Conductometry

UNIT 4 CONDUCTOMETRY
Structure
4.1 Introduction
Objectives
4.2 Electrolytic Conductance
Molar Conductivity
Variation of Conductance with Concentration
Limiting Molar Conductivity
Effect of other Factors on Conductance
4.3 Measurement of Electrolytic Conductance
The Wheatstone Bridge Principle
Measurement of Conductance of a Solution
4.4 Applications of Conductometry
4.5 Summary
4.6 Terminal Questions
4.7 Answers

4.1 INTRODUCTION
So far we have discussed potentiometric methods. In these methods we measure the
emf of a galvanic cell which is operating near zero current. Because, this emf is a
function of the ionic activities within the cell, it can be used to measure ionic
concentrations in titration, water samples, biological samples and other industrial and
environmental samples. We have also seen that both potentiometry and pH metry are
most widely used electroanalytical technique. In this unit you will study another
electroanalytical technique called the conductometry, which is one of the oldest and in
many ways simplest among the other electroanalytical techniques. This technique is
based on the measurement of electrolytic conductance.

An application of electrical potential across the solution of an electrolyte involves the

transfer of mass and charge from one part of the solution to the other. Such transport
processes enable an insight into the structure of such solution. A transport property of
great significance, which can be easily measured, is the conductance. Since an
electrolytic solution consists of ions and the nature of interaction existing in the
medium could be better understood in terms of the conducting power of these ions, it
is more convenient to speak of conductance rather than resistance. The conducting
ability of electrolytic solutions provides a direct prove of the existence of ions in
solutions. The experimental determinations of the conducting properties of electrolytic
solutions are very important as they can be used to study quantitatively the behaviour
of ions in solutions. They can also be used to determine the values of many physical
quantities such as solubilities and solubility product of sparingly soluble salts, ionic
product of self ionizing solvents, hydrolysis constant of salts, dissociation constants of
weak acids and bases and to form the basis for conductometric titration methods.

Objectives
After studying this unit, you will be able to:
• define electrolytic conduction,
• distinguish between the electrolytes and non-electrolytes solutions; and strong
and weak electrolytes,
• explain conductance of solutions, molar and equivalent conductivities,
• describe different factors effecting conductance, and

5
Electroanalytical • discuss the method of operation of a coductometer to measurement of
Methods-II
conductance.

4.2 ELECTROLYTIC CONDUCTANCE

An electrolytic solution contains free ions in addition to other kinetically identifiable
species. When electrical potential is applied across the solution the macroscopic
observations are, the flow of current through the solution and the chemical changes
generally resulting in the liberation or dissolution of the electrode material at the
points where the current enters or leaves the solution. This phenomenon of
decomposition of the solutions by electrical current is termed as electrolysis.

Electrolytic conduction, in which charges carried by ions, will not occur unless the
ions of the electrolyte are free to move. Hence, electrolytic conduction is exhibited
principally by molten salts and by aqueous solutions of electrolytes. The principle of
electrolytic conduction is best illustrated by reference to an electrolytic cell such as
that shown in
Fig. 4.1 for the electrolysis of molten NaCl between inert electrodes. The entire
assembly except that of the external battery of Fig.4.1 is known as the cell.

Fig. 4.1: Electrolysis of molten sodium chloride

The electrons are received from the negative end of the external battery by the
negative electrode of the cell. These are used up in the reduction reaction at this
electrode. The numbers of electrons received at the negative electrode are given back
to the positive end of the external battery from the positive electrode of the cell where
electrons are released as the result of oxidation reaction. Within the cell, current is
carried by the movement of ions; cations moves towards negative electrode called the
cathode and anions towards the positive electrode called anode. This movement of
ions give rise to what is known as the electrolytic conduction. The latter, thus, depends
on the mobility of ions and anything that inhibits the motion of ions causes resistance
to current flow. Factors that influence the electrical conductivity of solutions of
electrolytes include interionic attraction, solvation of ions, and viscosity of solvents.
These factors depend on the attraction i.e. solute-solute, solute-solvent and solvent-
solvent respectively. The average kinetic energy of the solute ions increases as the

6
temperature is raised and, therefore, the resistance of electrolytic conductors generally Conductometry
decreases, that is, conduction increases as the temperature is raised.

Electrolytes and non-electrolytes

The ionic compounds, which furnish ions in solution and conduct electric current, are
electrolytes e.g. NaCl, KCl, etc. There are covalent compounds, which also conduct
electric current in solutions. These include HCl, CH3COOH, etc. All other substances
which do not produce ions in solutions are called non-electrolytes, e.g. cane sugar,
benzene, carbon tetrachloride, etc.

Sometimes electrolytes are also called as true electrolytes and potential electrolytes. In
true electrolytes the cations and anions do exist even in the molten states, e.g. NaCl,
KCl. They are true electrolytes because they exist as Na+ Cl − and K+ Cl − in their
normal states and in the molten states. Also when they are dissolved in water they
ionise and conduct current.

Na+ Cl − → Na+ (aqueous) + Cl − (aqueous)

The potential electrolytes do not conduct electricity in the pure normal state rather
they conduct electricity when dissolved in water, e.g. HCl, CH3COOH and NH3.

Strong and weak electrolytes

Electrolytes can be classified as strong or weak. This has nothing to do with their
concentration but related to their extent of ionisation.

Strong electrolytes: The substances, which are completely ionized in aqueous

solutions are called strong electrolytes, e.g. NaCl, NH4Cl, KNO3, HCl, HBr, etc.

Weak electrolytes: The substances which ionise only to a certain extent are called
weak electrolytes, e.g. CH3COOH, HCN, etc.

