concentration of 9.26 m. The cell can be represented as
Na( m = 9.26 in Hg) | NaCl(aq, 0.2 M) | Na( m = ? in Hg)
The cell emf would be
RT 9.26
Ecell = 2.303 log log
F m
Substituting the values at 298 K, we get
9.26
0.03 = 0.0592 log
m
9.26 0.03
Simplifying, we get log = = 0.507
m 0.0592
Taking antilog and solving
9.26 9.26
= 3.214  m= = 2.88 m
m 3.214
Thus, the concentration of sodium metal in the sample of sodium amalgam

with lost label would be 2.88 m.
Let us take the second type of concentration cells, viz., electrolyte

concentration cells. However, before that answer the following simple question
to assess your understanding.
SAQ 1
Write the electrode reactions, cell reaction, and calculate the Ecell of the
following electrode concentration cell at 298 K.
Cd(0.001m in Hg) | CdSO 4 (aq,0.1M) | Cd(0.0001m in Hg)
8.2.2 Electrolyte Concentration Cells
In this type of concentration cells, the composition of electrode material of both

electrodes is same, but these are dipped in the electrolyte solutions of different
concentrations. For example, if we take two copper electrodes (Cu|Cu2+) in
which the concentrations of copper ions are different (say c1 and
c2respectively; c2 > c1) and combine them to form a galvanic cell, these will
give an electrolyte concentration cell as shown in Fig. (8.1).
Fig. 8.1: The arrangement of two copper half-cells in a electrolyte concentration

cell. 217
Let us ask a question; in which direction will the electrons flow in this cell? Or
which half cell would act as the anode and which one would be the cathode.
To answer this question we use the fact that the system would have a natural
tendency to equalise the concentration of copper ions in the two half-cells.
This is possible if the concentration of copper ions increases in the half-cell
with lower concentration and decreases in the one with higher concentration.
We know that the concentration of metal ion in metal-metal ion electrode can
increase by the oxidation of metal. Similarly, the concentration of metal ions
can decrease by their reduction. Thus, we can say that the electrode with
higher metal ion concentration would act as the cathode where metal ions
would get reduced and the one with lower concentration of metal ion would act
as anode where metal ions would be formed. On the basis of these
arguments, we can represent the cell by the following cell-diagram
Cu(s) | Cu2 + (aq,c = c1) || Cu2+ (aq,c = c2 ) | Cu(s) c2  c1 …(8.14)
By adding two half-cell reaction, the half-cell reactions would be
Anode: Cu(s) → Cu2 + (aq, c = c1) + 2e− …(8.15)
Cathode: Cu2 + (aq, c = c2 ) + 2e− → Cu(s) …(8.16)
The overall cell-reaction would be
Cu2+ (aq, c = c2 ) → Cu2+ (aq, c = c1) …(8.17)
This reaction represents the transport of cupric ion from a region of higher
concentration to that of lower concentration. The cell emf would be given in
terms of the following Nernst equation
You may note that in
the concentration RT c RT c
Ecell = − 2.303 log 1 = 2.303 log 2 …(8.18)
cells the net reaction F c2 F c1
involves only changes
in composition of As c2 is greater than c1, the cell emf would be positive and the cell reaction
species and there is
would be spontaneous.
no net oxidation or
reduction. You might have noticed that in the three different concentration cells
considered above, we have stated that the cell reaction corresponds to the
transfer / transport from the region of higher concentration (activity) to the
region of lower concentration (activity). Now the question is how does it
happen? What is the mechanism? Let us understand it with the example of the
electrolyte concentration cell given above.
You may see here that in the cell we have used a salt bridge (two vertical lines
in the cell diagram to separate the two half cells and allow for the completion
of the circuit. You would recall from the previous unit that when we use a salt
bridge containing high concentration of an inert electrolyte like KCl or KNO3,
the ion transport across the electrolytic solutions is in terms of the ions of the
electrolyte taken in the salt bridge. Actually, there is no direct transfer of ions
from a region of higher concentration to that of the lower concentration. What
happens is that when the circuit is completed, copper atoms from the anode
218 get oxidised to copper ions and the concentration of copper ions in the anodic
half-cell increases. At the same time, an equivalent amount of copper ions
from the cathodic half-cell get reduced and deposited on the cathode.
Effectively, whatever amount of cupric ions disappear at the cathode, an equal
amount of cupric ions appear at the anode. The changes are similar to that
would happen if an actual transfer of these ions had taken place from cathodic
half-cell to anodic half-cell.
With the passage of time the concentration of anodic half-cell electrolyte keeps
on increasing and that of the cathodic half-cell electrolyte keeps on
decreasing. This is accompanied by a decrease in the emf of the cell. Once
the concentrations of copper ions in the two half-cells become equal the emf of
the cell would become zero and the further reaction stops.
The electrolyte concentration cells are further divided into two types depending
on whether they involve transference of electrolyte or not. The two types are
A. Concentration cells without transference
B. Concentration cells with transference
Let us learn about these concentration cells
A. Concentration cells without transference
A galvanic cell using Zn|Zn2+ and Cu|Cu2+electrodes, can be constructed in

two different ways. In one of the ways, the two electrolytic solutions are
separated by a porous membrane which allows the ions to migrate through but
does not allow the mixing of electrolyte solution. Such a cell is called it cell
with transference. On the other hand, the second method involves using a
salt bridge to provide connectivity between the solutions of two electrolytes
and this gives a cell without transference. There are chemical cells; let us
take up an example to see how we can construct a concentration cell without
transference.
Let us take the following cell consisting of hydrogen electrode and silver-silver
chloride electrode in hydrochloric acid having concentration c1. As the two
electrodes dip directly into a solution of HCl; it is a cell without transference.
Pt(s) | H 2 (g,1 bar) | HCl( c 1 ) | AgCl | Ag(s) …(8.19)
In this cell, the

hydrogen electrode is
reversible to the
hydrogen ions
whereas, Ag-AgCl
electrode is reversible
to chloride ions.
Fig. 8.2: A schematic diagram showing cell without transference.
On the left-hand electrode, hydrogen gas gets oxidised to form hydrogen ions,
whereas at the right-hand electrode, chloride ions pass into solution and silver
metal is deposited. The half-cell reactions can be written as 219
1
Anode: H (g, 1 bar) → H+ (aq, c1) + e − …(8.20)
2 2
Cathode: AgCl + e− → Ag(s) + Cl− (aq, c1) …(8.21)
The overall cell reaction can be written as

1
H (g,1 bar) + AgCl(s) → HCl(aq, c1) + Ag(s) …(8.22)
2 2
The cell emf is given by the following Nernst equation,
0 RT
Ecell = ECl− − ln c1 …(8.23)
| AgCl| Ag(s) F
If we take two such cells having the concentration of HCl to be c1 and c2
respectively and combine them opposite to each other as shown in Fig. 8.3 we
get a concentration cell. If the emf of the two cells areE1 and E2 respectively,
then the emf of the concentration cell would be E1−E2.
The concentration cell can be represented as
Pt(s) |H2 (g,1 bar) | HCl( c1 ) | AgCl(s) | Ag(s) | AgCl(s),HCl( c2 ) | H2 (g,1 bar),Pt(s)
Fig. 8.3: A schematic diagram showing concentration cell without transference.
We can write the cell reaction for the cell at the left as
1
H2 (g, 1 bar) + AgCl(s) → HCl(aq, c1) + Ag(s) …(8.24)
2
For the cell on the right the cell reaction would be its opposite, i.e.,
1
HCl(aq, c2 ) + Ag(s) → H2 (g, 1 bar) + AgCl(s) …(8.25)
2
Combining the two cell reactions we get the overall reaction for the
concentration cell as
HCl(aq, c2 ) → HCl(aq, c1 ) …(8.26)
Thus, the net effective change in this concentration cell is the transfer of HCl
from a region of higher concentration (c2) to the region of lower concentration
(c1).
The emf of the concentration cell without transference described above can be
obtained as
0 2RT
Cell on the left: E1 = ECl− − ln c1 …(8.27)
| AgCl| Ag(s) F
220
0 2RT
Cell on the right: E2 = ECl− − ln c2 …(8.28)
| AgCl| Ag(s) F
As stated above, the emf for the concentration cell would be
Ecell = E1 − E 2 …(8.29)
0 2RT 0 2RT
Ecell = ECl− − ln c1 − ECl− + ln c2 …(8.30) The concentration
| AgCl| Ag(s) F | AgCl| Ag(s) F
terms in Eq. 8.27 to
2RT c1 2RT c2 Eq. 8.31 in fact, are
Ecell = − ln = ln …(8.31)
the mean ionic
F c2 F c1
activities (a1 and a2)
You may note here that there is an indirect transfer of HCl from the region of of HCl in the two
cells. The factor 2 in
higher (right cell) to the region of lower (left cell) concentration. With time, the
the expression
concentration of HCl in the left cell increases as per Eq. (8.24) whereas that in appears due to
the right cell decreases as per Eq. (8.25). conversion of product
of ionic activities of
Further, we see that in this concentration cell, the electrolyte is hydrochloric hydrogen ions and
acid, and one electrode (hydrogen electrode) is reversible with respect to chloride ions to mean
hydrogen ions while the other electrode (Ag-AgCl) is reversible with respect to ionic activity of HCl.
chloride ions. From this example, we can say that whenever two simple cells Its derivation is
whose electrodes are reversible with respect to an ion each of the electrolyte beyond the scope of
this course.
are combined in opposition, a concentration cell without transference is
obtained.
B. Concentration cells with transference The electrodes

