14 ELECTRICAL CONDUCTANCE AND

ELECTROLYSIS

Substances through which electricity can flow are called electrical conductors.
Substances which do not conduct electricity at all are termed insulators. Metals, graphite
or solutions of salts, acids and bases conduct electricity. Metals conduct electricity in the
solid and molten state. Graphite is the only non-metal which conducts electricity and that
only in the solid state. Conduction of electricity by metals and solutions of salts acids and
bases has been known for a long time. Salts conduct electricity also in the molten state.
Electrical conduction by chemical compounds in solution and in the molten state is
accompanied by physical and chemical changes. The phenomenon of chemical change by
the passage of electricity through substances in solution or the molten state is called
electrolysis.

14.1 Electrolytic Conduction

Conductors of electricity may be divided into two groups according to the mechanism
by which electricity is carried through them.
(a) The electronic, conductors where electricity is carried by electrons. Metals and
graphite fall in ths category.
(b) The electrolytic conductors where the electric current is carried by ions.
Solutions of acids, bases and salts fall in this category. Substances which
conduct electricity in solution are called electrolytes.
Examples are known of cases where the current is carried partly by electrons and partly
by ions.
The capacity of conducting electricity is not the same for all electrolytes. Strong
electrolytes are those which are good conductors Cf electricity whereas those electrolytes
which are poor conductors are called weak electrolytes. The distinction beveen the two
types is rather vague. Salts, mineral acids and hydroxides of alkali and alkaline earth
metals are grouped as strong electrolytes. Organic acids, ammonium hydroxide etc. are
weak electrolytes.

14.2 Metallic and Electrolytic Conduction

There are several points in which metallic conduction and electrolytic condition
differ. The following Table gives a comparison of the two types of conduction of
electricity.
380 Principles of Physical Chemistry

Table 14.1 Comparison of metallic conduction and electrolytic conduction

Metallic conduction Elect rolvtic conduction
(i) The current is solely carried by the (I) The current is carried by both
electrons in the conduction band cations and anions.
(Section 4.11.3).
(ii) The velocity of the electrons is (ii) Ionic velocities are much
very large. smaller than electron
velocities.
(iii) During passage of current no (iii) Passage of current brings about
chemical reaction occurs; only chemical reactions; heat is also
heating effect is produced. evolved.
(iv) Specific conductance of many (iv) Specific conductance is low;
metals are quite high; they are they are moderately good
very good conductors of conductors.
electricity.
(v) Temperature co-efficient in (v) Temperature co-efficient is
general is negative (alloys show positive.
complex behaviour).
(vi) Ohm's law applies. (vi) Ohm's law applies.
(vii) Conductance may be measured by (vii) Conductance is measured by a-
d-c or a-c current. c source; d-c current can be
used only by elaborate
arraruzements.

14.3 Electrolysis
Early in the investigation on the effect of passing current through solutions it was
discovered that decomposition of the solute took place. As soon as the current stopped
decom position ceased, clearly indicating that the decomposition was in some way
connected with the passage of the current. Also the products appeared only at the poles
where the electricity entered or left the solution. M. Faraday (1832-33) studied the
phenomena associated with electrolysis and introduced the nomenclature which is used
to-day. The pole, usually wires or plates, through which the electricity was supposed to
enter the solution was termed cathode and the pole where it was supposed to leave the
solution was called the anode; the former is the one attached to what is known by
convention as the 'positive pole' of the battery and the latter is attached to the 'negative
pole'. The cathode and anode are termed the electrodes. Faraday assumed the flow of
electricity through solutions to be associated with the movement of charged particles;
these were called ions (Greek: wanderer). He, however; did not say anything about their
origin. The particles carrying a positive charge and moving towards the cathode were
referred to as cations and the ones carrying a negative charge and moving towards the
anode were referred to as anions. On reaching the electrodes the charges on the ions were
thought to be neutralized and the particles deposited in the form of atoms or molecules.
 Electrical Conductance and Electrolysis 381

14.4 The Mechanism of Electrolytic Conduction

The first successful mechanism of electrolysis was put forward by R. Clausius (1857).
He made the following assumptions:
(1) in solution the electrolytes are automatically split into ions,
(ii) the ions exist only for a short interval and an equilibrium exists between the
ions and the undissociated molecules,
(iii) the free ions carry charge and carry current during the short period of their
existence.
(iv) only a very small number of the molecules would be split up into ions,
(v) as the ions are removed by discharge at the electrodes or recombination, fresh
molecules break up into the ions in order to maintain the equilibrium.

This theory was satisfactory to a large extent, but there was no quantitative expre-
ssion associated with it. The quantitative relationship was given by Arrhenius.
S. Arrhenius put forward his theory of electrolytic dissociation in 1887. According to
this theory it is assumed that when an acid, base or salt is dissolved in water, a fraction of
it breaks up spontaneously into positive and negative ions, and an equilibrium is
established between the undissociated electrolyte molecules and the ions. Thus for the
electrolyte MA,
MA(aq) M(aq) + A(aq) (12.1)
The ions are free to move independently and randomly in the liquid medium. When an
electric field is applied the ions are attracted towards the electrodes, the positive ions,
called cations, going to the cathode and the negative ions, called anions, to the anode. At
the electrodes the ions give up their charge and are liberated. By postulating that the
fraction of the electrolyte dissociated increased when the solution was diluted Arrhenius
was able to explain the concentration variation of conductance. Arrhenius gathered
support for his theory from van't Hoff s investigation of the colligative properties of
solutions (Section 9.20).
It is now believed that once electrolytes are placed in water the ions separate. The
ions get surrounded by water molecules and oppositely charged ions which form what is
called an ion atmosphere. When electricity is passed through the solution ions with their
ion atmospheres move to electrodes with opposite sign ( Section 14.13).

14.5 Faraday's Laws of Electrolysis

Micheal Faraday (1804) carried out a large number of experiments on electrolysis,
and derived quantitative relationships between the quantity of electricity passed through
the electrolyte and the amount of material liberated on the electrodes. The results of his
experiments were expressed in the fwm of two laws. These are known as Faraday's Law
of electrolysis
 382 Principles of Physical Chemistry
First Law of Electrolysis: The amount of substance dissolved from or liberated at an
electrode is proportional to the quantity of electricity passed through the electrolyte
solution.
The unit of the quantity of electricity is Coulomb, One Coulomb is the quantity of
electricity when one ampere current flows through a conductor for one second. One
coulomb is given the symbol C.
If 1 ampere current flows for t seconds then the quantity of electricity passed is
Q = I x t coulombs (14.2)
Now if in is the mass in gram of substance liberated at an electrode by passing Q
coulomb of electricity, according to Faraday' first law
in oc J X t

where I is the current in Ampere (A) and t is the time (in second) during which current
was passed.
Or /it zXIXt (14.3)

where z is a constant of proportionality, and is known as the electrochemical equivalent

of the substance. If! = I A and t = 1 second then, in z. Thus,
The electrochemical equivalent is the amount of substance liberated when I A current
is passed through the electrolyte for I second or when one Coulomb of electricity is
passed.
Second Law of Electrolysis: When the same quantity of electricity is passed through
different electrolyte solutions of different substances, 'equivalent masses' of the elements
are liberated at the electrodes.
The meaning of the term 'equivalent masses' as used by Faraday needs explanation
in the conLex of present ideas and is described in Section 14.6.
These laws have been found to hold under all conditions, provided the current is
carried entirely by the ions.
14.5.1 Verification of the First Law of Faraday
Faraday's first law may be verified by measuring the quantity of electricity flowing
through an electrical circuit. The apparatus used for the purpose is known as a voltameter,
or better a coulometer (Figure 14.1) because the same apparatus can be used to measure
the quantity of electricity passed. In this apparatus the amount of a metal deposited on a
clean electrode by passing a known current for a definite time through a solution of a salt
of the metal is determined. If AgNO3 solution is used as the electrolyte metallic Ag will
be deposited on the cathode, generally a platinum basin containing the silver nitrate
solution. The deposit is washed with water, dried and weighed. The mass of the metal
deposited can be accuratel y determined by weighing the electrode before and after
 Electrical Conductance and Electrolysis 383

passage of the current. If a current I ampere Key

flows for t seconds, the quantity of
electricity passed is I x t Q coulombs.
The mass of metal deposited on passing