The terms strong and weak are relative. The behaviour of electrolytes also depends on
the nature of solvents, e.g. NaCl behaves as strong electrolyte whereas acetic acid as a
weak electrolyte in water. On the other hand, when dissolved in ammonia both NaCl
and acetic acid show comparable behaviour towards electricity.

Conductance of solutions
The ease of flow of electric current through a body is called its conductance. In
metallic conductors it is caused by the movement of electrons, while in electrolytic
solutions it is caused by ions of electrolyte. The electrolytic conductance, G, of a
medium is equal to the reciprocal of its electrical resistance R in ohms:
1
G= … (4.1)
R
Ohm’s Law states that the current I (amperes) flowing in a conductor is directly
proportional to the applied electromotive force E (volts) and inversely proportional to
the resistance, R (ohms) of the conductor:
E
I= or I = EG … (4.2)
R
Since a solution is a three-dimensional conductor, the exact resistance will depend on
the spacing (l) and area (A) of the electrodes. The resistance of a solution in such
situation is directly proportional to the distance between the electrodes and inversely
proportional to the electrode surface area.

7
Electroanalytical B
Methods-II

2 2
Am Am

Consider the electrolytic cell shown above, its two electrodes are having a cross-
sectional area of A m2 and separated by l m. The resistance (R) of the electrolyte
solution present between the two electrodes is:
R ∝l

1
R ∝
A

l
R ∝
A

l
R= ρ … (4.3)
A
where ρ (rho) is proportionality constant is called resistivity (formerly called specific
resistance). It is a characteristic property of the material and it is the resistance offered
by a conductor of unit length and unit area of cross section.
A
ρ= R … (4.4)
l
In SI units, l and A are measured in meters and square meters respectively, and the
resistance is expressed in ohm, Ω (omega). Therefore, the unit of ρ is ohm meters (Ω
m). Formerly, resistivity measurements were made in terms of a centimetre cube of a
substance, giving ρ the units Ω cm.

Substitute the value of R from Eq. (4.4) in Eq. (4.1). The expression for the
conductance, G is
1 1 A
G= = =κ … (4.5)
R ρ ( A/l ) l
where K (kappa) is reciprocal of specific resistance called as specific conductance or
conductivity. It is measured in Ω-1 m-1. This quantity may be considered to be the
conductance of a cubic material of edge length unity. However, in SI system, the unit
for conductance is ‘Siemens’ and, given the symbol ‘S’. Hence, the unit for
conductivity will be S m−1 (1S = 1Ω−1 ) or S cm−1. It may be remembered that S m−1 =
1/100 S cm−1. However conductivity is customarily reported in smaller units as milli
Siemens per meter (mS m−1) and micro Siemens per cm (µS cm−1).

Cell constant: For a given cell, l and A are constant, and the quantity (l/A) is called
the cell constant (k).
l
Kcell =
A

Substitute this value in Eq. (4.5)

8
 κ = G Kcell … (4.6) Conductometry

Conductivity = observed conductance × cell constant

To obtain the value of the cell constant, it is not necessary to determine l and A
directly. Instead, it is measured by a solution of known conductivity. Potassium
chloride solutions are invariably used for this purpose, since their conductances have
been measured with sufficient accuracy in cells of known dimensions. A given
solution of potassium chloride of conductivity κ′ is placed in the cell and its
resistance R' is measured. The cell constant is then equal to κ ′ R'. Therefore,
Kcell = κ ′ R'
Cell constant = conductivity KCl solution × measured resistance
Conductance is an additive property, e.g. in an aqueous solution containing several
electrolytes, the total conductance is

G(total) = ΣGi + G (water) … (4.7)

where the summation is to be carried over all the electrolytes present in the solution
and G (water) is the conductance of water, which is utilized for making the solution.
G (water) is often negligible in comparison to ΣGi as repeatedly distilled water
(known as conductivity water) of very low conductance is employed for making the
solutions.

SAQ 1
The resistance of a conductivity cell containing 0.01 mol dm −3 KCl is 150 Ω. The
same conductivity cell gives the resistance of 0.01 mol dm −3 HCl 51.4 Ω. The
conductivity of the KCl solution is 1.41 × 10–3 Ω-1 cm-1. Calculate the following
values:
i) Cell constant, and
ii) Conductivity of the HCl solution.

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4.2.1 Molar Conductivity

In order to compare quantitatively the conductivities of electrolytes, a quantity called
molar conductivity is frequently used. The molar conductivity, Λ m (capital lambda)
is the conductivity per unit molar concentration of a dissolved electrolyte. It is related
to conductivity, κ by the relation:
κ
Λm = … (4.8)
c
where c is the concentration in mol m−3. The molar conductivity is usually expressed
in S m2 mol−1 or S cm2 mol−1. It may be remembered that S m2 mol−1 = 10,000 s cm2
mol−1.
It is to be remembered that c in Eq. 4.8 is to be expressed in mol m−3 unit. If the
concentration is given in terms of Molarity (mol dm−3 ), then the following conversion
is to be carried out

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Electroanalytical c (mol m−3) = Molarity × 1000 … (4.9)
Methods-II
Earlier equivalent conductivity (Λeq), which is given by the following expression, was
in use
1000 × κ
Λeq = … (4.10)
c
where c is the concentration expressed in terms of normality of the solution. Unit of
Λeq is Ω −1 cm 2 eq −1 . However, IUPAC recommends the use of molar conductivity
only.