should be reversible
If we take two identical cells differing only in the concentration of the
to one of the ions of
electrolyte and combine them to form a concentration cell in a way that we the electrolyte.
allow the electrolytes to be in direct contact with each other, then the cell
obtained would be called concentration cell with transference. In such a case
there will be formation of a liquid junction and consequently development of
liquid junction potential. Let us take an example to learn about such a system
and see how this system is different from the one without transference.
Let us take two hydrogen electrodes in which the pressure of hydrogen gas
around the platinum electrode is 1 bar each but the concentration of HCl in the
solutions is c1 and c2 (c2> c1) respectively.
Fig. 8.4: A schematic diagram showing concentration cell with transference.
Further, we combine the two in such a fashion that the two solutions of HCl
are separated by a porous plate. This allows transfer of ions across the
membrane, but the direct mixing of solution is not allowed. A schematic
diagram showing concentration cell with transference is given in Fig. (8.4). 221
Fig. 8.4: A schematic diagram showing concentration cell with transference.
Such a cell can be represented as
Pt(s) | H 2 (g,1 bar) | HCl( c 1 ) | HCl( c 2 ) | H 2 (g,1 bar), Pt bar(s) c 2  c 1 …(8.32)
You may note here that the two hydrogen electrodes are separated by a single
vertical line indicating a porous membrane (you know that a salt bridge is
indicated by two vertical lines). The half cell reactions can be given as
1
Anode: H2 (g, 1 bar) → H+ (aq, c1) + e− …(8.33)
2
1
Cathode: H+ (aq, c2 ) + e− → H2 (g, 1 bar) …(8.34)
2
The overall cell reaction would be
H+ (aq, c2 ) → H+ (aq, c1) …(8.35)
Let us try to visualise the changes taking place in the cell when one Faraday
of current passes through the cell.
In case of 1. Half a mole of hydrogen gas would get oxidised to give one mole of
concentration cell hydrogen ions at the anode
without transference
one of the electrodes 2. One mole of hydrogen ions would get reduced on the cathode and liberate
was reversible to the half a mole of hydrogen gas
cation whereas the
other electrode was 3. tH + moles of hydrogen ions will migrate across the boundary from left to
reversible to the right ( tH + is the transport number of hydrogen ions)
anion. However, in
case of concentration 4. t = (1 − t ) moles of chloride ions will move in the opposite direction,
cell with transference Cl − H+
the electrodes are i.e., from right to the left t is the transport number of hydrogen ions)
Cl −
reversible to one of
the ions of the These processes can be summarised as in Fig. (8.5) given below:
electrolyte.
Fig. 8.5: A representation of electrode reactions and the migration of ions in a

222 concentration cell with transference.
Therefore, to calculate the emf of the cell we need to consider the following
changes along with the overall electrode reactions, Eq.(8.35)
tH+ H+ (c1) → tH+ H+ (c2 ) …(8.36)
(1 − tH+ )Cl− (c2 ) → (1 − tH+ )Cl− (c1) …(8.37)
The total cell reaction can be obtained by combining Eq.(8.35), Eq. (8.36), and
Eq. (8.37)as follows:
H+ (c2 ) − tH+ H+ (c2 ) + (1 − tH+ )Cl− (c2 ) → H+ (c1) − tH+ H+ (c2 ) + (1 − tH+ )Cl− (c1)
…(8.38)
Rearranging,
H+ (c2 ) − tH+ H+ (c2 ) + (1 − tH+ )Cl− (c2 ) → H+ (c1) − tH+ H+ (c1) + (1 − tH+ )Cl− (c1)
…(8.39)
Simplifying
H+ (c2 )[1 − tH+ ] + (1 − tH+ )Cl− (c2 ) → H+ (c1)[1 − tH+ ] + (1 − tH+ )Cl− (c1)
[1 − tH+ ] [H+ (c2 ) + Cl− (c2 )] → [1 − tH+ ] [H+ (c1) + Cl− (c1)] …(8.40)
Now, we know that,

[1 − t ]=t …(8.41)
H+ Cl −
As in the case of cell
without transference,
Substituting, we get,
the concentration
terms here are the
tCl− [H+ (c2 ) + Cl− (c2 )] → tCl− [H+ (c1) + Cl− (c1)] …(8.42)
mean ionic activities
(a1 and a2) of HCl in
tCl− [HCl(c2 )] → tCl− [HCl( c1)] …(8.43)
the two cells
This simplified expression of the overall changes in the cell suggests that
when one Faraday of current passed through the cell, t − moles of HCl are
Cl
transferred from the region of higher concentration to that of lower
concentration. The expression for cell emf can be written as
t −
2RT (c ) Cl 2RT (c )
Ecell = − ln 1 t = t Cl−  ln 2 …(8.44)
F (c 2 ) Cl
− F (c1 )
You may note here that the electrodes are reversible to the cation and the
expression for Ecell has t−. It can be shown that if in the concentration cell with
transference the electrode is reversible to the anion then the expression for
Ecell would have the transport number of the cation.
In addition to the electrode reactions as given above and the consequent

migration of the ions across the membrane, there will be additional transfer of
ions across the membrane due to the difference in the concentration of the two
electrolytes. The ions will move from the region of higher concentration to the
region of lower concentration. As the hydrogen ions move faster than the
chloride ions, they would travel more distance as compared to chloride ions.
As a result of the difference in the speeds of the two ions there is an unequal
distribution of the cations and the anions across the boundary. That is, there
will be opposite charge accumulation across the boundary; positive charge 223
towards the left compartment and negative charge towards the right
compartment. Due to this charge distribution, an additional potential is
developed at the junction of the two liquids. This is called liquid junction
potential.
A schematic illustration of the development of liquid junction potential is given

in Fig. (8.6).
Fig 8.6: Schematic illustration of the development of liquid junction potential.
The overall emf of the cell would depend on the electrode reactions and
migration of ions discussed above as well as liquid junction potential.
Determination of transport numbers using concentration cells
One important application of concentration cells is the determination of

transport numbers. For this we take concentration cells having the same
electrolyte and measure their emf under the conditions of with and without
transference. Eq. (8.44) and Eq. (8.31) give the expressions for the emf of
concentration cells with and without transference respectively, i.e.,
2RT (c2 )
(Ecell )wt = tCl− ln …(8.44)
F (c1 )
2RT c2
(Ecell )wot = ln …(8.31)
F c1
Dividing Eq. (8.44) by Eq. (8.31) we get,
(Ecell )wt
t Cl− = …(8.45)
(Ecell )wot
Thus, the ratio of the cell emf under conditions of with transference and
without transference gives the transport number. Having learnt about
concentration cells; its different types and their principle, let’s now take up
some important applications of emf measurements. However, before that
answer the following simple questions to assess your understanding of
concentration cells.
SAQ 2
Two potassium amalgam electrodes having molalities of potassium as 0.015
and 0.0225 respectively are dipped in a solution of 0.01 M potassium chloride
to form an electrode concentration cell. Write the cell diagram and the cell
reaction for the concentration cell.
224
SAQ 3
Outline the requirements for the construction of concentration cells with and
without transference.
8.3 APPLICATIONS OF EMF MEASUREMENTS