1 1<
different quantities of electricity can be
determined. The results show that the mass
of metal deposited is proportional to Q, the i cathode
quantity of electricity passed. anode

The same set up can be used to

determine the quantity of electricity Q by Solution of electrolyte
using equation (14.2).
Figure 14.1 Coulometer

14.5.2 Verification of the Second Law of Faraday

The second law can be verified by using solutions of HC1, AgNO3 and CuSO 4 in an
apparatus as shown in Figure 14.2 which consists of three coulometers arranged in series.
In all cases the cathode used is of platinum (an inert metal). The same amount of current
is passed for a definite time, and the amount of positive ions liberated at the cathode in
- Key

Pt Cu

HCl Solution AgNO3Solution CuSO4Solution

Figure 14.2 Three coulometers in series

each coulometer is determined. It is found that the amount discharged is in the proportion
of half mole of hydrogen: one mole of silver: half mole of copper, i.e. to 1 : 107.88
31.78 (which were regarded as their respective equivalent masses). This verifies the
second law. The discharge reactions are

+ e = H2; Ag + e = Ag; f Cu2 + e = 2 Cu

 384 Principles of Physical Chemistry

14.6 Faraday and Significance of the Faraday's Laws

Using the first law it was found that the quantity of electricity required to deposit
one mole of silver, was 96,500 Coulombs. Now one ion of silver is deposited at the
cathode as an atom of silver as follows:
Ag+ e
That is to say that one electron deposits one atom of silver. To deposit one mole of silver
one mole of electrons will be required. Hence one mole of electrons carries 96,500
Coulombs of electricity. In honour of Michael Faraday 96,500 Coulombs of electricity
was named as one Faraday of electricity. So we write
I F = 96,500 Coulombs 96,500 C (C stands for Coulomb)
and we say that to deposit one mole of silver IF of electricity are required.
Now according to the First Law of Faraday IF will deposit one mole of silver, 2 F
will deposit 2 moles of Ag and 3 F will deposit 3 moles of silver.
Since one mole of electrons carry 96,500 Coulombs of electricity the charge carried
96,500
by one electron = C = 1.60 x 10 C
6.02x 1023
Copper and aluminum are deposited as follows:
Cu' + 2e = Cu
3+
Al +3e Al
It follows that to deposit one mole of copper two moles of electrons are required, i.e. 2 F
of electricity are required and to deposit one mole of aluminium 3 F are required. When
96,500 C or 1 F of electricity is passed through separate electrolytic cells containing Ag,
Cu2 and Al3 ions respectively the amount of metal deposited at the cathodes in the
different cells were found tt be Ag, 1 mol; Cu, mol; Al, mol, i.e. in each case the

amount of metal deposited = mol

number of charges on the ion . As mentioned earlier these
amounts are what Faraday referred to as the equivalent masses of the metals in the second
law.
We will see later that to discharge one mole of oxygen at the anode the reaction is
40H 21-120 + 02 + 4e
and 4F of electricity will be required.
The Second Law of Faraday may now be stated as follows:
The number of Faradays required to liberate one mole of a metal or discharge one
mole of a gas is equal to the number of electrons showed in a balanced equation for the
electrode reaction, CY
 Electrical Conductance and Electrolysis 385
coulometer for 1 hour 10
2.0 ampere current is passed through a Ag
Example 14.1:
of Ag
deposited in the coulometer. (R.A.M. of Ag = 107.88)
minute. Calculate the mass

Solution:
Time = (60 + 10) x 60 seconds = 4200 seconds
Electricity passed = 2.0 x 4200 = 8400 C
82LF=0.087F
96500

Ag is deposited as shown: Ag + e = Ag
i.e. One F deposits one mole of Ag
Hence moles of Ag deposited 0.087
107.88 g -
Mass of Ag deposited = 0.087 x
=9.39g
200 cm3 of oxygen (measured at
Example 14.2: Calculate the time required to discharge 4 A.
r,t.p.) by electrolysing dilute sulphuric acid solution with a current of
4 OH - = 2H 2 0 + 02 + 4e
Solution: Oxygen is discharged as shown: of electricity will be required.
It shows that for the discharge of one mole oxygen 4 F

Now 200 cm3 = ------- mol = 0.008333 mol

24000
4 F = 0.03333 F = 3217 C
Quantity of electricity required = 0.008333 x

Hence the time required = 3217= 804 seconds

14.7 The Conductance of Electrolytic Solutions

The power of conducting electricity by any conductor is described in terms of its
conductivity or conductance. Conductance is reciprocal of resistance. If the electrical
resistance of a conductor is measured the conductance may be calculated as

Conductance = Resistance

Resistance of an electrical conductor may be measured by using Ohm's law written as:
E (14.4)
R= -
1
I is the current in ampere and
E is the
where R is the resistance measured in ohms(),
potential difference (volts) between the two ends. This law can be applied in case of
solutions except at very high voltages or with very high frequency alternating current.
 386 Principles of Physical Chemistry

In
order to be able to compare the resistances of different substances the term specific
resistance has been introduced. The resistance, R,
of a conductor is directly proportional
to its length, 1, and inversely proportional to its area of cross-section,
a; i.e.,
Roc!

Or R =XL
(14.5)
where P(rho) is a constant for the conducting material and is called its specific
resistance or resistivity. When 1 = 1 cm and a = 1 sq cm, R
= p. The specific resistance
is then defined as follows:

The specific resistance of a substance is the resistance in ohms between the

opposite faces of a cube of the material having an edge one centimeter long.
The unit of specific resistance can be found from equation (14.5)
Rxa ohmxcm2
p= = - = ohm - cm (Q - cm)
/ cm

The reciprocal of resistance is called conductance, /1 (lambda).

A ohni (c-') (14.6)

The reciprocal of specific resistance is known as the specific conductance, K (kappa). By

definition

specific conductance (K)= -- =- .- x-- (14.7)

p R
The unit of specific conductance can be derived as follows:

specific conductance (K)= --- =_.! = - . X-- ' = ) Jflcin (14.7a)

p R a ohm ctn
The specific conductance of a solution is dependent on its concentration. In order to
compare the conductance of different electrolytic solutions, molar conductance (A,,1) is
used. The molar conductance is defined as,
"The conductance of all the ions produced when 1 mole of an electrolyte is
dissociated into its ions in a volume V mL."
This is obtained by multiplying specific conductance (K)
by the volume V in niL that
contains I mole of the electrolyte. In other words,

A,= K V (14.8)
where V is the volume of the solution in niL
containing 1 mole of the electrolyte.
 Electrical Conductance and Electrolysis 387

The unit of Jim may be derived as follows:

'1m KX V
1! (14.9)
=—x---x V
R
1 cm cm3
=
ohm cm 2 mol
-1
The unit of urn is then ohm C177217101

Example 14.3: A metal rod of length 3.2 cm and area of cross-section 0.45 sq. cm offers
a resistance of 1.8 ohms. Calculate its specific conductance.
1 3.2
Solution: Using equation (14.6) specific conductance K =-
1.8 0.45
= 8.0 ohm cm