SAQ 2
Write the units of the following:
a) Conductivity
b) Equivalent conductivity
c) Cell constant
d) Molar conductivity

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SAQ 3
From the following data, calculate the molar conductivity of KCl in aqueous solution:
Conductivity of 5.0 × 10 −4 mol dm −3 KCl = 7.44 × 10 −3 S m–1
Conductivity of the water = 0.06 × 10 −3 S m–1

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4.2.2 Variation of Conductance with Concentration

The conductivity of an ionic solution increases with increasing concentration. For
strong electrolytes, the increase in conductivity with increase of concentration is sharp.
However, for weak electrolytes, the increase in conductivity is more gradual. In both
cases the increase in the conductivity with concentration is due to an increase in the
number of ions per unit volume of the solution. For strong electrolytes, which are
completely ionised, the increase in conductivity is almost proportional to the
concentration. In weak electrolytes, however, the increase in specific conductance is
not large due to the low ionisation of the electrolytes, and consequently the
conductivity does not go up so rapidly as in the case of strong electrolytes. Table 4.1
shows the variation of molar conductivity of a number of electrolytes at various
concentrations at 298 K.

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 Table 4.1: Molar conductivity (104 × S m2 mol–1) of electrolytes in aqueous Conductometry
solutions at 298 K
c/mol dm–3 KCl NaCl HCl AgNO3 CH3COOH CH3COONa
1.0 111.9 89.9 332.8 - - 49.1
0.1 129.0 106.7 391.3 109.1 5.2 72.8
0.05 133.4 111.1 399.1 115.7 7.4 76.9
0.01 141.3 118.5 412.0 124.8 16.3 83.8
0.005 143.5 120.6 415.8 127.2 22.9 85.7
0.001 146.9 123.7 421.4 130.5 49.2 88.5
0.0005 147.8 124.5 422.7 131.4 67.7 89.2

It is observed that in contrast to the conductivity, the molar conductivity, Λ m

invariably increases with decreasing concentration for both weak and strong
electrolytes. If we plot the molar conductivities of a large number of electrolytes
against the square root of the concentrations we find that these fall into two distinct
categories. In the case of strong electrolytes (for example KCl, NaCl or acids such as
HCl, H2SO4, etc), there is a small increase in molar conductivities with the decrease in
concentration. Since these electrolytes dissociate almost completely even in
concentrated solution, the number of ions do not change much with concentration. The
conductivity should not vary much since it is directly related to the number of ions
present in solution. The minor changes observed are due to interionic interactions. In
the case of weak electrolytes (for example CH3COOH, ammonia, organic fatty acids,
etc), the ionization will increase with dilution, and hence, the molar conductivity
increases with dilution. Thus the conductivity is directly proportional to the degree of
dissociation of a weak electrolyte.These above results are depicted in Fig.4.2 in which
the molar conductivity, Λ m, of two electrolytes (KCl and acetic acid) at a constant
temperature is plotted against √c. It may be seen from the figure that two different
types of behaviours are exhibited by these electrolytes. The strong electrolyte, KCl
shows a linear plot (almost straight lines). On the other hand, the weak electrolyte,
CH3COOH seems to approach the dilute solution limit almost tangentially. It is,
however, impossible to draw a sharp line of demarcation between the two categories
as many substances are known to exhibit intermediate behaviour, e.g., nickel sulphate.
Such electrolytes are sometimes called moderately strong electrolytes.

Fig. 4.2: Variation of molar conductivity on dilution (a) for aqueous solution of potassium
chloride (strong electrolyte) (b) acetic acid (weak electrolyte)

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Electroanalytical The conductance of a solution depends on the number of ions and the speed with
Methods-II which the ions move in solution. In case of strong electrolytes, the number of ions is
the same at all dilutions (since strong electrolytes are completely ionized) and the
variation of equivalent conductance with dilution is therefore due to the change in the
speed of the ions with dilution. In a concentrated solution of such electrolytes, the
interionic attractions among the oppositely charged ions would be quite appreciable.
The ions may also form some ion-pairs of the type A+B − that would not contribute to
the conductance. These interionic forces considerably lower the speed of the ions and
hence the conductivity of the solution. As the dilution is increased the interionic
attractions decrease with the result that the ions will move more freely and
independently of their co-ions and thus increasing the equivalent conductance with
dilution. At infinite dilution, the ions are quite far apart, the interionic attractions are
almost absent and each ion moves completely independent of its co-ions. The molar
conductivity then approaches a limiting value at infinite dilution and represents the
conducting power of 1 mole of the electrolyte when it is completely split up into ions.
It is denoted by Λ ∞.

It can be concluded that in case of weak electrolytes, the increase in molar

conductivity with dilution is mainly due to (a) an increase in the number of ions in the
solution (degree of ionization increases with dilution), and (b) smaller interionic
attractions at higher dilutions.

4.2.3 Limiting Molar Conductivity

An important relation can be obtained by extrapolating the curve for strong
electrolytes (Fig.4.2) to c → 0 where all interionic effects are absent. The limiting
value obtained by this extrapolation is called the molar conductivity at infinite
dilution.

Observing the linearity of Λ m versus c for strong electrolytes in dilute solutions,

Kohlrausch suggested the following empirical relation for the variation of equivalent
conductance of strong electrolytes with dilution.