You would recall that in the previous unit we had discussed about a number of
applications of emf measurement of simple galvanic cells e.g., the prediction
of spontaneity and the determination of equilibrium constant for cell reactions
in galvanic cells working under standard conditions. Further, in the context of
applications of Nernst equation we took a number of applications of emf
measurements of the galvanic cells working under non-standard conditions.
Here, we are going to take up two important applications of emf
measurements that find extensive use in analytical chemistry. We begin with
the determination of pH of an aqueous solution.
8.3.1 pH Determination of Aqueous Solutions
You have learnt in the Unit 7 of BCHCT-133 course and Experiment 6 of the
BCHCL-134 course about the concept of pH as a scale to quantitatively
express the concentration or ‘potential’ of H+ ions in the aqueous solutions
especially of dilute solutions (< 0.01 M). It is defined as the negative logarithm
(to the base 10) of the molar concentration of hydrogen ions in solution. That
is,
pH = − log10 [H+ ] or − log10 [H3O + ] …(8.46)
Thus, to know the pH of a given solution we need to measure the

concentration of hydrogen ions in it. There are a number of ways in which we
can use emf measurement to find the concentration of hydrogen ions in an
aqueous solution. The commonly used methods are:
a) Using voltaic cell involving hydrogen electrode
b) Using redox electrode: quinhydrone electrode
c) Using membrane electrode: glass electrode
Let’s learn about these one by one
a) Using voltaic cell involving hydrogen electrode
In the previous unit, you have learnt about the standard hydrogen electrode in
which hydrogen gas is bubbled at a pressure of 1 bar around the platinum
electrode partially dipped in an aqueous solution of 1M HCl. Its electrode
potential is defined to be zero at all temperatures. However, if the
concentration of HCl is different from 1 M then the electrode potential would be
different and would depend on the concentration of hydrogen ions. In other
words, the measured electrode potential of the hydrogen electrode can
provide the concentration of hydrogen ions. However, as you know that we
cannot measure the electrode potential of a single electrode, so we need to
combine it with some other standard electrode and construct a galvanic cell.
The measured emf of the cell so obtained can then be related to the
concentration of hydrogen ions and hence to the pH of the solution. 225
2+
Let us take Cu | Cu electrode in which copper electrode is dipped in an
aqueous solution of 1M copper ions, and combine it with the hydrogen
electrode obtained by partially dipping a platinum electrode in the solution
whose pH is to be measured and passing hydrogen gas at 1 bar pressure
around it. The voltaic cell so obtained is represented as
Pt(s),H2 (g) | H+ (aq, c ) || Cu2+ (aq, 1 M) | Cu(s) …(8.47)
The half-cell reactions would be
At anode: H2 (g, 1 bar) → 2H+ (aq, c ) + 2e− …(8.48)
At cathode: Cu2 + (aq, 1 M) + 2e − → Cu(s) …(8.49)
The overall cell reaction would be
H2 (g, 1 bar) + Cu2+ (aq, 1 M) → Cu(s) + 2H+ (aq, c ) …(8.50)
0
The standard cell emf, E cell would be
Ecell = ER0 − EL0
Ecell = 0.34 − 0.00 = 0.34 V
The emf of the constructed cell is given by the following Nernst equation
0 RT [H+ ]2
Ecell = Ecell − ln …(8.51)
2F [Cu2 + ] pH
2
Substituting the values at 298 K, we get
0.0592
Ecell = 0.34 − log[H+ ]2 …(8.52)
2
Simplifying,
Ecell = 0.34 − 0.0592log[H+ ]  Ecell = 0.34 + 0.0592pH …(8.53)
Thus, by measuring the emf of the cell we can get the value of pH of the
solution. The method is quite simple and straight forward, however, using a
hydrogen electrode is not very practical as firstly it is quite cumbersome to set
up and secondly, the platinum electrode may lose its ability over time due to its
poisoning. A better method involves using quinhydrone electrode-a redox
electrode.
b) Using quinhydrone electrode (redox electrode)
You have learnt in the previous unit that a redox electrode consists of an inert
electrode dipped in a solution containing a mixture of the oxidised and the
reduced forms of a substance. The substance could be ionic or molecular
species. We use the compound, quinhydrone (represented as Q.QH2) for
measuring the pH of a solution. It is sparingly soluble in water and produces
equal concentrations of the oxidised species, quinone (Q), and the reduced
226 species, hydroquinone (QH2).
A shiny platinum electrode dipped in the test solution saturated with

quinhydrone forms the quinhydrone electrode and is reversible to protons. The
electrode reaction involves transfer of electrons between the quinone and
hydoquinone and can be represented as:
Q + 2H + + 2e − ⇌ QH2
The potential of the electrode is given by the following expression
RT [QH2 ]
EQ/QH2 = EQ0 |QH2 − ln …(8.54)
2F [Q] [H+ ]2
At 298 K, the standard potential of the quinhydrone electrode is found to be

0.6994 V. Further, since the amounts of the oxidised and reduced forms are
equal, the expression simplifies to
RT 1
EQ/QH2 = 0.6994 − ln + 2 …(8.55)
2F [H ]
Substituting the values at 298 K and simplifying, we get
0.0592
EQ/QH2 = 0.6994 + log [H+ ]2 = (0.6994 − 0.0592pH) V …(8.56)
2
Thus, we see that the potential of the electrode depends on the pH of the
solution. Now, since we cannot measure the potential of a single electrode we
combine it with a standard electrode (typically saturated calomel electrode)
and construct a galvanic cell and measure the emf of the cell. The cell so
obtained is represented as
Hg( l ),Hg 2Cl2 (s) | KCl(satd.) || H+ (aq,c ) || Q,QH2 | Pt(s) …(8.57)
The cell emf will be given as
Ecell = ER − EL
The electrode potential of saturated calomel electrode at 298 K is 0.2682 V.

Ecell = (0.6994 − 0.0592 pH) V − 0.2682 V = (0.4312 − 0.0592 pH) V 227

Rearranging, we get
(0.4312 − Ecell )
pH = …(8.58)
0.0592
Thus, the measurement of the emf of the cell obtained by combining

quinhydrone electrode formed from the test solution and the saturated calomel
electrode provides the pH of the test solution.
The quinhydrone electrode has an advantage over the hydrogen electrode as

it is quite easy to set up. However, it has a disadvantage that it gives accurate
results only if the pH of the solution is less than 8. In more alkaline solutions
errors arise due to the aerial oxidation of hydroquinone and the ionization of
the hydroquinone that acts as an acid. Let us take up a yet another method of
pH determination using emf measurements.
c) Using glass electrode (membrane electrode)
In the previous unit you have learnt that a membrane electrode consists of a
membrane that separates two solutions of different concentrations of the same
electrolyte and is selectively permeable to one of the ions of the salt. This ion
diffuses through the membrane whereas the other ion will not be able to do so.
As a consequence, a potential develops across the membrane. The potential
a glass electrode of such an electrode depends on the concentrations of the solutions of the
electrolyte.
A calomel electrode One such electrode, a glass electrode is used for the measurement of pH of
can also be used in aqueous solutions. It consists of a glass tube having a thin glass membrane
place of Ag - AgCl bulb (that is permeable to H+ ions) at one end. The bulb is filled with a solution
electrode
of a constant pH (e.g., 0.1 M HCl) and a reversible electrode like Ag−AgCl
electrode (silver wire coated with silver chloride) is dipped in it. When this
glass electrode is dipped in an aqueous solution whose pH is to be
determined, a potential is developed across the glass membrane. This
potential depends on the difference in the concentrations of hydrogen ions
across the glass membrane. The glass electrode having Ag−AgCl electrode
can be represented as
Ag(s) | AgCl | Cl− (aq) | H+ (0.1 M) | glass membrane | H+ (Unknown ) …(8.59)
and the potential of the glass electrode is given by the following Nernst
equation
RT
0
E = Eglass − ln[H+ ] …(8.60)
nF
Substituting the values of R, T, F and n; the equation at 298 K becomes

0
E glass = E glass − 0.0592 pH …(8.61)
Generally, an electrode like saturated calomel electrode (SCE) is combined

with the glass electrode that acts as a reference. The combination is called
combination glass electrode and is represented as
228 Ag|AgCl |Cl−(aq)| H+(0.1M) |glass membrane| H+(Unknown)|| SCE …(8.62)

The emf of this combination is given as
Ecell = ESCE − Eglass …(8.63)
Substituting for Eglass from Eq. 8.61

0
E cell = E SCE − (E glass − 0.0592 pH) …(8.64)
The potential of saturated calomel electrode is = 0.2682 V
Substituting the value, we get,

0
E cell = 0.2682 V − (E glass − 0.0592 pH) V …(8.65)
On simplification we get,
0
Ecell − 0.2682 + Eglass
pH = …(8.66)
0.0592
Thus, we find that there is a direct relationship between the pH and ECell.
0
However, we need to find the value of E glass . As this value depends on the
membrane; this is obtained by calibration with a buffer solution of known pH.
You may look into experiment 6 of BCHCL-134 course for the method of
0
calibration for determination of E glass for glass electrode.
Having learnt about pH determination using emf measurements let us take up

another important application of emf measurement, i.e., potentiometric
titrations.
8.3.2 Potentiometric Titrations