Example 14.4: An electrolyte solution of concentration 0.1 mol U' has a specific
1
conductance of 0.01289 ohm cm . Calculate its molar conductance.
Solution: The volume in inL (V) containing one mol of the electrolyte
1000 10000 m
0.1
Cm niol '
The molar conductance = 0.0 1289 x 10000 = 128.9 ohm
14.8 Experimental Determination of Conductance
The basic principle of the experimental determination of electrolytic conductance is
that of the Wheat.stone's bridge, A simplified circuit diagram of a conductance bridge is
shown in Figure 14.3. This conductance bridge was originally devised by Kohlrausch,
and is known as Kohlrausch's conductance bridge. For measuring conductance of
solutions direct current cannot be used because electrolysis will take place and
polarisation of the electrodes occurs; further complication will be caused by evolution of
gases in many cases. Also secondary reactions at the electrodes will spoil the
experiments. This difficulty has been eliminated by use of high frequency alternating
current from a small induction coil called a 'buzzer' or better from an oscillator. The a-c
source generates usually 1-3 kilo cycles/sec. Due to rapid change of polarity at the
electrodes polarisation is reduced considerably and electrolysis is stopped. The
galvanometer in the Wheatstones bridge circuit is generally replaced by a small sensitive
telephone.
388 Principles of Physical Chemistry

a-c current is generated from the

'buzzer' by a storage battery. Two
wires connect the a-c source to the
two ends of the meter bridge at M
M. In the gap R is placed a variable
decade resistance. M, M and M' are
M M
thick metal plates. The solution is
placed in a special conductance cell,
C, which is connected to the other
gap in the bridge between M and
M'. The detector, in this case the
telephone, is connected to M' and a
sliding jockey, S, that connects to
the bridge wire AB, A scale,
usually one metre long and Figure 14.3 Schematic diagram of Wheatstone bridge
graduated in millimeters, runs along the wire. The jockey, S, can be moved along the
wire so that each position of the jockey, represents a. definite resistance in the wire.
When the circuit is completed a buzzing sound is heard in the telephone. A suitable
resistance (R) is placed in the gap, R. The sliding contact is then moved along the wire
until there is no sound in the phone or the sound is minimum. This is the null point. The
resistance is usually so chosen that the null point is at about the middle of the scale. If the
length of the wire, AB, is 100 cm and null point is at a distance 1 cm from the end A, then
the principle of the Wheatstone's bridge gives

R. /
Cell resistance (14.10)
(100-1)

or Cell resistance = R 100-1

-
or Cell conductance = (14.11)
R(l00—l)

Since 1 and R are known the conductance of the solution in the cell is at once calculated.
This simple bridge can give only moderately good values of conductance; It is very
difficult and sometimes impossible to get a sharp minimum in the bridge. Use of a small
variable parallel plate condenser, like one used in a radio for tuning, connected parallel to
the conductivity cell improves the minimum, but even then there are other sources of
error.
Many good and sophisticated bridges are commercially available. The principle of
all these bridges is the same as above but the a-c current is generated by an electronic
oscillator. For better sensitivity the current is amplified before being fed to the detector.
 389
Electrical Conductance and Electrolysis

The detector generally is a cathode-ray tube (magic eye as in a radio) or in more

expensive and sensitive instruments it is a cathode ray oscilloscope. Precise and reliable
conductance values can be obtained from such improved instruments only.

14.9 Conductance Cell: Cell Constant

A conductance cell is a devise to measure the conductance of electrolytic
solutions. Different forms of cells are in use for conductance measurement. A cell which
which
is commonly used is shown in Figure 14.4. The container is a glass vessel, A,
carries two thick platinised platinum (fine particles of platinum, black in colour,
securely fixed so that their
deposited on the platinum foil electrolytically) foils, PP,
sealed to the platinum foils and
distances are not altered. Two metallic wires, BB,
protected by glass tubes serve as the leads for connecting to the measuring bridge.
Several other forms of cells are shown in Figure 14.5.

Ii
A

P
iI']
r;gure 14.4 A conductance cell Figure 145 Different types of conductance cells

It is known from equation (14.5) that the resistance of a conductor is given by

R =px-1-
is the distance between the two electrodes and a is the
In the case of conductance cell 1
area of cross-section of the electrodes, as the resistance of the column of solution
cell constant,
between the two electrodes is measured. For a particular cell i/a, known as
is a constant. As the dimension of the electrodes and the distance between them can
hardly be measured accurately the usual practice is to determine the cell constant by
measuring the conductance of a solution whose specific conductance is accurately known
are used for the purpose. The
at a particular temperature. Standard solutions of KC1
specific conductance of any solution may then be obtained from the equation (14.7).
(14.12)
Specific conductance Observed conductance x cell constant
 390 Principles of Physical Chemistry
The specific conductance of KC1 at different concentrations are given in Table 14,2
Table 14.2 Specific conductance of KC1 solutions at different
concentrations at 25°C
Concentration (mol U') Specific conductance(o/wz' cnr')
1.0 0.11173
0.1 0.0 12886
0.01 0.001411
Example 14.5:
A conductivity cell has a resistance of 170 ohms when filled with 0.01
mol U' solution of KCI at 25°C.
The specific conductance of this solution is 0.001411
ohm' cnr'. The same cell when filled with NaCI
solution of concentration 0.01 mol U'
has a resistance of 235 ohm. Calculate the specific conductance and molar conductance of
the NaC1 solution.
Solution: From equation (14.12) cell constant =- p'k' conductance
observed conductance
1
0.001411x (1/170)
--=0.001411x170

= 0.24 cm-1
Specific conductance of NaC1 solution = cell constant x observed conductance

= 0.24 x
235
0.001021 olz,iz' c1111
Volume (V) of solution containing one mol of NaCI
= 1000 = 100000 ,nL
0.01
From equation (14.8) molar conductance = specific conductance x V
EE 0.001021 x 100000
102.1 ohm-] cm inot1
14.10 Conductivity Water
For conductance measurements it is necessary to use very pure water because the
impurities, if present, might contribute to the total conductance, thereby giving incorrect
results. Water for conductance measurements known as conductivity water, can be
obtained by three distillations of ordinary water with addition of small amounts of
potassium permanganate in an all glass (pyrex) distillation set. Purer water can be
obtained by using tin-plated copper condensers. Alternatively, the water may be passed
through mixed bed ion-exchange resins when dc-ionized water can be obtained. For most
purposes the water should not have a specific conductance more than 2 x 10 --6 ohm- ' c,i'
at 25°C.
 Electrical Conductance and Electrolysis 391

14.11 Conductance and Electrolyte Concentration

It has been mentioned that the specific conductance of solutions depends on the
concentration of the electrolyte. A look at Table 14.1 will reveal it clearly. As the current
is carried by ions the specific conductance will depend on the actual number of ions per
unit volume of the solution. Hence the specific conductance progressively decreases with
increasing dilution (i.e. decreasing concentration). However, the molar conductance, A,,,
increases with dilution and tends to attain a limiting constant value for strong
electrolytes; but for weak electrolytes, like ethanoic acid, NH40H etc., the molar
conductance rises rapidly at low concentrations. The behaviour of both strong and weak
electrolytes are shown in Figure 14.6
The plots for A 1 vs Jrnoiarity for strong
electrolytes like KC1, Na 2SO4, CH3COONa
15
follow almost a linear relation at low
concentration and the straight lines can be
extrapolated to zero concentration to give' NaSO4

A,,, the molar conductance at infinite

Na Acetate

dilution*: But the curve for ethanoic acid

shows a rapid upward trend for -IFC values Acetic Acid

approximately below 0.05. Extrapolation of 0________________________

such a curve to zero concentration is 0 0.05 0.10 0.15 0.20

neither feasible nor at all reliable. " Molarity

Figure 14.6 Molar conductance vs square root
of concentration

Table 14.3 Molar conductance (ohm' cm2 mor') of different

electrolytes in aqueous solutions at 25°C

C
mol C' NaC1 KC1 HCI AgNO3 HAc

0.0000 126.45 149.86 426.16 133.4 (390.7)

0.0005 124.50 147.81 422.74 131.4 67.7
0.001 123.74 146.95 421.36 130.5 49.2
0.01 118.51 141.27 412.00 124.8 16.3
0.10 106.74 128.96 1.391.32 109.1 5.2

* At very tow concentrations the line shows an upward trend even in case of strong electrolytes like KCI,
NaCl etc.
392 Principles of Physical Chemistry

The measurement of Am at very low concentrations serves as an excellent method for

distinguishing between strong and weak electrolytes. Some data on molar conductance
are given in Tables 14.3 and 14.4.
Table 14.4 Molar conductance (ohm' cm 2 inor')
at infinite dilution at 18°C

Electrolyte A° Electrolyte A°
LiC1 98.9 CH3COOAg 88.0
KCI 129.9 KNO3 126.3
NaCl 108.9 KCI03 119.4
HC1 381.0 AgCI03 109.0
HNO3 377.5 KOH 238,0
NaOH 216.5 LiNO3 95.2
NaNO3 105.3 CH3 COONa 77.0
L1C1 98.8

It is to be noted that values of A, are different at different temperatures.