Λm = Λ ∞ – b c … (4.11)

where b is a constant for the given electrolyte and Λ ∞ is the molar conductivity of the
electrolyte at infinite dilution. The validity of this equation may be seen from the plot
for electrolytes like HCl, KCl, etc. To obtain Λ ∞ of such electrolytes the curve is
extrapolated to c → 0 and the intercept so obtained gives the value of Λ ∞ . The same
method cannot be used for obtaining Λ ∞ for weak electrolytes because of the steep
increase in Λ at high dilutions. Λ ∞ may also be computed from the molar
conductivities at infinite dilution of the respective ions, since at infinite dilution, the
ions are independent of each other according to the law of independent migration of
ions and each contribute its part to the total conductivity, therefore,

Λ ∞ = Λ ∞+ + Λ ∞− … (4.12)

where Λ ∞+ and Λ ∞ − are the ionic conductivities at infinite dilution of the cation and
anion, respectively.

The molar conductivity of the ionic species is a measure of the amount of current
carried by ions in question. Comparison of the molar conductivities of ions is,
therefore, more meaningful when related to per unit charge, for example when
Λ ∞ (Na+) is compared with ½Λ ∞− (Mg2+) rather than Λ ∞− (Mg2+) or in terms

12
equivalent conductivities. The value of the limiting ionic molar and equivalent Conductometry
conductivities for some ions in water at 25oC are given in Table 4.2.
Table 4.2: Limiting ionic molar conductivities and limiting ionic equivalent
conductivities of selected ions in water at 25o C

Λ ∞ /(S cm2 Λ ∞ /(S cm2 eq–1) Λ ∞ /(S cm2 Λ ∞ /(S cm2

Cation Anion

mol–1) mol–1) eq-1)

H+ 349.8 349.8 OH − 198.3 198.3

+
Li 38.7 38.7 F− 55.4 55.4
+
Na 50.1 50.1 Cl − 76.3 76.3
+
K 73.5 73.5 Br − 78.1 78.1
Be+2 90.0 45.0 I − 76.8 76.8
2+
Mg 106.2 53.1 NO3 − 71.5 71.5
2+
Ca 119.0 59.5 SO42 − 160.0 80.0
2+
Ba 127.2 63.6 CH3COO − 40.9 40.9
3+
Al 183.0 61.0 C6H5CO − 32.4 32.4
Cu2+ 107.2 53.6 HCO3 − 44.5 44.5
+
Ag 61.9 61.9 CO32 − 138.6 69.3
2+
Zn 105.6 52.8 Fe(CN)63 − 302.7 100.9
3+
Ce 209.4 69.8 Fe(CN)64 − 442.0 110.5

Ionic Mobilities and Transport Number

The next question which arises in connection to the values of conductivity, given in
Table 4.2, is why should there be a difference between the values of limiting molar
conductivities of similarly charged ions, if these ions are just acting as carriers of
electric charges only?
The answer lies in the fact that different ions have different mobilities in solution. The
mobility of an ion in solution is mainly dependent upon the size of the hydrated ion.
The ionic mobility is defined as the velocity with which an ion would move under a
potential gradient of 1 V m–1 in a solution. It provides a link between theoretical and
measurable quantities. For instance, ionic mobility, (u), is related to limiting molar
ionic conductivity (Λ ∞ ) by the following equations:

Λ ∞+ = z+u+F and Λ ∞+ = z–u–F … (4.13)

where z+ and z– are the valency of the ions, u+ and u– represent the ionic mobilities
and F is the Faraday constant. In the above equation, if one of the two quantities, Λ ∞
or u, is known, the other can be calculated.

To find the values of Λ ∞ ∞

+ or Λ + ,we define yet another quantity, called transport or
transference number of an ion indicated by the symbol t+ or t–. It is defined as the
fraction of the total current carried by an ionic species and can be expressed
mathematically as,

t+= Λ ∞
+ /Λm and t– = Λ ∞− /Λm … (4.14)

The transport number and the limiting molar conductivity are measurable quantities.
Hence, the molar ionic conductivity value can be calculated from Eq. (4.14). The

13
Electroanalytical limiting molar conductivities of some common ions are given in Table 4.2. These
Methods-II values are important in predicting the molar conductivity of electrolytes and course of
conductometric titrations. Finally, once the molar ionic conductivity value is obtained,
we can then make use of Eq. (4.13) to calculate the ionic mobility. Some typical
values of ionic mobility (in infinite dilute solutions) are listed in Table 4.3.

Table 4.3: Limiting ionic mobilities in water at 298 K

Cation 108 u+ / m2 v–1 s–1

H+ 36.24

Li+ 4.01

Na+ 5.19

K+ 7.62

Ag+ 6.42

Anions 108 u– / m2 v–1 s–1

OH– 20.58

Cl– 5.74

Br– 7.92

I– 8.09

NO3– 7.41

It is interesting to look at Table 4.2 in more detail. You will see the Li+ ion, because
of its larger hydration shell, has a lower mobility than the potassium ion. Similar
argument can be applied to the F– & Br– ions. Exceptional mobilities are observed for
the H+ and OH– ions. This is because, in these case charge is transported through
proton jump mechanism along with general migrations mechanism, consider he case
of H+ ion.
H H H H
|1 | |3 |4
+ 2
H ⇒ −H − O− H - - - O − H- - - O − H - - - O − H
+

H H H H
|1 |2 |3 |4
- - - H − O- - - H – O − H - - - O− H - - - O− H
+

H H H H
|1 |2 |3 |4
– H − O – - - -H – O- - - H – O − H - - - O − H
+

You can see how hydrogen ion jumps from O1 to O2, O2 to O3, ......., this result is
equivalent to as the migration of charge from left to right. This conduction mechanism
is more like a charge than ion movement. Such conduction is possible because of the
peculiar structure of water and therefore only found in hydrogen-bonded solvents.

4.2.4 Effect of other Factors on Conductivity

Beside concentration, there are some more factors which affect the conductivity of the
electrolyte solution.