You are familiar with volumetric determinations wherein a known volume of the
given sample whose concentration is to be determined is made to react with a
suitable reagent of known concentration with which it reacts stoichiometrically.
The volume of the reagent required for the stoichiomeric reaction is
determined and then used to find the concentration of the sample in question.
The completion of the reaction between the sample and reagent is determined
by a suitable indicator that changes its colour at the end point, indicative of the
completion of the reaction. However, sometimes it may not be possible to
perform such a titration because of unavailability of a suitable indicator or
sometimes the sample may be deeply coloured that may mask the colour
change of the indicator. In such cases an alternative process of titration is
followed with the help of an instrument that can monitor the change in some
physical property of the system. The potential of an electrode set up using the
solution is one such physical property and potentiometer is the instrument.
The titrations based on potential measurement are called potentiometric
titrations. We would take up two types of potentiometric titrations. We begin
with potentiometric titration between an acid and a base.
Acid-base potentiometric titration
You are familiar with acid-base titrations and are aware of the fact that in the
course of an acid base titration the pH of the solution changes. For example, 229
in the titration of a sample of hydrochloric acid with NaOH, to begin the

solution pH will be low (in the acidic range). When we titrate it with NaOH the
added base would neutralise some of the hydrogen ions and as a
consequence the concentration of hydrogen ions decreases and the pH
increases. (You know that the pH of a solution is inversly related to the
concentration of hydrogen ions.). This way the progress of titration can be
follllowed by measuring the pH of the solution.
You have learnt above that the pH of a solution can be measured with the help
of a glass electrode or a quinhydrone electrode whose potential is directly
related to the pH of the solution being measured. Thus, we can say that a pH
titration is essentially a potentiometric titration. The pH meter used for the
measurement of pH in fact measures the emf of the cell formed using the test
solution and converts it to the pH that is displayed on the instrument panel. It
will be worthwhile that you have a relook at Experiment 7 of BCHCL-134
course.
The plot of change in emf of the cell formed from the test solution as a function
of the volume of titrant gives a potentionmetric titration curve. A schematic
diagram showing the potentiometric titration curve of a strong acid and a
strong base is given in Fig. (8.7).
Fig. 8.7: Schematic potentiometric titration curve for a strong acid strong
base titration.
The equivalence point is determined from the sharp change in the emf of the
solution at the equivalence point. It is located by plotting derivative plots about
which you would learn in BCHCL-136 course.
Redox potentiometric titration
As you know, a large number of analytical determinations involve estimation of

strengths of oxidising or reducing agents. These are typically carried out by
titrating the sample with a suitable reagent and involve oxidation-reduction or
redox reactions. These titrations use redox indicators for the purpose of
determining the end point. We can use emf measurement to follow such
titrations and to determine the equivalence point. In such determinations we
construct a galvanic cell using the redox electrode formed from the test
solution and a reference electrode. You would recall from the previous unit
that a redox electrode consists of an inert metal like platinum in contact with
an aqueous solution of the ions of an element in different oxidation states. The
inert metal does not react with the species in solution, it merely acts as a
carrier of electrons. Let us understand the principle of redox potentiometric
230 titration with the help of an example.
Let us take the following redox titration between cuprous ions and ferric ions.
Cu + + Fe3+ ⇌ Cu2 + + Fe2 + …(8.67)
In order to perform this titrations potentiometrically i.e., by emf measurement,

we create the following galvanic cell
Pt ( s ) | Cu + , Cu 2 + || KCl ( satd.) | Hg 2 Cl 2 ( s ) | Hg ( l ) …(8.68)
You may note that before we start the titration the cell mentioned above does
not exist as the test solution contains only Cu+ ions. However, when we add
even a drop of the titrant (Fe3+ ions), the cell will come into existance because
the added ferric ions would oxidise some cuprous ions and we would have the
redox couple, Cu2+|Cu+.The potential of the redox electrode will be governed
by the following nernst equation
[Cu + ]
E = E0 − 0.0592 log …(8.69)
Cu2 + |Cu+ Cu2 + |Cu+ [Cu2 + ]
[Cu+ ]
As we add more and more of ferric ions the ratio would keep on
[Cu2+ ]
changing and the electrode potential and therefore the cell emf will also on
keep changing.
When, all the cuprous ions are oxidised i.e., at the equivalence point once
again there will not be any redox couple (we will have Cu2+ and Fe2+ ions) and
the potential will be the average of the standard potentials of the Cu2+| Cu+
and Fe3+| Fe2+ redox couples. After the equivalence point, on addition of more
ferric ions the reaction vessel will have Fe3+| Fe2+ redox couple and its
electrode potential will be governed by in following expression
[Fe2 + ]
E 3+ 2+ = E0 − 0.0592 log …(8.70)
Fe |Fe Fe 3 + |Fe 2 + [Fe3 + ]
Addition of more and more of ferric ion solution would change the ratio
leading to the change in electrode potential and hence the cell emf. A
schematic diagram showing the change in the cell emf with the volume of the
titrant is given in Fig. (8.8). Such a curve is called a redox potentiometric
titration curve.
Fig. 8.8: A schematic diagram showing the redox potentiometric titration curve
for titration between Cu+ and Fe3+ ions. 231
The equivalence point of the titration can be obtained by drawing a differential

curve. You would learn about these in the course BCHCL-136. Having learnt
about the applications of emf measurements let’s now take up electrolytic
cells. However, before that, answer the following simple question to assess
your understanding.
SAQ 4
pH titration is a potentiometric titration. Justify.
8.4 ELECTROLYTIC CELLS

In this and the previous unit on electrochemistry we have so far discussed
about galvanic cells in which we use the Gibbs energy of a spontaneous
reaction to get useful electrical work. Now, we would consider the other type of
electrochemical cells in which a current is passed through the cell by an
applied external voltage, to make an otherwise non-spontaneous chemical
reaction to proceed. We mentioned in the previous unit that in an electrolytic
cell we dip two electrodes into a solution of an electrolyte and connect them to
an outside source of electricity. As a consequence, the ions in the electrolyte
move towards the oppositely charged electrode and undergo chemical
reactions at the electrodes; the process is called electrolysis. On the basis of
detailed studies on different types of electrolytic reactions Michael Faraday the
British chemist and physicist discovered two simple and fundamental rules that
govern the decomposition of electrolyte solutions and melts by the passage of
electric current. These are called Faraday's laws of electrolysis. We would
take up these laws; however, before that let’s first learn about electrolytic cell
with the help of an example and compare it with the galvanic cells.
You would recall from the previous unit that in Daniell cell the following
reaction takes place spontaneously
Zn(s) + Cu2 + (aq) → Zn 2 + (aq) + Cu(s) …(8.71)
Fig. 8.9: A schematic diagram showing a) galvanic and b) electrolytic cell.
At anode, zinc is oxidised to zinc ions whereas the copper ions get reduced to
copper at the cathode, Fig. (8.9(a)). The electrons flow from zinc to copper
electrode in the external circuit whereas within the cell the sulphate ions carry
current from copper to zinc electrode. The zinc electrode is negative whereas
232 the copper electrode is positive and the cell emf is 1.1V.
Now when we apply a voltage greater than 1.1V by using an external battery
such that the electrons are forced into the zinc electrode (acts as cathode
now) and removed from the copper electrode (acts as anode now);
Fig.(8.9 (b)). As a consequence, the zinc ions will get reduced and the copper
metal would get oxidised to copper ions as per the following reactions.
Cathode: Zn2 + (aq) + 2e− → Zn(s) (reduction) …(8.72)
Anode: Cu(s) → Cu2 + (aq) + 2e − (oxidation) …(8.73)
The overall reaction would be
Cu(s) + Zn 2 + (aq) → Cu2 + (aq) + Zn(s) …(8.74)
This reaction is opposite to the spontaneous reaction given in Eq. (8.71) i.e., it
is a non-spontaneous reaction. Thus, we see that by applying a voltage
greater than 1.1V, an otherwise non-spontaneous reaction is made to occur. It
is important to note a few points of differentiation between voltaic and
electrolytic cells here. First, in electrolytic cells the signs of anode and cathode
become opposite to that in the voltaic cell; anode is positive now whereas
cathode becomes negative. Secondly, and very importantly, we still have
oxidation at anode and reduction at cathode. Thirdly, the cell emf becomes
negative. These are summarized in the Table given below.
Cell Type EMF Electrode Process Sign

Voltaic / Positive Anode Oxidation Negative
galvanic
Cathode Reduction Positive
Electrolytic Negative Anode Oxidation Positive
/Faradaic
Cathode Reduction Negative
Having understood the difference between voltaic and electrolytic cell, let us
now take up electrolysis of different systems in terms of the electrode
reactions and products of electrolysis. It is important to note that the basic
principles involved in galvanic and electrolytic cells are similar.
8.4.1 Electrolysis in Different Systems

The term electrolysis can be broken into two parts viz., electro and lysis. You In electrolysis we
know that lysis refers to cutting or breaking, so electrolysis can be seen as the force a current
process of splitting of a substance by the input of electrical energy. This is one through a cell to
of extensively used process in the preparation of a number of industrial produce a chemical
chemicals and other industrial processes. We would take up the applications change for which the
cell potential is
of electrolysis a little later; for now, let us understand about the products of
negative; in other
electrolysis of some systems and the reasons thereof. We begin with the
words, electrical work
electrolysis of water to give hydrogen and oxygen gases. is used to make an
otherwise
Electrolysis of Water
nonspontaneous
We know that water is a stable compound and it does not decompose on its chemical reaction
own to form hydrogen and oxygen gas. This is due to very high standard possible.
Gibbs energy change for the following reaction.
2H2O(l ) → 2H2 (g) + O2 (g) G0 = 474.4 kJ mol −1 …(8.75)