14.12 The Conductance Ratio

The conductance of one mole of a particular electrolyte in solution will depend on
(a) the number of ions and (b) the speeds of the ions. The difference in the
molarconductance of different electrolytes may be attributed to difference in speeds (see
Section 14.13). The variation of molar conductance of a given electrolyte with
concentration was explained by Arrhenius (Section 14.6) by assuming that the extent of
dissociation of the electrolyte increases with increasing dilution. At infinite dilution the
dissociation would be complete and the value of A would not change with further
dilution, i.e., the molar conductance would reach its limiting value, A°. Since the molar
conductance at any concentration, A, is proportional to the number of ions, the extent of
dissociation at the concentration, c, would be given by
A (14.13)
A°

Arrhenius named this quantity the degree of dissociation. As will be seen in Section
14. 11, all strong electrolytes are now supposed to be completely dissociated into ions in
solution, and the term has little significance except in the case of weak electrolytes which
are regarded as incompletely dissociated. The ratio is now given the non-committal
AO

term, conductance ratio.

 Electrical Conductance and Electrolysis 393

14.13 Debye-Mickel- Onsager Theory

Based on his analysis of the data available and his own experimental results the
following empirical equation relating molar conductance (he was using equivalent
conductance) with concentration was put forward by Kohlrausch
AA0 A[ (14.14)

where A is a constant. The constant A is characteristic of the electrolyte. The first

satisfactory theoretical interpretation of the equation, however, was given in 1920 by
Debye, Huckel and Onsager, and the constant A in Kohlrausch's equation became
meaningful.
Development of the study of crystals by X-rays and the electronic theory of valency
led to the view that when a salt, strong acid or strong base is dissolved in water these are
completely ionized. In the Debye-Huckel-Oflsager theory this is accepted as a fact and
the increase of molar conductance with dilution is explained in terms of decreasing inter-
ionic attraction at low concentration.
Debye-Huckel-Oflsager theory is based on the following assumptions:
• Strong electrolytes are completely dissociated into ions
• Due to Coulombic forces between the charges of the ions, they do not behave
like molecules in their transport and thermodynamic properties
• Since the solution as a whole is neutral, the total number of positive charges
must be equal to the total number of negative charges.
• A given ion will have more ions of the opposite sign close to it than ions of
the same sign. This cluster of ions is called the ionic atmosphere.
1'on atmosphere

Ion moving

Retardation
At rest in motion

Figure14.7 Ion atmosphere Figure 14.8 Asymmetry effect

When an electrical potential is applied to an electrolytic solution, two effects

produced by the ionic atmosphere prevent the ions to move at the expected speed and
hence conducting the amount of current. These effects are:
(i) Relaxation effect (sometimes known as asymmetry effect):
In an electrolytic solution, each ion is surrounded by an atmosphere of counter-
ions, e.g., ions having opposite charge (ionic atmosphere). in other words, cations are
 394 Principles of Physical Chemistry

surrounded by an atmosphere of anions and vice versa. In the absence of an external field
the ion, along with its surrounding ionic atmosphere, remains fairly steady and the ionic
atmosphere remain symmetrial around the central ion. When such a system is subjected
to an external electric field, the central ion and its ionic atmosphere moves toward the
oppositely charged electrode. As the central ion starts moving out of the ionic
atmosphere a new ionic atmosphere of opposite charge starts building around it. The old
ionic atmosphere will eventually die out. The destruction of an ionic atmosphere and the
completion of the formation of a new ionic atmosphere do not take place all at once.
There is a time lag between these two processes. This time lag is termed as relaxation
time. During this relaxation time the old ionic atmosphere pulls the moving ion backward
and thus retards its motion.
The relaxation effect, also called the asymmetry effect, may be looked upon from a
different perspective. Once the external field is applied, the central ion starts moving
toward the electrode of opposite charge and more of the ionic atmosphere is left behind
than is present on the front side. These excess ions of the ionic atmosphere which are left
behind will tend to retard the speed of the moving ion due to electrostatic force. Thus the
effect arises because of the asymmetry of the ionic atmosphere, and hence the effect is
called asymmetry effect. An approximate representation of the above statements is given
in Figure 14.8.
The arrow at the top of the 'ion atmosphere' represents the velocity with which the
cation would have moved to the cathode if no retarding force was in operation. The small
arrow below the ion atmosphere shows the retarding force. Since in a solution of one
mole of the electrolyte the number of ions is constant this retardation of the velocity of
the ions brings about an overall decrease in molar conductance from its ideal value that
the solution would have in absence of any other force.

(ii) Elect roplioretic effect:

The electrophoretic effect is caused by the tendency of the applied electric field to
move the ionic atmosphere along with the associated solvent molecules in a direction
opposite to the direction in which the central ion (which may also be accompaiti'd by a
few solvent molecules) is moving. It may well be imagined that the central ion is moving
against the flow of the ionic atmosphere with reduced speed. This effect is called
elect ropho relic effect.
Finally, the migration of the ions is opposed by usual frictional resistance of the
medium which is again dependent on the dielectric constant of the medium, the radius of
the ionic atmosphere and the viscosity of the medium.
At infinite dilution, the asymmetry and electrophoretic effects are practically zero,
and the speed of the ions, and hence the molar conductivity is determined by frictional
force of the medium only.
On the basis of these arguments Debye and Mickel were able to derive an expression
to explain the variation of conductance with concentration of the electrolyte. This can be
written in the modern form as below:
AC =A°l —(A+BA).J
,n (14.15)
 Electrical Conductance and Electrolysis 395

= molar conductance of the electrolyte solution of concentration C mol U'

A',,,
= molar conductance of the electrolyte solution at infinite dilution
A and B constant terms for a particular solvent at a given temperature
On increasing the dilution the average distance between ions increases and, therefore,
the retarding force decreases, and there is an increase in A, with increase in dilution. The
above explanation, which is only a fragmentary reflection of a more detailed picture,
leads to a relation between molar conductance and concentration of the same form as
Kohlrausch's equation. Debye, Huckel and Onsager were able to calculate the constant A
and B for many electrolytes in dilute solution. The calculated values were found to be in
agreement with the values found from the slopes of the experimental data plotted as A,
Vs

The theory which explains many other facts, however, fails when applied to solutions
of moderate or higher concentration, i.e., 0.1 to 1 nzol U' and above. Although no
satisfactory theoretical treatment for such solutions is still available, mention may be
made of the concept of the formation of ion- pairs or ion triplets, primarily by Fuoss,
Bjerrum and others. Because of the proximity of the ions at high concentrations there
may be specific attraction between the oppositely charged ions, so that two oppositely
charged ions in an ion -pair will virtually behave like an undissociated molecule so far as
conductance is concerned. The ion-pairs cannot be regarded as molecules as these can
exchange partners. The concept of ion-pair is of importance particularly in solutions of
low dielectric constant.

14.14 Independent Migration of Ions: Kohlrausch's Law

Kohlrausch examined the values of A 0 of a number of strong electrolytes with
common anions or cations and found some regularity in the A, values of various
electrolytes. He observed that when the electrolytes were considered in pairs having one
common ior the difference between the A, values were constant (Table 14.5).