14
a) Effect of temperature and pressure: The conductivity of all electrolytes Conductometry
increases with increasing temperature. The variation of molar conductivity at
infinite dilution with temperature is given by an empirical equation.

Λ ∞ (t) = Λ ∞ (25)[1+ x(t – 25)] … (4.15)

where Λ ∞ (t) and Λ ∞ (25) are the value of molar conductivities at t and 25oC
respectively, and x is a constant for each electrolyte. For salts x is about 0.022 to
0.025 and for acids and bases it is usually 0.016 to 0.019. It means that molar
conductivity increases approximately by 2% for every one degree rise in
temperature. For strong electrolytes, even at appreciable concentration, Eq.
(4.15) holds well, whereas in case of weak electrolytes, the variation of Λ with
temperature is not so regular. The rise in conductance with temperature is due to
the decrease in the viscosity of the solution, increase in the speed of the ions and
an increase in the degree of ionization in cases of weak electrolytes.

The conductivity increases slightly with increase in pressure. The effect is

mainly through changes in the viscosity of the medium, which decrease by an
increase in pressure. Consequently, the equivalent conductance of the solution
will increase with rise in pressure.

b) Effect of solvent: In solvents of low dielectric constants, having small ionizing

effect on the electrolytes, the electrostatic forces between oppositely charged
ions would be appreciable and equivalent conductance will have small value.
However, solvents with high dielectric constants yield more conducting
solutions.

c) Viscosity of the medium: The dependence of conductance on viscosity of the

medium is given by Walden’s rule, according to which the equivalent
conductance of an electrolyte is inversely proportional to the viscosity of the
medium, i.e.

Λ ∞ η0 = constant … (4.16)

where Λ0 is the equivalent conductance at infinite dilution and ηo is coefficient

of viscosity of the solvent. If ions are not solvated, i.e., they have the same size
in all the solvents, then it follows from Walden rule that Λ ∞ η0 should be
constant and independent of the nature of the solvent. This is true only for ions
like tetra-alkyl ammonium cations, which are not solvated. Ions where extensive
solvation occurs, effective radii of the ions will not be constant and Walden rule
will not be obeyed.

SAQ 4
List the factors which are affecting the conductivity of the solution.

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4.3 MEASUREMENT OF ELECTROLYTIC

CONDUCTANCE
The conductance of a solution can be determined by measuring the resistance offered
by solution contained within the two electrodes of a conductivity cell. For measuring

15
Electroanalytical resistance, the Wheatstone bridge principle is employed. Therefore, before taking up
Methods-II the measurement of conductance of solution, let us study the principle of Wheatstone
Bridge.

4.3.1 The Wheatstone Bridge Principle

A Wheatstone bridge (Fig. 4.3) is employed to measure the resistance of an electronic
conductor. It works on the principle of obtaining balance between two arms with the
help of a balance indicator (e.g. a galvanometer) at the condition of potential being
equal.

Let Rx be an unknown resistor, R1 and R2 two standard resistors, R3 an adjustable

resistor and G a galvanometer. The bridge is connected to a source of power S, a
battery, and a tapping key K is placed in the path to control the connections.

i1 i2
R1 R2

S
B D
G K
_
i1

R3 i2 RX

Fig. 4.3: A DC Wheatstone bridge circuit

To measure the resistance Rx, the tapping key K is held down momentarily and the
bridge is balanced by adjusting R3 to get no deflection in galvanometer under these
conditions.

In the bridge the total current is divided into two paths: i1 through R1 and R3, and i2
through R2 and Rx. Under the balancing conditions, the potential at points B and D
must be the same, i.e. the ohmic voltage drop through the resistors R1 and R2 must be
the same. Hence, the potential at B (EB) must be equal to potential at D (ED).
EB = ED … (4.17)

Or i1 R1 = i2R2 … (4.18)

Similarly, i1 R3 = i2 Rx ... (4.19)

Dividing Eq. (4.18) by Eq. (4.19), we get
R1 R2
=
R3 RX

R2 R3
and Rx = ... (4.20)
R1

16
Thus, we can calculate Rx as R1, R2 and R3 are all known. Conductance G, being the Conductometry
reciprocal of resistance will be,
R1
G= … (4.21)
R2 R3

Alternatively, the conductometric cell can be incorporated into operational amplifier

control circuit, as shown in Fig. 4.4. The amplifier balances the potential of two
inputs. The current from the input potential, Ei, is balanced by the current from
amplifier output which passes through a feedback resistor (Rf). The output potential,
E0 is in terms of resistance:
E0 = Ei (Rf/Rx + 1)
where Rx is the resistance of conductometric cell.

With respect to the solution conductance,G, above equation becomes

E0 = Ei(RfG + 1)

Rf

_
D
E0
+
Rx
Ei

Fig. 4.4: An operational amplifier control circuit for conductometric measurement.

Rx is the solution resistance and Rf is the feedback resistance

4.3.2 Measurement of Conductance of a Solution

The Principle of the Wheatstone bridge discussed above can be used to measure the
conductance of solutions. However, the following considerations must also be kept in
mind:

i) Since a direct current would polarize the electrodes in the conductivity cell by
electrolyzing the solution to avoid polarization an alternating current (ac) source
of power must be used in place of a dc source (battery) usually ac voltages of
3-6 volts with frequency of 50 Hz or 1000 Hz used across points A and C of Fig.
4.5.

ii) A suitable conductivity cell (with electrodes dipped in the solution) is located
between points C and D. Thus, Rx represents the resistance of the conductivity
cell.

iii) Since, the cell also acts like a small capacitor (Cx), and to balance its capacitive
resistance a variable capacitor, CB, must be inserted into the bridge.

iv) The balance indictor (BI) may be an ac galvanometer, but some other devices
are also be used:
• An earphone can act as a balance indicator if the frequency of the ac
source is in audio-range.