233
That is, the reaction is highly non-spontaneous. If we dip two non-reactive

platinum electrodes in water taken in a beaker and connect them to a 6V
battery to form an electrolytic cell we find that no reaction is observed. It is so
because pure water contains only about 1  10−7M each of hydrogen and
hydroxide ions from autoionisation. Therefore, only a negligible amount of
current can flow. However, if we add a few drops of dilute sulphuric acid (or a
small anount of a soluble salt) to water, we immediately observe formation of
hydrogen and oxygen gases at the cathode and anode respectively. The
electrode reactions are given as
Anode: 2H2O(l ) → O2 (g) + 4 H+ (aq) + 4e− …(8.76)
Cathode: 4H2O(l ) + 4e− → 2H2 (g) + 4 OH− (aq) …(8.77)
Overall reaction: 6H2O(l ) → 2H2 (g) + O2 (g) + 4OH− (aq) + 4 H+ (aq)
Or 2H2 O(l ) → 2 H 2 (g) + O 2 (g) …(8.78)
You may note that here sulphuric acid does not participate in the electrode
reactions, it just provides ions for the flow of current.
Electrolysis of Molten Sodium Chloride
The electrolysis of sodium chloride is used to produce industrially important

chemicals. Its electrolysis is carried out in the molten state as well as in
aqueous solutions. The products of electrolysis are different in the two cases.
The electrolysis of molten NaCl is an important industrial process used
commercially to obtain sodium metal from sodium chloride. Two electrodes
dipped into molten sodium chloride are connected to a battery. As the melting
point of NaCl is extremely high (~800 oC), it is mixed with CaCl2 to decrease
the melting point. On passing current, globules of sodium metal are observed
at the electrode connected to the negative pole of the battery, and the
evolution of chlorine gas is observed at the positive electrode. The electrode
reactions are given as
Anode: 2Cl− (aq) → Cl2 (g) + 2e− …(8.79)
Cathode: 2Na + (aq) + 2e− → 2 Na(s) …(8.80)
Of the possible The overall reaction is

electrode reactions at
2NaCl → 2Na(s) + Cl2 (g) 
the cathode, the one
with less negative
Electrolysis of aqueous solution of Sodium Chloride (Brine)
(more positive)
electrode potential If we electrolyse aqueous solution of sodium chloride (brine) we get hydrogen
will occur. Similarly, of gas, chlorine gas and sodium hydroxide as the products. The question comes
the possible electrode
up is that why the products are different from that obtained from molten salt.
reactions at the
The reason for this is that in the electrolysis of a molten salt, only the ions from
anode, the one with
more negative (less the salt are available to undergo reactions at the electrodes. However, in case
positive) electrode of the electrolysis of an aqueous solution of an electrolyte, we have water as a
potential will occur. part of the system and when we pass current through the system, we also
need to consider the possibility of water undergoing reaction at one or both the
234 electrodes. In case of electrolysis of solution of NaCl, there are two species
each that can get reduced or oxidised. Let us first look at the reaction at
cathode, i.e., reduction. Two possible reactions are
Cathode: Na + (aq) + e− → Na(s) E 0 = −2.71 V …(8.81)
2H2O(l ) + 2e− → H2 (g) + 2OH− (aq) E 0 = −0.83 V …(8.82)
As the reduction potential for the reduction of sodium ions is highly negative; it
is water that will get reduced at the cathode in preference to sodium ions. It is
important to note that in cases of reactions involving formation of gaseous
products in electrolysis some extra voltage is required in addition to the
reduction potential of the electrode reaction. This is called overpotential or
overvoltage and is of the order of about 0.4 to 0.6 V for gases like hydrogen
and oxygen. The overpotential is required to overcome interactions at the
electrode surface. In the present case even if we consider 0.6 V as the
overpotential it would still be easier for water to get reduced as its electrode
potential would still be lesser negative (−0.83V − 0.60 V = − 1.43 V). On the
other hand, at the anode also there are two possibilities as given below
Anode: 2Cl − (aq) → Cl2 ( g) + 2e − E 0 = 1.36 V …(8.83)
2H2O( l ) → O 2 ( g) + 4 H+ (aq) + 4e − E 0 = 1.23 V …(8.84)
For oxidation the electrode reaction with lesser positive potential is preferred.
Here, the electrode potentials are comparable, and one may expect both the
reactions to occur to some extent i.e., both the gases (Cl2 and O2) may form.
However, due to a higher overpotential of oxygen the effective potential for the
reaction 8.84 becomes (1.23 + 0.60 = 1.83) and it is the chlorine gas that is
formed at the anode. Thus, the effective reactions at the electrodes and the
overall reaction for the electrolysis of brine would be
Cathode: 2H2O(l ) + 2e− → H2 (g) + 2OH− (aq) …(8.85)
Anode: 2Cl − (aq) → Cl2 (g) + 2e − …(8.86)
Overall reaction:
2NaCl (aq) + 2 H2O( l ) → 2Na + + H2 (g) + 2OH− (aq) + Cl2 (g) …(8.87)
Electrolysis of Sulphuric Acid
The electrolysis of sulphuric acid solution is an interesting system let us

understand what happens when we electrolyse sulphuric acid solution. You
know that sulphuric acid is a strong acid and practically completely ionized in
its solution. Therefore, a solution of sulphuric acid will have three species i.e.,
hydrogen ions, sulphate ions and water that can undergo electrode reactions.
Let’s first look at the possible reactions at the cathode. The following two
reactions are possible
Cathode: 2H+ + 2e− → H2 (g) E 0 = 0.00 V …(8.88)
2H2O(l ) + 2e− → H2 (g) + 2OH− (aq) E 0 = 1.83 V …(8.89)

235
As per the values of electrode potential it is the hydrogen ions that will get
reduced to give hydrogen gas at the cathode. Now, let us look at possible
reactions at the anode
Anode: 2SO24− (aq) → S2O82− (aq) + 2e− E 0 = 2.01 V …(8.90)
2H2O(l ) → O2 (g) + 4 H+ (aq) + 4e− E 0 = 1.23 V …(8.91)
On the basis of electrode potentials, we expect that the water will undergo
oxidation in preference to the sulphate ions even if we consider the over
potential for oxygen gas. Thus, the electrode reactions and overall reaction in
the electrolysis of sulphuric acid can be given as
Cathode: 4H+ + 4e− → 2 H2 (g) …(8.92)
Anode: 2H2O(l ) → O2 (g) + 4 H+ (aq) + 4e− …(8.93)
Overall: 2H2O(l ) → O2 (g) + 2 H2 (g) …(8.94)
This expression is same as the expression for the electrolysis of water. You
may recall from above that when we discussed about electrolysis of water, we
had added a few drops of sulphuric acid to provide ionic conductivity.
So far we have discussed about the electrolysis qualitatively in terms of the

products of electrolysis. From industrial perspective, it is also important to
know about the amount of the products formed in an electrolytic process. The
quantitative aspect of electrolysis can be understood in terms of Faraday’s
laws of electrolysis. Let’s learn about these laws and their significance.
However, before that solve the following simple questions to assess your
understanding of the phenomenon of electrolysis.
SAQ 5
Give the sign and nature of process on anode in an electrolytic cell.
SAQ 6
Write the possible electrode reactions in the electrolysis of aqueous solution of
potassium chloride. Using the electrode potential values given in Table 7.1,
predict the reactions that would actually take place and write the overall cell
reaction.
8.4.2 Faraday’s Laws of Electrolysis

As stated above, Faraday formulated two laws that govern the decomposition
of electrolyte solutions and melts by the passage of electric current. These
laws can be stated as under:
Faraday’s first law of electrolysis: It states that the amount of chemical
236 reaction which occurs at any electrode of the electrolytic cell during
electrolysis by passage of current through the solution (or melts) proportional
to the quantity of electricity passed through the electrolyte. In simple words,
the amount of substance produced at each electrode is directly proportional to
the quantity of charge flowing through the cell.
Faraday’s second law of electrolysis:states that the amounts of different

substances formed at the electrodes by the passage of a given quantity of
electricity through an electrolytic cell or through different electrolytic cells
connected in series are proportional to their chemical equivalent weights
(masses). This law allows us to calculate the quantity of electricity that has
passed through the electrolytic cell from the amounts of the substances
formed at the electrodes and vice-versa. That is, if we know the amount of
electricity passed, we can calculate the amounts of the substances formed or
consumed at the electrodes.
We can rationalise these statements by considering the electrolysis of molten