Table 14.5 Differences in values of A, for several pairs of electrolytes

with a common ion

Electrolyte A0 at 298 K Difference Electrolyte A0 298 K Difference

c,n 2nioi 1 Q' c,nmc'
KBr 151.92 23.41 KBr 151.92 2.06
NaBr 128.51 KCI 149.86
KC1 149.86 23.41 NaBr 128.51 2.06
NaCl 126.45 NaCl 126.45
KNO.3 144.96 23.41 LiBr 117.09 2.06
NaNO 3 121.55 LiCI 115.03
 396 Principles of Physical Chemistry

These observations led Kohlrausch (1875) to state that the molar conductance at
infinite dilution is different for different electrolytes and is equal to the sum of the
conductanc of the constituent ions of the electrolytes. This is known as the Kohl rausch 's
law of independent ionic migration. The law may be expressed in the form
A,,=2+A (14.16)
where 2 and A° are called the ion conductance of the cation and anion respectively. The
above equation means that each ion of an electrolyte contributes independently to the
value of A at infinite dilution. For example, the molar conductance of KC1 at infinite
dilution is 149.86 ' cm2 ,nol. The ion conductances of K and Cl are 73.50 and
76.30 Q cm2 moU'. According to Kohl rausch 's law of independent ionic migration,
A° _O O
,u(KCI) 'UK' + ' cr

= 73.50 + 76.30 Q' cm2 nIol'

= 149.80 Q' cm n1ol1
This is in agreement with the value measured directly. The Kohlrausch's law of
independent ionic migration is useful for calculation of A° for weak electrolytes for
which A,, cannot be ascertained from the plot of Am vs as shown in Figure 14.6.

Table 14.6 Ion conductance at 25°C

Cation (QC111 inol') Anion 20_( 2' c,n2nol')

if 350.0 01-1 - 198.0

Li 38.7 Cl - 76.3
Na 50.1 Br 78.4
K 73.5 I 76.8
Rb 77.8 NO3 71.4
Cs 77.3 C104 68.0
NH4 73.4 SO42 160.0
Ag 61.9 CO32 140.0
127.2 C204" 48.0
Fe3 204.0 I CH-?COO - 40.9

The computation is done by addition and subtraction of A 0 values for different

strong electrolytes.
Example 14.6: The molar conductances at 25°C of HO, NaCl and CH3 COONa are
426.1, 126.4 and 91.00 ' cm2 ,noF' respectively at infinite dilution. Calculate the molar
conductance of CH3COOH at infinite dilution.
 Electrical Conductance and Electrolysis 397

Solution: From Kohlrausch's law

AO
110— A, +2 = 426.1 2cm2 n:oF' (i)

A°NaCI =20Na + 2° = 126.4 Q' cm2 mol' (ii)

and A°CH 3 COONa =2°CHCOO +20
Na
= 91.00 92 cnz2rnoi' (iii)

Adding equations (ii) and (iii) and subtracting equation (i) from the sum we obtain
2°+2,
CH3COO•
=390.70 92 - 'cm 2 n101'
Or, =390.70 Q cm2mol'

Example 14.7: Calculate the molar conductance at infinite dilution of NH4 0H, given
that the molar conductance of NH40, NaCI and NaOH at infinite dilution at 25°C are
149.7, 126.4 and 248.1 -1 cm •' nzol -I respectively.
Solution: We can write.
A°NH Oil = 2°,H ,. + A' -
01f = 2°,H.
+ A' + 2 a + 2°0H - - 2 Na' - a
= A 11 , +A° —A°NaCI
NaOH

= 149.7 + 248.1 - 126.4 = 271.4 Q' cininol1

14.15 Absolute Velocity of Ions: Ionic Mobility

The difference in the ion conductances may be traced to the difference in the speeds
with which the ions move under a given potential gradient. A direct measurement of the
speeds with which ions move, i.e., their absolute velocities were first made by Oliver
Lodge. A simple apparatus of the type as shown in Figure 14.9 was used. In the tube was
placed a gel into which was incorporated some indicating material. For example, in
measuring the speed of hydrogen ion the anode and the cathode vessels are filled with
dilute sulphuric acid and sodium
sulphate. The tube is filled with a gel of + E* -
agar-agar to which phenolphthalein and
a trace amount of alkali was
incorporated so as to give a pink colour
to the gel. On passing electric current
through the electrodes the hydrogen ion - --
moves towards the cathode. The rate of
movement is followed by noting the
rate of disappearance of the colour in Figure 14.9 Apparatus used by Lodge to measure
the gel due to neutralization of alkali by the absolute velocity of ions
the hydrogen ions.
The success of the method depends on producing sharp boundaries and observing the
movements of the boundaries accurately. However, the speeds will depend on the
potential gradient across the electrodes. In order to compare the speeds of different ions a
term ionic mobility has been introduced. The ionic mobility is defined as
398 Principles of Physical Chemistry

"The velocity of an ion in cin per second when it moves under unit potential gradient",
i.e., when the potential between two electrodes placed 1 cm apart is I volt.
The ionic mobility, u, is related to ion conductance A by the expressions
k OC 1 a or2a =ku a (14.17)
and A oc u c or, =ku (14.18)
In equations (14.17) and (14.18), 2a and Ac are the ion conductance of anion and cation
respectively and k is a constant of proportionality. The value of the constant k has been
shown to be equal to one Faraday.
If we consider the ion conductance at infinite dilutions it can be shown that
+ A = k(u +u) (14.19)
These relations enable one to calculate the ionic mobility from the values of ion
conductance.

Example 14.8: The ion conductance of IF and Cl- ions, in ohm-1 cm inor', are
respectively 350 and 76.3. Calculate their ionic mobility. (1F= 96500C)
350 =
Solution: Ionic mobility of H =
96500
36.27 x i- 4 cm2 sec' V1
76.3 -
Ionic mobility of Cl- = 7,91 xi0" cm2 sec-!V
96500 -
Some values of ionic mobility are given in Table 14,7.

Table 14.7 Ionic mobility of some ions at 25°C (cm2 sec-1 V')
Ion ux 10 Ion ULI X IC
36.30 OH- 20.50
.4-
Li 4.01 C1- 7.91
Na+ 5.19 I- 7.95
K4' 7.61 7.40
NO3
Ca2 6.16 SO41- 8.27
7.21

The high values of ionic mobility for IF and OW compared to others should be
noted. The explanation of this fact has been given in terms of the Grotthus's mechanism
of electrolytic conductance. It is supposed that IF or OW approach a group of water
molecules and a series of transfer of the charge between the water molecules in the group
takes place. As a result of this the ion is transported through the solution. This is
illustrated below for H4-.

H 0—H 0—H 0—H H-0 H-0 H-0

I I I
H H
I I I
H H H H

'this explanation is not, however, applicable to other ions.

 Electrical Conductance and Electrolysis 399
Another interesting fact is that the heavier members of the alkali metal group have
higher mobility. This is explained by the higher degree of hydration of the lighter ions
which makes its effective size large.

14.16 Applications of Conductance Measurements

• Conductance of electrolytes depends on the number of ions and their speeds. The
measurements of conductance of electrolytic solutions have been utilized for determining
(a) the end points of acid-base titrations,
(b) the end points of precipitation titrations,
(c) the solubility of sparingly soluble salts and
(d) the kinetics of reactions.
For conductometric titration experiments a known volume of the solution to be
titrated is placed in a beaker and a conductivity cell dipped into it. The conductivity cell
is now connected to one end of the Wheatstone's bridge. The other solution is then added
to the solution in the beaker in instalments and the conductance measured after each
addition. This is continued beyond a sharp change in conductance value. The
conductance values are then plotted against the volumes of titre added. In each case the
straight line portions of the graph are extrapolated and the point at which the straight
lines intersect is taken as the end point of the titration.
(a) C'onductornetric titrations involving acids and bases
(1) Titration of strong acid and strong base:
Let us consider the titration of a solution of HCI by NaOH solution. The net reaction
in this neutralization reaction is the production of water from H and Off. The
neutralization reaction can be written as
H(aq)-1-Cl(aq)+ Na(aq)+Oi-f (aq) — p H 2 0(1)+ Na(aq)+ C1(aq)
If we cancel tht, common terms from both sides the net ionic reaction becomes
H(aq) + OW(aq) - H2O(1)
In presence of the acid or base all the water will remain practically undissociated.
However, H ion of the acid is gradually replaced by Na as NaOH is added to the acid
solution. Since the ionic conductance of H is much higher than that of Na there will be
a decrease of the conductance as the addition of NaOH continues. This will go on until all
the acid is neutralized. If more NaOH is added after the neutralization point, the
conductance of the solution in the titration vessel will again increase as the iOflC mo9ility
of 0H is very large (Table 14.7). If the conductance values are graphiail ., 1.otLed
against the corresponding volumes of NaOH added, a coiLductontric titration cur-,e is
-. .i obtained (Figure 14.10(a)). The point of intersection of the two straight lines gives the
> endpoint of titration. Thus acid-base titration can oc canicU out uonuuctometrically,
M Principles of Physical Chemistry

0 IN-
0
0
C)

C-)

0 point
U Neutralization point U

L
Volume of alkali added (mL) Volume of alkali added (mL)
(a) stro y acid i's strong base (b) weak acid vs strong base
Figure 14.10 Conductometric titration curves

(ii) Titration of weak acid and strong base.