17
Electroanalytical • A magic eye, which gives a green fluorescence as a result of electrons
Methods-II
striking a phosphor coating inside the glass tube, is used in several
commercial instruments.
• For much precise conductance measurements a cathode ray oscilloscope is
used as the balance indicator.
A

R1 R2

ac
B BI D

Conductivity cell
R3

RX
CB
CX
C

Fig. 4.5: A conductivity bridge circuit

v) Conductance (G=1/Rx) can be read directly on commercially available
instruments as a panel mounted meter. Now several digital instruments are also
available, such instruments give the conductance directly as the numerical value.

Conductometer
From above discussion we can conclude that conductance is reciprocal of resistance
and the resistance of a cell can be measured by placing it in an arm of a Wheatstone
bridge. The inverse of the resistance gives the conductance and can be directly read
on a conductivity measuring instrument, known as “Conductometer”.

A typical conductometer, consists of an ac source, a Wheatstone bridge circuit, a null

detector or direct reading display and a conductivity cell.

To avoid the effects of polarization, i.e. the change is composition of the measuring
cell, alternating current (ac) is used. The instrument has an arrangement to convert the
supply of 50 Hz to higher frequency, say 1000 Hz. For measuring low conductance
solutions, the lower frequency is preferable and for high conductive solutions higher
frequencies are preferably used.

Several inexpensive conductometers are commercially available. The instruments

come as a line-operated unit with and without digital readout. Fig. 4.6 gives the view
of a typical conductometer, which can be operated as with given instructions.

Read
.4 .8 1.2 Cal.
0 1.6
2.0 Sensitivity

mS range
selector

Conductometer

Fig. 4.6: Conductometer

18
Cells Conductometry

Various types of cells have been designed and are in use for the measurement of
conductance of a solution. These are made of Pyrex glass fitted with electrodes of
platinum or gold. To overcome the imperfections in the current and the other effects at
the electrodes, these are coated with a layer of finely divided platinum black. This is
achieved by electrolyzing a 3% solution of chloroplatinic acid containing a little of
lead acetate. The distance between the electrodes is determined by the conductance of
the solution to be measured. For highly conducting solution, the electrodes are widely
spaced whereas for low conducting solutions the electrodes are mounted near each
other. A cell suitable for conductometric titration is depicted in Fig. 4.7 (a, b and c);
the electrodes are firmly fixed in the Perspex lid which is provided with opening for
the stirrer and the jet of the burette. A magnetic stirrer can be used in place of
mechanical stirrer.

For most purposes a special cell is not required and good results are obtained by
clamping a commercially available dip cell [shown diagrammatically in Fig. 4.7 (b)]
inside a beaker which is placed on a magnetic stirrer. With this arrangement, the
dipping cell should be lifted clear of the solution after each addition from the burette
to ensure that the liquid between the electrodes becomes thoroughly mixed. Since
absolute conductivity values are not required it is not necessary to know the cell
constant.
For spot checking on a process stream or tank, a dip-type of conductivity cell is used.
In some titrations on open beaker with fixed electrodes is sufficient. However, for
fairly dilute solutions an open beaker would not be satisfactory because atmospheric
CO2 may alter the conductance.

Fig. 4.7: Typical designs of conductivity cells

Procedure
1. Plug the instrument to an ac supply.

2. Put the frequency selector switch to required frequency (say 1000 Hz).

3. Set the mode selector on CAL and set the range selector on the desired setting
e.g., 2, 20 or 200. These figures refer to the full scale meter value in milli
Siemens (mS). With the help of sensitivity knob keep the pointer roughly
midway between the lowest and highest sensitivity say at 1 position.

19
Electroanalytical 4. Connect the conductivity cell electrodes to the appropriate terminals of the
Methods-II instrument. Clean the conductivity cell with distilled water (Conductivity water).

5. Take the standard KCl solution (say 0.1M) in a clean beaker. Introduce a
stirring rod (to be used for magnetic stirring) in the solution and put the solution
beaker on a magnetic stirrer plate.

6. Insert the conductivity cell in the solution. Ensure that the platinum plate
electrodes are completely immersed in the solution and they do not touch the
stirring rod or the sides or the bottom of the beaker.

7. Switch on the instrument and allow it to warm up for 2-5 minutes.

8. Measure the conductance, Gs , of the standard KCl solution by putting meter

switch to READ position.

9. Remove the KCl solution from the beaker, wash the conductivity cell properly
with distilled water. Take the unknown solution in the beaker and measure its
conductance, Gu , in the manner as for standard KCl solution.

10. Calculate the cell constant, from the conductance and conductivity values of the
standard,
Conductivi ty (specific conduc tan ce)
K cell =
Observed conduc tan ce of the s tan dard
κs
= cm −1
Gs

11. Calculate the conductivity (specific conductance) of the unknown solution =

cell constant × observed conductance
κ u = K cell G u
12. For titration work, the value of cell constant, Kcell is not required to be
calculated, since the cell constant will remain unchanged during the course of
any given titration.

Notes
i) When the range selector is switched to a new position, it is essential to check the
calibration again. Set the meter again to read one with the sensitivity control, if
any deviation is observed.
ii) The conductivity cell, when not in use, should be kept in distilled water to
prevent drying the platinum electrodes.
iii) In case of fouling the conductivity cell electrode plates, clean them by keeping
in dilute K2Cr2O7 containing H2SO4 solution (i.e. dilute chromic acid) for 24
hours and then washing with running water followed by rinsing with distilled
water.