sodium chloride as discussed above. In the electrolysis of molten sodium
chloride, the electrons pushed into the negative electrode (cathode) are picked
up by sodium ions to form sodium metal. At the same time, an equivalent
number of electrons are pulled up by the battery from the positive electrode
(anode). These electrons are provided by the chloride ions that get oxidised to
chlorine gas by losing electrons to the electrode. Now, if we pass more
current, i.e., we push in more electrons to the cathode then more sodium and
chlorine would be formed. A look at the electrode reactions reveal that there is
a stoichiometric relationship.
1
Anode: Cl− → Cl2 (g) + e − …(8.95)
2
Cathode: Na + + e− → Na (s) …(8.96)
Thus, when one mole of electrons passes through the cell, one mole of
sodium metal is deposited at cathode, and one-half mole of chlorine gas is
evolved at the anode. You know that an electron carries 1.602  10−19
coulombs of charge, therefore, the charge carried by passing 1 mole
(6.022  1023) of electrons will be equal to
1.602  10−19 C  6.022  1023 mol −1 = 96485 C mol −1 …(8.97)
This quantity of electricity is called a Faraday of electricity and is represented

as, F. In the laboratory the amount of electricity passed through the electrolytic
cell is determined by measuring the amount of current and the time for which it
is passed. You know that the current (I) has the units of coulombs per second
(Cs−1), so the product of current and time would give charge in coulombs.
C
Q (C) = I    t (s) …(8.98)
s
The first law of electrolysis provides a method for calculating the amount of
product formed at an electrode on passing a certain amount of current. This
can also be used to calculate the amount of current that needs to be passed
through the electrolytic cell for getting a certain amount of the product. Let us
take some simple examples to understand it. 237
Example 8.2: Calculate the amount of chlorine gas evolved during the
electrolysis of molten sodium chloride on passing a current of
0.5 A for an hour through it. (Given: Mm (Cl2) =70.90 gmol-1)
Solution: You know that in the electrolysis of molten sodium chloride, chlorine
gas is evolved at the anode due to the oxidation of chloride ions as
per the following reaction
1
Cl− (aq) → Cl2 (g) + e −
2
This means that passage of 1 mole of electrons (1F) through molten sodium
chloride would evolve half a mole of chlorine gas. So, first we need to
calculate the amount of electricity passed.
We know that Q = It
Q = 0.5 C s −1  1h  60 min h −1  60 s min −1 = 0.5  1 60  60 C = 1800 C
In order to calculate the number of Faradays, we divide this with Faraday’s

constant as
1800 C
Q = 1800 C = = 0.0187 F
96485 C F −1
As per the cathode reaction 1F of electricity would evolve ½ mole of chlorine;

the moles of chlorine evolved by passing 0.0187 F of electricity would be
Number of moles of chlorine evolved= 0.5 mol F−1 0.0187 F = 0.00935 mol
The molar mass of chlorine is 70.90 g mol−1, so the mass of chlorine evolved
would be
= 0.00935mol  70.90 g mol −1 = 0.6629 g
If needed, we can calculate the volume of chlorine gas evolved by using ideal
gas equationV = nRT .
p
Example 8.3: Calculate the time for which a 0.6 A current be passed through
a sample of molten sodium chloride to get 1 g of sodium metal.
(Given: Mm (Na) =23 gmol-1)
Solution: You know that in the electrolysis of molten sodium chloride sodium
metal is formed at the cathode due to the reduction of sodium ions
as per the following reaction
Na + + e− → Na(s)
This means that passage of 1 mole of electrons (1F of electricity) through

molten sodium chloride would form one mole of sodium metal.
We desire to get 1 g of sodium, so we convert it to number of moles by

dividing with the molar mass of sodium i.e.= 23 g mol−1.
1g
The number of moles of sodium required = = 0.04348 mol
23 g mol −1
238
As per the electrode reaction, to get 0.04348 mol of sodium we need to pass
−1
Q = 0.0434 mol  96485 C mol = 4195 C
We know that Q = I  t
4195 C
4195 C = 0.6 C s−1  t (s)  t (s) = = 6991s
0.6 C s−1
Thus, we need to pass 0.6 A current for 6991 s through molten sodium
chloride to get 1 g of sodium metal.
Example 8.4: Two electrolytic cells; one containing an aqueous solution of

copper sulphate and the other containing an aqueous solution
of silver nitrate are connected in series and a constant current of
2A is passed through them for a certain amount of time. If 16 g
of silver was deposited in the electrolytic cell containing silver
nitrate, calculate the time for which the current was passed, and
the mass of copper deposited in the electrolytic cell containing
copper sulphate. (Given molar masses of silver and copper are
107.87 and 63.55 g mol−1 respectively)
Solution: We need to consider the following two reactions occurring on the

cathodes of the two electrolytic cells connected in series.
Cell with AgNO3 as electrolyte: Ag + (aq) + e − → Ag(s)
Cell with CuSO4 as electrolyte: Cu2 + (aq) + 2e − → Cu(s)
If we write the electrode reaction in case of copper ion as
1 2+ 1
Cu (aq) + e − → Cu(s)
2 2
We find that for every mole of the electrons passed through the cells the
amounts (in moles) of silver and copper deposited in the respective cells are in
the ratio of 1 : ½. We are given the mass of silver deposited that can be used
to calculate the moles of silver, which in turn can be used to calculate the
moles of copper.
The mass of silver deposited= 16 g
The molar mass of silver= 107.87 g mol−1
16 g
➔ the number of moles of silver deposited = = 0.1483 mol
107.87 g mol −1
This means that 0.1483 moles of electrons have been passed, we can
calculate the quantity of electricity passed by using Faraday’s constant as
follows
Quantity of electricity passed = Q = 0.1483 mol  96485 C mol −1 = 14309 C
We know that = Q (C) = I ( A)  t (s)
Q(C)
Rearranging, t (s) =
I (A) 239
14309 C
Substituting the values, we get t (s) = = 7154 s
2A
Now, as stated above, amounts (in moles) of silver and copper deposited in
1
the respective cells are in the ratio of 1 :
2
0.1483
Therefore, the amount of copper deposited will be = = 0.07415 mol
2
In terms of mass, we get = 0.07425 mol  63.55 g mol −1 = 4.7122 g
Thus, the current was passed for 7154 s and 4.7122 g of copper would be
deposited on the cathode of the electrolytic cell containing CuSO4.
You may note that earlier constant current sources were not available and we
could not get the amount of current passed by multiplying the current with
time. The amount of current passed in an electrolytic cell was obtained by
connecting an other electrolytic cell in series and this cell typically was made
up of silver and contained silver nitrate as the electrolyte. It was called as a
coulometer as it was used to get the current in coulombs. After the
electrolysis was complete in the cell under observation, the amount of current
was calculated by measuring the increase in the mass of coulometer due to
silver deposited in the silver coulometer. You can now look at the above
example by taking the second electrolytic cell as coulometer.
Having learnt about the quantitative aspects of electrolysis in terms of

Faraday’s laws and their applications we would like to take up some important
applications of electrolysis. However, before that solve the following simple
questions to assess your understanding of Faradey’s laws of electrolysis.
SAQ 7
For how long a constant current of 5.0 A be passed through a solution of silver
ions to get 25 g of silver metal? (Given: Mm (Ag) =107.87 gmol-1)
SAQ 8
The electrolysis of aqueous solution of KI is similar to that of aqueous sodium
chloride. Calculate the volume of iodine gas evolved at the anode under
normal conditions of temperature and pressure (1 atm, 273 K). Assume the
gas to behave ideally.
8.5 APPLICATIONS OF ELECTROLYSIS

Electrolysis is used extensively in the area of extraction, refining and
protection of elements. There are a number of elements that are produced
commercially almost exclusively by this process. Some of the important ones
are the metals like magnesium and aluminum and non-metals like chlorine,
and fluorine. In addition, a number of inorganic compounds like, sodium
240 hydroxide, sodium persulphate, potassium permanganate and potassium
dichromate are also prepared by electrolysis. Let us take up some general
applications of electrolysis
Extraction of elements
Most of the metals in the earth’s crust exist in the combined form as metal
oxides. Extracting metals from these ores requires reduction of the metal ions,
which is a non-spontaneous process. There are two methods based on
electrolysis for the extraction of metal. In one of the methods, the ore is treated
with a strong acid to get a salt. The aqueous solution of the salt is then
electrolysed to obtain the metal. The other method involves the electrolysis of
the ore in molten state. This process is performed in a furnace. The advantage
of electrolytic extraction is that the metal is obtained in fairly pure state which
can then be refined.
The chlor–alkali process is one of the most important industrial electrolytic

processes based on the electrolysis of aqueous NaCl solution discussed
above. This process gives two very important industrial chemicals viz.,
chlorine and NaOH (alkali) hence the name of the process.
Refining of metals (electrorefining)
Though electrolytic extraction of metals and non-metals provides elements in