Let us consider that ethanoic acid is titrated against NaOH. The initial conductance
Of the acid solution is very low because of low ionization of the weak acid. However, as
NaOH is gradually added to the acid solution a salt, CHCOONa, will be formad which
ionizes readil y to form Na and CH3 CQO ions. The ethanoate ions at first tend to
suppress iurther ionization of the acid due to CO!fllflOfl ion effrct. But after a while the
conductance of the system increases because the conducting power of the completely
ionized salt exceeds that of the weak acid. This continues to increase up to the end point,
V [Figure 14.10(b)]. Beyond this point as more NaOH is added the conductance rapidly
increases due to highly conducting 0H. Consequently, the linear portion of the
conductance curve in the alkaline re g ion is steeper. The end point is the point of
nc ::iion of the two lines - one ill the acidic region and the other in the alkaline region.
Tjt-(:j;: of weak acid and weak base:
For weak acid and weak base the conductance initially rises due to the formation of
salt, say ammonium ethanoate from NH4 OH and CH3 COOH. On further addition of
NH4OH the conductance continually rises
till the neutral point is reached. After this
the conductar.ce remains almost constant
because NH4 0H is a very weak base and
contributes only very slightly to
conductance. The titration curve for a
weak acid - weak base is shown in
I - #T Neutralization point
Figure 14.11. The point of intersection of
the inear portions gives the neutral vv
Volume of alkali adeed (ML) co
pointtA"Umost all acid-base titrations can
be performed conductometrically. Figure 14.11 Titration of weak acid weak base c',J
 Electrical Conductance and Electrolysis 401

Conductometric titrations have the following advantages over volumetric titration:

(i) No indicators are required and, therefore, coloured solution can be
conveniently titrated.
(ii) For weak acid and weak base no suitable indicators are available but
conductometric titrations can be conveniently carried out.
(iii) More accurate results are obtained by conductometric titrations because
the end-point is determined graphically from a number of measurements
and not from a single measurement as in volumetric titration.
(iv) Conductornetric titrations can be accurately carried out for very dilute
solutions, where indicator colour change is not sharp.
(v) Volumetric titration does not give correct end point for polybasic acids,
while conductometric titration can be conveniently used in such cases.
However, it must be kept in mind that in order to minimize the volume change as
little as possible the titre should be about 10 times stronger than the solution to be
titrated. Also, the temperature of the solution should be kept constant during titration.
(c) Conductance titration in precipitation reactions:
In a precipitation reaction there is a net decrease in the number of ions in the
solution due to removal of the ions from both the reacting substances. For example, when
a solution of MgSO4 is added to a solution of Ba(OH)2 the Ba2 ions and SO42 are
removed as BaSO4 and Mg2 ions and OI-f are removed as Mg(011)2 according to the
equation:
Ba 2 aq) + 20H(aq) + Mg 2 (aq) + SO/ (aq) = BaSO 4(s) + Mg(OH)2(s)
Therefore, upon addition of a solution of
MgSO4 to Ba(OH) 2 solution there is a sharp
fall in the conductance and this continues
until the equivalence point is reached as equivaiance
shown in figure 14.12. \ point
However, after the equivalence point
is exceeded, the conductance rises due to the
contribution of Mg 2 and SO42 ions from
L11 AA AR,f.-.Cfl
.1UUU
1,,t,s,, T11..
JVJJL.J4 3 UIULIU1I. i 11k... 1LL.."."'-".
rn
Vol MgSO4 added
be used for quantitative estimation of either
Figure 14.12 Precipitation titration by
Ba2 , Mg 2 or SO42 . In several other
conductance measurements
precipitation reactions the same method can
be used and no indicators are needed. Conductance titrations can be used for quantitative
estimations of cations and anions in a variety of reactions. The principle, in all cases, is
the change in the conductance of the reaction system due to addition or removal of some
ions
 402 Principles of Physical Chemistry

(d) Dcterinination of solubility of sparingly soluble salts:

Conductance measurement can be used for measurements of solubility of slightly
soluble substances like BaSO4 PbSO4, AgCI etc. The method is based on the difference in
the conductance of the ions of the salts. For the purpose a saturated solution of the salt is
prepared in conductivity water and allowed to stand until almost all the insoluble fraction
settles down. The clear solution from the top is taken and its conductance is measured in
a conductance cell whose cell constant has been determined earlier. The cell is
thoroughly washed and filled with the same conductivity water and the conductance of
the water measured in the same cell. The observed conductance is then converted to
specific conductance. The condueancc of water is then subtracted from the conductance
of the solution. The value s> obtained is the conductance .due to the salt. The molar
condtance ('L) of a saturated solution is given by equation (14.8)
KX 1000

C.

' 11r i is the specific conductance and c is the concentration of the solution in niol U1.
Since the ,'alt is sparingly soluble, the solution is very dilute and Am may be considered to
be equal to. 410t; the molar conductance at infinite dilution. The value of A for AgCI
can he founc.t by applying Kohltausch's law of independent ionic migration. According to
this law, A ( c, ) = /1 , + 2 r . Substituting A, in above equation c can be calculated
provided K is known. This will gi';e the value of c in mol U' from which the solubility in
g U' may be calenlated.
Exanple 14.9: The specific c onductance of a saturated solution of BaSO 4 at 25°C is
3.590 x 10 olniz ' c'n and that of the conductivity water used is 0.618 x 10 olznz'
crn 1 . The limiting ion ,:onduc i. ance at infinite dilution for Ba 2 and SO4 2 ions are 127.2
and 160 ( o/iin cm 2 inol' respectively. Calculate the solubility of BaSO4 at this
r nexature (RFM of BaSO4 233).

Solution: The specific conductance of the solute,

K =3.590x10 6 -0.618x10=2.972x 10
1000K 1000K
Solubility in niol L c= =

1000x2.972x10
= ----=1.03x10
287.2
Solubilit..Y in g U' = 1.035 x 10 x (233) =2.41 x 10
14.17 Transport Number (or Transference Number)
In an electrolytic solution the current is carried by both cations and anions. In a
solution of an electrolyte where the number of ions is fixed or does not vary much, the
conductance would be mainly governed by ionic velocities. If u., represents the ionic
 Electrical Conductance and Electrolysis 403
velocity of the cation and u- that of the anion then the current carried by the cation will
be proportional to u, and the current carried by anion will be proportional to u. The total
current carried through the solution will be proportional to (u + + u_).
The fraction of the current curried by each ionic species is called the transport number
of that ion
The transport numbers of anions and cations are given by
- A.u_ — __ U_ (14.20)
= A,u + A.0 = u+ + u-
A. u+
and (14.21)
A._ + A.u, = u_ + u+
where t+ and t_ are the transport number of cation and anion respectively and A is the
proportionality constant. It is evident that t+ + t_ = 1 since
11+ U-
+ =1
u_+u+ u++u_
So
and t_=l—t+
Due to the unequal velocities
of the cation and ther anion there + Anode a Middle b Cathode -
will be a change in the ••••• ••••••••••
concentration of the ion around the 1
00000!0000000000 00000
cathode and the anode. To explain
this let us consider an arrangement 2 •0S{..1..... i,
O0& 000000000 0000000
of electrolysis as shown in Figure
14.13. The whole cell is divided •••• • • • 1 6 6 6 909099 :.s.
into three imaginary compartments 3 000 000000000 000 0000
by the dotted lines aa and bb, the s........ • • S S • S • S S :.
left is the anode compartment, the 000j000000000;00000
right oie is the cathode
compartment and between aa and a 11
bb is the middle compartment.
Figure 14.13 Mechanism of ionic transport
Let us assume that before electrolysis starts there are five anions (solid circles)
and five cations (hollow circles) in each of the cathode and anode compartments and ten
cations and ten anions in the middle compartment. The following cases may now be
considered:
(I) There is no electrolysis
The number of anions and cations are the same in each compartment. This corresponds to
the situation in line 1 in the diagram.
404 Principles of Physical Chemistry