4.4 APPLICATIONS OF CONDUCTOMETRY

The high sensitivity of the conductometric measurements makes it an important
analytical tool for environmental analysis and certain other applications. A continuous
or spot check measurement of conductance is employed, usually, with a dip electrode
cell and meter. In certain cases continuous recording of conductance is also employed.
Since conductance depends on ionic concentrations, the purity of steam distillate,
demineralized water, and the ionic contents of raw water can be checked with

20
measuring conductance directly. Metal industries, electroplating baths and rinse baths Conductometry
are monitored by conductance methods.

Perhaps the most common application of direct condutometry has been for estimating
the purity of distilled water. Kohlrausch with a painstaking work after 42 successive
distillations of water in vocuo obtained a conductivity water with specific
conductance, κ = 4.3 × 10‾8 S cm‾1 at 18 °C. Traces of an ionic impurity will increase
the conductance appreciably. Ordinary distilled water in equilibrium with the carbon
dioxide of the air has a conductivity of about 7.0 ×10–7 S cm–1. The sea water has
much higher value of conductivity and the conductometric measurements are widely
used to check the salinity of water in oceanography.

Measuring conductance of soil helps in finding the moisture content of soils at various
places with portable instruments. All soils contain varying amount of water soluble
salts upto 0.1% or even more. These salts are usually present as sulphate, chloride,
carbonate or bicarbonate of sodium, potassium, calcium and magnesium and
contribute to the conductance of the soil. The soil may be classed as saline and non-
saline depending on the nature and quantity of the salts present. Conductivity of a
saturated extract with water of saline soil at 25 °C has a conductivity greater than
4 mS cm−1.

Based upon the relative change in the conductance/resistance of a solution with the
addition of an other electrolyte, methods have been developed for the titration of a
strong acid with a strong base, weak acid versus strong base or a weak base and a
mixture of a strong acid and weak acid versus a strong base. Other types of titrations
which can be performed conductometrically include displacement titrations: a salt of a
weak acid (sodium acetate) versus a strong acid like HCl or a salt of weak base
(ammonium chloride) versus sodium hydroxide; precipitation titrations: silver nitrate
versus KCl; complexometric titrations: mercuric nitrate versus KCN or EDTA versus
metallic ions and oxidation – reduction
(redox) titrations like the titration of Fe(II) versus KMnO4.

Conductometric methods based upon precipitation or complex formation reactions are

not as useful as those involving neutralization processes. Conductance changes during
these titrations are seldom as large as those observed with acid-base reactions because
no other reagent approaches the great ionic conductance of either hydronium or
hydroxide ion.
The main advantage to the conductometric end point is its applicability to very dilute
solutions and to systems that involve relatively incomplete reactions. For example,
while neither a potentiometric nor indicator method can be used for the neutralization
titration of phenol (Ka= 10–10) a conductometric end point can be successfully applied.

Direct measurement of conductivity is potentially a very sensitive procedure for the

determination of various parameters like the degree of dissociation of a weak
electrolyte and its dissociation constant, ionic product of water, solubility and
solubility product and hydrolysis constant of a salt

SAQ 5
At 298 K, the resistance of 2.00 × 10−2 M KCl is 195.96 Ω and that of 2.50 × 10–3 M
K2SO4 is 775.19 Ω. The conductivity (κ) of 2.00 × 10−2 M KCl at 298 K is 0.2768 S
m−1. Calculate molar conductivity of K2SO4 solution.

…………………………………………………………………………………………...
…………………………………………………………………………………………...
…………………………………………………………………………………………...

21
Electroanalytical
Methods-II 4.5 SUMMARY
In this unit, various parameters like resistance (R), conductance (G), resistivity (ρ),
conductivity( κ ), equivalent conductivity(Λeq), molar conductivity(Λm), molar
conductivity at infinite solution(Λo) and cell constant have been defined in detail along
with their units for measurements. The relationships among these parameters have also
been worked out. Various factors affecting the conductance of solution are also given.
At the end detailed procedure for the measurement of conductance is given.

4.6 TERMINAL QUESTIONS

1. What are electrolytes? How are they classified?

2. Define molar conductivity and equivalent conductivity of an electrolyte. How

are they related to each other?

3. Write expression for a cell constant and conductivity of an electrolyte.

4. Why are platinum electrodes in conductometric cell are coated with Pt black?

5. What are the various factors affecting the conductance of solution?

6. How will you measure electrolytic conductance of a solution?

7. Explain the necessity of maintaining a constant temperature in conductometric

measurements.

8. The conductivity of 0.1 M HCl is 0.0394 Ω–1 cm–1. What is the molar
conductivity of the solution?

9. The resistance of 0.1 M solution of a salt occupying a volume between two

platinum electrodes 1.80 cm apart and 5.4 cm2 in area was found to be 32 ohms.
Calculate the molar conductivity of the solution.

10. A certain conductance cell was filled with 0.0100 M solution of KCl, whose
conductivity is 0.001409 Ω –1 cm–1 (S cm–1) at 25 oC, it had a resistance of
161.8 Ω, and when filled with 0.0050 M NaOH, it had a resistance of 190 Ω.
Calculate the cell constant, conductivity and molar conductivity of NaOH
solution.

11. A conductivity cell shows a resistance of 3950 Ω at 25 oC when filled with the
experimental solution and 4864 Ω at the same temperature when filled with
0.02 M KCl solution. If the conductivity of the solution is 2.767 × 10–3 S cm–1,
calculate the conductivity of the experimental solution.