fairly pure form; they need to be further refined. Some of these refining
processes also involve electrolysis. In such a process, the anode is made of
the extracted metal and the electrolyte happens to be solution of metal ion. In
such a process the pure metal is deposited at the cathode. For example, in the
electrolytic refining of copper the block of impure copper is made the anode
and acidified aqueous solution of copper sulphate is taken as the electrolyte in
the electrolytic cell. The cathode where the purified metal gets deposited is
made of pure copper tubes. When electric current is passed through the cell,
the copper ions from the solution get reduced and deposited on the pure
copper cathode. An equivalent amount of these are brought back into the
solution by oxidation of copper from the impure block of the extracted metal.
This process continues and the pure metal keeps depositing on the cathode
and the anode keeps dissolving.
Once the process is over, a number of less reactive metals, such as gold,
silver, and platinum, that are present in the impure copper are recovered as a
mud that collects on the bottom of the electrolytic cell; it is called anode mud.
On the other hand, the metals in impure copper block that are more reactive
than copper remain as ions in the electrolytic bath. Other metals like silver and
gold are also refined in a similar process.
Electroplating
A number of metals are protected from corrosion by plating them with other
metals that are less prone to corrosion. For example, iron can be protected by
a coating of zinc. Sometimes, such a coating is done for the decorative
purposes also. For example, a thin coating of metallic silver is electroplated on
an
underlying base of iron. The process is similar to the one described for
purification of copper. In electroplating the item to be electroplated is made the 241
cathode in an electrolytic cell and the electrolyte contains ions of the metal to
be plated. On passing electric current through the cell, the metal ions get
reduced and deposited on the article made as cathode. In a similar process,
steel is electrogalvanized to protect it from corrosion. The steel object to be
electroplated is made the cathode and is dipped in the electrolyte containing
zinc ions. Let us summarise what have we learnt in this unit.
8.6 SUMMARY
In this second unit on electrochemistry, we continued with our discussion on
galvanic cells and took up concentration cells. These are galvanic cells that
contain two equivalent electrodes having same half-cell reactions; however,
these differ in concentration of electrolytes or the composition of electrode
material. In such cells there is no overall chemical reaction; the change in
emfis due to the change in the concentration of the composition of the
electrolyte or the electrodes. In case of electrode concentration cells, the
composition of the electrodes is different whereas in case of electrolyte
concentration cells it is the composition of the electrolyte in which the
electrodes are dipped is different. In this context we discussed about the
concept of liquid junction potential; its significance and elimination by salt
bridge.
Thereafter, we took up two important experimental applications of emf

measurements. The first application was the measurement of pH of aqueous
solutions. In this context we discussed different methods that can be used for
the determination of pH of aqueous solutions using emf measurement. The
second application we discussed was the potentiometric titrations. Herein we
discussed the principle of acid-base and redox of potentiometric titrations. This
was followed by discussion on the other type of electrochemical cells, viz.,
electrolytic cells. We started this discussion by differentiating between the
voltaic and electrolytic cells and then discussed about the electrolysis of
different types of systems that include molten NaCl and aqueous solutions of
NaCl and sulphuric acid. Towards then, we took up the quantitative aspect of
electrolysis and explained the Faraday’s laws of electrolysis and discussed
their significance. In the end we discussed industrial application applied of
electrolysis.

1. What are electrode concentration cells? Give any two examples.
2. An electrolyte concentration cell is formed by combining two zinc

electrodes having the concentration of zinc ions as c1 and c2 respectively,
where c1 is greater than c2. Write the cell diagram, half-cell reactions and
the cell reaction for it.
3. List different methods based on emf measurement that can be used for the
determination of pH of aqueous solutions.
4. Consider the following two electrodes and construct a concentration cell

from them.
242 Ag + (aq, 0.50 M) | Ag (s) and Ag+ (aq, 0.25 M) | Ag(s)

Write the cell diagram, half-cell reactions and the cell reaction for the same
and calculate the value of Ecell
5. What is a glass electrode? Describe the construction of glass electrode.
6. Draw a schematic graph for a potentiometric titration
7. Write the possible electrode reactions in the electrolysis of aqueous

solution of sodium sulphate. On the basis of electrode potential values
given in Table 7.1, predict the reactions that would take place and write
the overall cell reaction.
8. Calculate the constant current in amperes that will be required to pass

through a sample of molten MgCl2 for 24 h to get 600 kg of chlorine.
9. Give the polarity and nature of process on anode in a galvanic cell.
8.8 ANSWERS
Self-Assessement Questions
1. For the given concentration cell, the electrode reactions would be as
follows
Anode: Cd (0.001 m in Hg ) → Cd2 + (aq) + 2e −
Cathode: Cd2 + (aq) + 2e − → Cd (0.0001 m in Hg )
Overall reaction would be
Cd ( 0.001 m in Hg ) → Cd ( 0.0001 m in Hg )
The cell emf, Ecell would be
0 RT 0.0001
Ecell = Ecell − 2.303 log
2F 0.001
0
As E cell will be zero, so by substituting different values, we can write
0.0592 0.001
Ecell = log = 0.0296 log10 = 0.0296 V
2 0.0001
2. Before we write the cell reaction, we need to remember that for an

electrode concentration cell reaction to be spontaneous, the electrode
with higher concentration should be the anode. Therefore, we can write

the cell diagram as
K ( c = 0.0225 m in Hg) | KCl ( aq, 0.01 M ) | K ( c = 0.0150 m in Hg )
The electrode reactions would be
Anode: K (c = 0.0225 m in Hg ) → K + (aq) + 2e −
Cathode: K + (aq) + 2e − → K (c = 0.015 m in Hg )

K (c = 0.0225 m in Hg ) → K (c = 0.015 m in Hg ) 243
3. The following are the requirements for the construction of concentration

cells
For concentration cell without transference
• The two half cells are separated by a salt bridge,
• Two half cells are combined in opposition of each other, and
• one of the electrode is reversible to the cation whereas the other electrode
is reversible to the anion.
For concentration cell with transference
• The two half cells are separated by a porous plate allowing the passage
of ions, but the direct mixing of solution is not allowed, and
• The electrodes are reversible to one of the ions of the electrolyte.
4. The process of pH measurement of a solution using glass electrode

actually involves the measurement of a potential developed between the
hydrogen ions in the solution and the ones contained in the electrode.
Therefore, if we perform an acid-base titration using a glass electrode for
measuring the pH then we can say that we have performed a
potentiometric titration.
5. The anode in an electrolytic cell has a positive sign and the nature of
reaction at anode is oxidation.
6. In the electrolysis of aqueous solution of KCl, there are three species that
can undergo electrode reactions. These are potassium ions, chloride ions
and water molecules. At cathode, the following reduction reactions are
possible
Cathode: K + (aq) + e− → K (s) E 0 = −2.92 V
2H2O(l ) + 2 e− → H2 (g) + 2OH− (aq) E 0 = −0.83 V
As the electrode potential for the reduction of potassium ions is highly

negative; it is water that will get reduced at the cathode in preference to
potassium ions. The choice will remain the same even if we consider an
overpotential of about 0.4-0.6 V for formation of hydrogen.
At the anode again there are two possibilities:
Anode: 2Cl− (aq) → Cl2 (g) + 2e− E 0 = 1.36 V
2H2O(l ) → O2 (g) + 4H+ (aq) + 4e− E 0 = 1.23 V
For oxidation reaction the electrode reaction with lesser positive potential
is preferred. Here, the electrode potentials are comparable, and one may
expect both the reactions to occur to some extent i.e., both the gases (Cl2
and O2) may form. However, due to a higher overpotential of oxygen, it is
the chlorine gas that is formed at the anode. Thus, the effective reactions
at the electrodes and the overall reaction for the electrolysis of KCl would
244 be
− −
Cathode: 2H2O(l ) + 2e → H2 (g) + 2OH (aq)
Anode: 2Cl− (aq) → Cl2 (g) + 2e −
Overall reaction:
2KCl (aq) + 2 H2O( l ) → 2 K + + H2 (g) + 2OH− (aq) + Cl2 (g)
7. In the electrolysis of a solution containing silver ions the following reaction

will occur at cathode.
Ag + (aq) + e − → Ag(s)
That is, the passage of 1F of electricity would deposit one mole of silver
metal. We need to get 25 g of silver, so we convert it to number of moles
by dividing with the molar mass of silver
25 g
The number of moles of silver = = 0.2318 mol
107.87 g mol −1
As per the electrode reaction, to get 0.2318 mol of silver we need to pass
Q = 0.2318 mol  96485 C mol −1 = 22365 C
of charge; we know that Q = It
22365 C
22365 C = 5.0 C s −1  t (s)  t (s) = = 4473 s
5.0 C s −1
Thus, we need to pass 5.0 A current for 74 min 55 s through the solution
of silver ions to get 25 g of silver metal.
8. As the electrolysis of aqueous solution of KI is given to be similar to

aqueous sodium chloride, this means that iodine gas will be liberated at
the anode. The electrode reaction would be
1
I − (aq) → I (g) + e −
2 2
This implies that on passage of 1 Faraday of electricity half a mole of

iodine will be liberated.
We are given the current strength and time, so let us first calculate the
coulombs of electricity passed.
We know that Q = I  t
Q = 5A  60 min  60 s min −1 = 18000 C
18000 C
The number of Faradays = = 0.187 F
96485 CF −1
0.187
Number of moles of iodine liberated will be = = 9.35  10 − 2 mol
2 245
nRT
We know that the volume of an ideal gas at NTP is given as V =
p
9.35  10 −2 mol  0.0821 L. atm K −1mol −1  273 K