(II) The anions and cations move with the same speed
On electrolysing for a certain time, equal number of the two ions would have
migrated in opposite directions and the system would resemble the line 2 where two ions
of each kind have migrated in opposite direction. The number of anions and cations ions
in the middle compartment will remain the same since it has lost two ions and has gained
two ions. For electrical neutrality four anions from the anode and four cations from the
cathode must be discharged. In line 3 is shown the liberation of the ions on the
electrodes, the cation on the cathode and anion on the anode. Since the ions are lost from
the solution they are shown outside the system. The whole solution has become dilute,
but the composition in the middle compartment remains unchanged.
(III) The anions move at twice the speed of the cations.
Let us assume that the anionic velocity is twice the velocity of the cation, the system
would be represented by the line 4. Two cations move to the cathode chamber while four
anions move to the anode chamber. The anode compartment has now nine anions and
three cations but the cathode compartment has only one anion and seven cations. On
continued electrolysis therefore, the concentrations around cathode and anode would
change but the composition in the middle compartment will remain constant if
electrolysis is not continued too far. The change in concentration in the anode and the
cathode compartment naturally depends on the velocity of the ions leaving their
chambers. Thus
equivalent mass of electrolyte lost at anode compartment - u+
14.22)
equivalent mass lost at cthnde compartment u

and the total loss, therefore. shail e proportional to u -4 u_. Consequently L and L, will
be givn by

_________jUiY,l ;Th2. Lost in cathode chamber (14.20)

. )
total loss in anode and cathode chamber in equivalent mass

U-
since
14+ + U-

and similarly
equivalent mass lost in anode chamber
(14.21)
= total loss in the anode and cathode in equivalent mass

It is needless to say that if u and u. are equal then t+ t_ = 0.50. The above relations
show that if the change of concentration around anode or cathode resulting from
ekctrolysis can be measured the transport number of the ions can be found out.
In many instances the electrode itself takes part in the electrolysis. For example, if
silver nitrate is electrolyscd between si 1 electrodes the electrodes will go into solution.
This will result in an i!lcrease iather than a decrease, in concentrati,n at the anode
 Electrical Conductance and Electrolysis 405

chamber. The amount of silver dissolved will be governed by Faraday's laws of

electrolysis and may be determined by placing a coulometer in the circuit. The loss of
electrolyte due to migration can then be calculated from the initial concentration, final
concentration and the amount of material deposited or dissolved.

14.18 Measurement of Transport Number

Transport number may be measured by different methods, e.g. Hittorrs method,
moving boundary method and from the electromotive force of concentration cells.
(a) Hittorfs method: This
method is based on the measurement of change in the
concentration of the electrolyte in the neighbourhood of the cathode and the anode as a
result of the passage of electricity. The form of the apparatus usually used in the
laboratory for the purpose is shown in Figure 14.14. It consists of three parts which can
B
be separated from one another by means of + -
the stop-cocks SS. The parts can be named
the cathode chamber, the anode chamber S S -
and the middle chamber. The chambers are
provided near the bottom with stop-cock
Sj, S2, S3 , through which liquids can be
drained off. Electrodes are inserted into the -
cathode and anode chambers. The Mcd. -
electrodes are connected to a d-c supply
source B, through a variable resistance R, a - - - -
milliammeter mA and a copper or silver - • -
coulometer (not shown in the Figure). The
latter is for measuring the quantity of - - - -Ag
electricity passed. The method of measure- Ag z-

ment may be illustrated by the IS2

determination of transport number of silver #S1
and nitrate ions. In this case the electrodes
consist of stout silver wires. Figure 14.14 Hittorfs apparatus
The transport number tube is filled with a dilute AgNO3 solution of exactly known
concentr1iOfl (0.1— 0.05 mo! L'). All air bubbles are carefully removed. A small current
(10-20 mA) is passed through the solution for a known period, say two hours. Any
fluctuation in the milliammeter reading is adjusted by the variable rasistance R to
maintain steady value of the current. From the time and the current the total quantity of
electricity in Coulomb passed through the solution is calculated. This is checked with the
coulometer in the circuit. As a result of passing the current electrolysis takes place, Ag is
deposited on the cathode and dissolved in the anode.
However, due to migration of ions, the concentration of the solution in the anode
chamber and in the cathode chamber has changed but that in the middle chamber remains
unchanged (Section 14.17 and Figure 14.14). Immediately after stopping the current the
stop-cocks SS are closed to prevent diffusion. The solutions from the anode and the
cathode chambers are separately taken out by opening stopcocks, S 1 and S2 . These
solutions are separately weighed in two different bottles and analysed for silver content,
 406 Principles of Physical Chemistry
usually by titrating against standard NH4SCN solution with ferric alum as indicator. Since
the initial concentration of the AgNO 3 is known the fall in concentration in cathode and
anode chambers are calculated.
Example 14.10: A dilute solution of C'uSO4 was electrolysed using two Pr electrodes.
The amount of Cu per unit mass of the anodic solution was found to be 0.6350 and
0.6236 g after and before electrolysis respectively. The amount of Ag deposited in silver
coulometer in the series was 0.1351 g. Calculate the ransport numbers of Cu2 and SO42
i ons. (RAM of Cu = 63.5 and Ag = 107.88)
Solution:
The mass of Cu" in anodic solution before electrolysis = 0.6350 g
And, the mass of Cu" in anodic solution after electrolysis = 0.6236 g
So, the loss in the mass of Cu in anodic solution = (0.6350 - 0.6236) = 0.0114 g
The mass of Ag deposited in the voltmeter = 0.1351 g
Now, this amount of Ag must be equivalent to 0,1351x(63.5/2) = 0.0397 g of Cu
107.88
deposited in voltmeter.
Lossof Cu at the anode = 0.0114
Thereiore, the tf2 = 0.287
Total loss of Cu 0.0397
And = 1 - 0.287 = 0.713
(b) Moving boundary method: From the very (lefiflitlon of transport numbers as shown
in ao (14.20) and ( 4.21), it can e sce; that transport number may be directly
caiCute(i f citijc and aflioijC ve l oc i ties +
or ar t,, parameter proportional to the ionic
'e}o( s can ix' determined. The rui
hovniaty method utilizes this principle.
The ttingement is shown in Figure 14.15. p
The scution of an electrolyte MA, which is B

to be studied,s placed between the solu- IMA

tions oI two other salts MA' and MA such
that M'4 has the anion A common with MA
and MA' and MA have the common cation
R
M. The salts are to he co chosen that the
densities increase downwards. Also, the
speed of the ion M' should be less than that 0^1)
of M while the speed of A' should be less -
than that of A ion. Figure 14.15 Moving boundary method
This is essential to maintain sharp boundaries b tween the three solutions of electrolytes.
The initial sharp boundary between the solutions of VA and MA i s shown by the
 Electrical Conductance and Electrolysis 407
is shown by R.
horizontal line P whereas the initial sharp boundary between MA' and MA
In passing current from the source B ionic migration starts and the boundary P moves
The distance travelled by the
downwards, say to P', while the boundary R moves to R'.
two boundaries in time t are PP' and RR', which are directly proportional to the cationic
and anionic velocities respectively. Therefore,
______ PP, (14.23)
1
= + = PP'+RR'
- u- RR' (14.24)
+ U- PP'+RR'