12. The resistance of a conductivity cell was 702 ohms when filled with 0.1 M KCl
when filled with 0.1 M KCl solution (K = 0.14807 ohm–1 m–1) and 6920 ohm when
filled with 0.01M acetic acid solution. Calculate the cell constant and molar
conductance for the acid solution.

4.7 ANSWERS
Self Assessment Questions
1. i) Kcell = κKCl /Gobs. or = κKCl × Robs.
= 1.41 × 10–3 Ω−1 cm−1 × 150 Ω = 0.2115 cm−1

22
 ii) κ = Kcell Gobs. = Kcell /Robs. = 0.2115 cm−1/51.5 Ω = 4.11 × 10–3 Ω−1 cm−1 or Conductometry
(S cm−1)

2. a) conductivity: S m−1 or Ω−1 m−1

b) Equivalent conductivity: Ω−1 cm−1 eq−1
c) Cell constant : m–1 or cm–1
d) Molar conductivity: S m2 mol−1 or S cm2 mol−1

3. κKCl = κsol. − κwater

(7.44–0.06) × 10–3 = 7.38 × 10–3 S m−1

7.38 ×10 −3 S m −1
Λm = K/c = −4 3 −1
= 1.476 × 10–2 S m2 mol−1
5.0 × 10 × 10 mol m
4. Concentration ionic mobility, temperature and pressure, nature of solvent,
viscosity of medium, etc.

5. Consider following equation:

Kcell = κ × R
= 0.2768 S m–1 × 195.96 Ω = 54.24 m−1.
Conductivity of K2SO4 solution can be given by,
K cell 54.24 m −1
κ= = = 0.06997 S m−1 .
R 775.19 Ω
Concentration of K2SO4 in mol m−3 unit:
c = 1000 × 2.50 × 10−3 mol m−3
= 2.50 mol m−3
Molar conductivity of K2SO4 can be expressed as
κ 0.06997
Λm = = Sm2 mol−1
c 2.50
= 0.028 S m2 mol−1

Terminal Questions
1. The ionic compounds which form ions in solution and conduct electric current
are called electrolyte e.g. NaCl, KCl, etc. They can be classified strong and
weak electrolyte, on the basis of their degree of ionisations.

2. Molar conductivity: It is the conductivity for unit molar concentration of a

dissolved electrolyte.
κ κ 1000 κ
Λm = = S m 2 mol −1 = S cm 2 mol −1
c M × 1000 M
Equivalent Conductivity: It is the conductivity of 1 g equivalent of an electrolyte
when present in V cm3 of solution
Λeq = κV

If c is the concentration of the solution in g equivalent per dm3, then

1000 κ
Λeq =
c
Its unit is S cm2 eq–1

23
Electroanalytical Relationship
Methods-II
Molar Conductivi ty (S cm 2 mol −1 )
Λeq =
n
where n = charge unit

3. Cell constant: The quantity (l/A) is called the cell constant.

Conductivity: It is the reciprocal of specific resistance. Conductivity of an
electrolyte in a cell can be expressed as:
conductivity = observed conductance × cell constant

4. To overcame the imperfection in the current and the other effects at the
electrode.

5. Concentration, ionic mobilities, temperature, solvent and viscosity of medium:

for further details, please go through the section 4.2.2, 4.2.3 and 4.2.4.

6. Detailed procedure is given in the Sub Section 4.3.2.

7. Because conductivity of all electrolytes increases with increasing temperature.

8. Λm = K/c, therefore,
Λm = 0.0394 ( Ω–1 cm–1)/ 0.1 M =0.0394 (Ω–1 cm–1)/0.1 × 10−3 mol cm−3
= 394 Ω–1 cm2 mol–1

9. Cell constant = l/A, 1.8/5.4 = 1/3 cm–1

Observed conductance = 1/32 Ω–1
K = Cell constant × conductance=1/3 × 1/32 = 1/96 Ω-1cm–1
Λm = K/c = 1/96 (Ω–1 cm–1) × 1/0.1 M
=1/96 (Ω–1 cm–1) × 1/0.1 × 10−3 (mole cm–3) =104.16 Ω–1 cm2 mol–1

10. Cell constant = KR = 0.001409 Ω–1 cm-1 × 161.8 Ω = 0.228 cm–1

κ NaOH = Cell constant/R = 0.228 cm–1/190 Ω = 1.2 × 10–3 Ω–1 cm–1
Λm = K/c = 1.2 × 10–3 Ω–1 cm–1/ 0.0050 × 10−3 mol cm–3 = 240 Ω–1 cm2 mol–1

11. Cell constant = KR = 2.767 × 10–3 (S cm–1 ) × 4864 (Ω)

Conductivity of the experimental solution = K= Cell constant/R
= 2.767 × 10–3 × 4864 (cm–1)/3950(Ω) = 3.407 × 10–3 S cm–1

12. Cell constant = KR = (0.14807 ×702) (ohm–1 m–1) (ohm) =103.94 m–1 =
1.039 cm–1
Conductivity of acetic acid K = (1/R) (l/A)
= (1 / 6920 Ω) (1.039) cm–1
= 1.501 × 10–4 Ω–1 cm–1
= 1.501 × 10–2 Ω–1 m–1
Concentration = 0.01 M = 0.01 mol dm3 = 0.01 × 103 mol m–3
Λm = K/c = 1.501×10–2 Ω–1 m–1/ 0.01×103 mol m–3
= 1.501 × 10–3 mol–1 Ω–1 m2

24