V = = 2.096 L
1atm
Thus, the volume of iodine liberated will be 2.096 liters.
Terminal Questions
1. The concentration cells in which the composition of electrode material is
different are called electrode concentration cells. The two examples are
as under
i. An electrode concentration cell constructed by combining two

hydrogen electrodes in which the pressure of the hydrogen gas is
different. It can be represented as
Pt (s);H2 (g, p2 ) | H+ (aq,1M) | H2 (g, p1); Pt (s)p2  p1
ii. A concentration cell constructed by combining two potassium

amalgam electrodes having different molalities of potassium metal in
them.
K = (c = p m in Hg ) | KCl (aq, 0.01) | K (c = q m in Hg ) pq
2. As we know that in an electrolyte concentration cell the electrode having

lower concentration of the electrolyte forms the anode. So, we can write
the cell diagram as
Zn(s) | Zn 2 + (aq, c = c1 ) || Zn 2 + (aq, c = c 2 ) | Zn(s) c 2  c1
The half-cell reactions would be as under
Anode: Zn(s) → Zn2 + (aq, c = c1 ) + 2e−
Cathode: Zn2 + (aq, c = c2 ) + 2e− → Zn(s)
The overall cell-reaction would be
Zn 2 + (aq, c = c 2 ) → Zn 2 + (aq, c = c1)
3. The following methods based on emf measurement can be used for the
determination of pH of aqueous solutions.
a) Using voltaic cell having a hydrogen electrode
b) Using quinhydrone electrode-a redox electrode
c) Using glass electrode- a membrane electrode
4. In an electrolyte concentration cell, the electrode with lower concentration

of the electrolyte acts as an anode, therefore the electrode with silver ion
concentration of 0.25 M would be the anode. The cell diagram can be
given as
Ag(s) | Ag + (aq, 0.25 M) || Ag + (aq, 0.50 M) | Ag(s)

246
The electrode reactions would be as follows:
Anode: Ag(s) → Ag + (aq, 0.25 M) + e −
Cathode: Ag + (aq, 0.50 M) + e − → Ag(s)
Ag + (aq, 0.50 M) → Ag + (aq, 0.25 M)
The cell emf, Ecell would be
0 RT 0.25
Ecell = Ecell − 2.303 log
F 0.50
0
As Ecell will be zero, so we can write that
Ecell = 0.0592 log 2 = 0.018 V
5. Glass electrode is an example of membrane electrode that is used for the

measurement of pH of aqueous solutions. A glass electrode consists of a
glass tube having a thin glass membrane bulb (that is permeable to H+
ions) at one end. The bulb is filled with a solution of a constant pH (e.g.,
0.1 M HCl) and a reversible electrode like Ag−AgCl electrode (silver wire
coated with silver chloride) is dipped in it.
6. A schematic graph for a emf titration is given below
7. We know that sodium sulphate dissociates in water as follows
Na 2SO4 (s) → 2Na + (aq) + SO24− (aq)
Thus, in an aqueous solution of sodium sulphate there will be three

species that can undergo electrode reactions. These are sodium ions,
sulphate ions and water molecules. At cathode, the following reduction
reactions are possible
Cathode: Na + (aq) + e− → Na(s) E 0 = −2.17 V
2H2O(l ) + 2e− → H2 (g) + 2OH− (aq) E 0 = −0.83 V
247
As the electrode potential for the reduction of sodium ions is highly

negative; it is water that will get reduced at the cathode in preference to
sodium ions. The choice will remain the same even if we consider an
overpotential of about 0.4-0.6 V for formation of hydrogen.
At the anode again there are two possibilities:
Anode: 2SO24− (aq) → 2S2O82− (aq) + 2e− E 0 = 2.01V
2H2O(l ) → O2 (g) + 4H+ (aq) + 4 e− E 0 = 1.23 V
On the basis of electrode potentials, we expect that the water will undergo
oxidation in preference to the sulphate ions. Thus, the electrode reactions
and overall reaction in the electrolysis of sulphuric acid can be given as
Cathode: 4H2O(l ) + 4e− → 2H2 (g) + 4 OH− (aq)
Anode: 2H2O(l ) → O2 (g) + 4H+ (aq) + 4 e−
Overall reaction: 2H2O(l ) → O2 (g) + 2 H2 (g)
8. In the electrolysis of molten magnesium chloride, the following reaction

will occur at anode
2Cl− (aq) → Cl2 (g) + 2 e−
That is, the passage of 2F of electricity would liberate one mole of

chlorine. We need to get 6 kg of chlorine; so we first convert it to number
of moles by dividing with the molar mass of chlorine
6 kg  1000 g kg−1
The number of moles of chlorine = = 84.63 mol
70.90 g mol −1
As per the electrode reaction, to get 84.63mol of chlorine we need to pass
Q = 84.63 mol  2  96485 C mol −1 = 1.633  107 C
We know that Q = It
1.633  10 7 C = I (A)  24 h  60 min h −1  60 s min −1
Solving, we get
1.633  107 C
I(A) = = 189 A
86400 s
Thus, we need to pass 189 A current for 24 hours to get 6 kg of chlorine.
9. The anode in a galvanic cell is the negative electrode and the nature of
reaction occurring at anode is oxidation.
248

Block 2

Uploaded by

Copyright:

Available Formats

Block 2

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Block 2

Uploaded by

Copyright:

Available Formats

Unit 5 Conductance-I

5.5 Concentration Dependence of

This will be followed by an introduction to the concept of molar conductivity

Expected Learning Outcomes

❖ define electrolytic and metallic conduction;

❖ describe the mechanism of conduction in metallic and electrolytic

❖ define and differentiate between the terms; conductance and

❖ list and explain the factors affecting conductivity of electrolytic solutions;

❖ describe the method of measurement of conductivity of electrolytic

❖ establish a relationship between conductance and conductivity of a

❖ define molar conductivity and explain its significance;

❖ discuss the concentration dependence of conductivity and molar

❖ state Kohlrausch’s law of independent migration of ions and give its

❖ solve problems based on conductivity, molar conductivity and

5.2 ELECTROLYTIC CONDUCTANCE

You have learnt

Fig. 5.1: A schematic diagram of experimental set up to demonstrate electrolytic

Having learnt the mechanisms of metallic and electrolytic conduction let us

5.3 CONDUCTIVITY AND ITS MEASUREMENT

In order to understand the physical meaning of conductivity, let’s consider a

In addition to the concentration of the electrolyte, the conductivity of

• the nature of the electrolyte;

The nature of the electrolyte: different electrolytes dissociate / ionise to

The dielectric constant of the solvent: the ionisation of an electrolyte

Viscosity of the solvent:the viscosity of the solvent is a measure of solvent–

Temperature: the conductance of a solution generally increases with an

5.3.1 Measurement of Conductivity

The first limitation is taken care of by using alternating current (usually a

The variable resistance is changed to achieve null (balance) state. The

Fig. 5.6: A schematic diagram showing different types of conductivity cells.

Determination of cell constant

In a typical laboratory conductivity cell, the surface area of the electrode is of

Substituting the values

Cell constant = 0.01290 S cm-1  72

Cell constant = 0.93 cm-1 (You know that Ω = S-1)

Example 5.2: The resistance of a conductivity cell containing 0.1M KCl

Substituting the given values for KCl, we get

128 Cell constant = 0.01290 S cm-1 100 S-1 = 1.29 cm-1

From Eq. (5.10), we know

5.4 MOLAR CONDUCTIVITY

given temperature. Such a quantity was defined by German physicist

Fig. 5.7: A schematic representation of the relationship between molar

Example 5.3: The conductivity of a 0.1 M aqueous solution of acetic acid is

Let us take one more example

Substituting the value of conductivity and concentration in the expression for

132 Conductivity of 0.01 M acetic acid

Having learnt about conductance, conductivity, molar conductivity, and their

5.5 CONCENTRATION DEPENDENCE OF

Fig. 5.8: A schematic diagram showing the concentration dependence of

The strong electrolytes by definition are completely ionised practically at all

5.5.1 Concentration Dependence of Molar Conductivity

This implies that we need to consider the effect of change in concentration on

Thus, if we plot Λ against square root of concentration ( c ) for dilute

5.5.2 Kohlrausch’s Law of Independent Migration

Based on such observations, Kohlrausch proposed that at infinite dilution,

Λm0 (AB) = 0m (A + ) + 0m (B− ) …(5.16)

Ion 0/ S cm2 mol-1 Ion 0/ S cm2 mol-1

H+ 349.6 OH– 199.1

Li+ 38.7 F– 55.4