The transport numbers are thus measured. It should be noted that electrolytes MA,
MA' and WA should be carefully chosen to get good results. In practice it is necessary to
form one boundary and observe the rate of its movement to measure the transference
number of one ion; thatof the other ion may then be calculated as t, + t = I -
Under this condition the transference number is calculated as follows: Suppose that
the boundary of the moving cation is swept through a distance I in a tube of cross section
1 x a. If IF
a, so that the volume swept out by the passage of Q coulombs of electricity is
of electricity flows through the solution t+ equivalent mass of cation must pass through
any given point. Let c, be the concentration of the solution in equivalent mass L- I ; then
the volume of solution containing I equivalent mass of electrolyte is 1000/c. Hence during
the passage of I f elcti the io1i boundary will sweep through a volume 1000

t+ . For the passage of Q coulombs, therefore, the same boundary will sweep out a volume
of
1000xt xQ
cxF
10O0xt xQ
Hence lxa—
cxF
lxaxcxF
or,
1000 Q
mol U' HCl
Examle 14.11: A moving boundary experiment was carried out with 0.100
solution with CdC12 as the indicator electrolyte. The boundary moved through a distance
of 6.50 cm in a tube of cross section 0.11 cm 2 . If a constant current of 0.0056 A was
passed for 2100 seconds, calculate the transport numbers of H and Cl- ions.
Solution: Here a = 0.11 cm2, 1 = 6.50 cm, c = 0.100 i nol U'
lxaxcxF = 0.11x6.5x0.1x96500 = 0.5867
tH = Or,
1000Q l000xO.0056x2100
tcr =1-0.5867=0.4133
 408 Principles of Physical Chemistry

14.19 Factors Affecting Transport Numbers

The transport number of ions varies with change of concentration: such changes are
quite complicated and the extent of change is also small. Transport number also depends
on the temperature; t, usually increases slightly with rise of temperature. The anion
transport number, therefore, generally decreases with increase of temperature. In Table
14.8 the transport numbers of some cations are given.

Table 14.8 Cation Transport Number at 20°C

Electrolyte t+ Electrolyte t+
HG! ().823 ZnSO4 0.395
LiCI 0.338 CuSO4 0.397
NaCI 0.395 BaG12 0.449
KG! 0.490 A gNU30.461
KBr 0.488 K2SO4 0.483
KNO 3 0.508 M9SO4 0.395
CsCI 0.501 Ba(NO3)2 0.465
KI 0.487 MCl2 0.402

For the same cation or the anion the transport number depends on the electrolyte.
Thus t, values for K in KGI, KBr and KNO 3 are 0.490, 0.488 and 0.508 respectively.
Similarly t. values for Glin HG!, LiG1, NaCl and KG! are 0.177, 0.662, 0.605 and 0.5 10
respectively. This is easy to understand because the transport number is not a unique
property of the ion but depends on the relative speeds of the cation and anion in an
electrolyte.
Abnormal Transport Numbers: It is sometimes found that the transport numbers of
some 10n3 decrease rapidly with increase in concentration of the ions. Examples are the
transport number of silver in ammoniacal solution, cadmium in cadmium iodide. This
change in transport number is attributed to complex formation, whereby the metallic ion
forms a part'of a Complex anion and travels to the anode. For cadmium this is represented
as follows:
2CdI2 Gd 2+ + [Cd!4]2

QUESTIONS AND PROBLEMS

1. What are electrolytes? Distinguish between strong and weak electrolytes.
2. State four ways in which metallic and electrolytic conduction differ.
3. Write a short essay on the theories of electrolytic dissociation. What is the modern concept about
strong electrolytes?
4. State Faradays Laws of electrolysis and explain these clearly. Describe experiments by which the
laws can be verified.
5. Explain the terms (i) Faraday, (ii) Coulomb, (iii)) Coulometer.
6. How does a coulometer work? What advantages are there to the use of a coulometer?
7. How many grams of 02 and 1-12 are produced in 1.0 hour when water is clectrolysed at a current of
0.50 A? What would be the volumes of the two gases measured at STP?
8. 200 mL of 0.1 inol L' solution of A8NO3 is electrolysed by a current of 0.2 ampere. 1-low many
minutes will be required to deposit half the silver in the solution on the cathode? [Ans. 80 min 25 see]
9 Explain clearly conductivity and specific conductance.
 409
Electrical Conductance and Electrolysis
Describe a suitable experiment by which the specific conductance of an electrolyte solution can be
10.
measured. Why is it necessary to use an a-c current source?
11. What is cell constant? Stae its unit.
had a resistance of 1748.6 ohm at 25°C in a crtain cpndu9tancc cell.
A solution of 0.01 mol U KC1 ohm cni, calcula\e
Given that the specific conductance of the above KCI solution is 1.411 x 10
the cell constant of the working cell.[Ans. 2.47 cmKCI I
12. A conductance cell Was 9alibrated by filling it with 0.02 mol U' solution of
and measuring the resistance at 25°C, which was found to be 457.3
2.768 x 10-3 ohn( coo per litre. The
ohm. The cell was then filled with a calcium chloride solution containing 0.555 g CaCl2
measured resistance was 1050 ohm. Calculate (a) the cell constant of the cell, and. (b) specifi,c
conductance of th C12 solution. [Ans. (a).266 cm _',(b) 1.206 x 1(1 oii,ii cm I
is 102 ohms at 18°C. The specific
13. The resistance of a conductivity cell containing 0.020 mol VKCI
conductance of this KCI solution at 18°C is 0.002394 ohm . Calculate the cell constant.
[Ans. 0.2442 cm]
What is meant by molar conductance? What is the significance of molar conductance at infinite
14. dilution? How does molar conductance vary with electrolyte concentration for (a) strong electrolytes
and (b) weak electrolytes?
Describe how Debye-Huckel theory explains the variation of molar conductance of strong electrolytes
15.
with concentration.
What is conductance ratio? Describe how the degree of dissociation of weak electrolytes may he
16.
determined?
Show how the dissociation constant of a weak acid can be calculated from conductance
17.
measurement.
Formic acid is 7.2% dissociated in a 0.1 ma! U' solution at 20°C. Calculate the dissociation constant
of the acid.
18. What is ionic mobility and how can this be measured?
State and explain the principle of independent ionic migration and mobility. Explain the relation
19.
AO +2 -A°.
C of solution containing 0.001 ,nol E' HC1 and 0.005 ro1 U 'NaC/.
20. Calculate the conductance at 25 0 [Ans. 1.058 x10 ohm ­' cn(
The values of ionic conductance at nfThite dilution may be used.
•. . system where (a) a strong acid is titrated with a strong base
21. Explain the conductanc a strong base. Explain your answer with suitable graphical
s.- weni. -ia. iLi1

What are e advantages of conductometric titrations over ordinary titrations? Explain your answer
22.
with suitabc examples.
Explain clearly the term 'Transport Number'. Describe one method for measurement of transport
23.
number. UCI, LiC1, KCI and CuCl2? If not, explain
24. Will the transport number of chloride ion be the same in
ho" the transport number will change and why?
25. Describe Hittorff's method for measurement of transport number of Ag in AgNO3 solution.
A moving boundary experiment was carried out with a 0.10 owl U solution of [-IC! at 25°C. Sodium
26. Three milliamperes
ions are caused to follow hydrogen ions under a potential gradient of 1.76 V COO .
cross-sectional area, and it is observed that the
current are passed through the tube of 0,3 cm 2
boundary moves 3.08 m in 1,0 11our. Calculate the hydrogen ion mobility. Given that the chloide ion
mobility is 7.64 x 10 cm V­ s calculate the transport number of hydroenjoflS.
[Ans. 36.3 x0 cm V' s'; 111+ = 0.831
cm' and the
27. A saturated solution of AgCI in water had a specific conductance of omi'
3.4 x 10, Calculate
coO . tle
specific conductance of water at the samp tcpiperature was 1 .6x10 [Ans. 1.88 xiO g U I
oh,n' cm.
solubility of AgCI. Given X°A g+ = 61.9 ohn( cm and )°ci 76.3and NH4CI are 258, 136 and 150
Ca(OH)2 , CaCl2
28. Molar conductances at infinitj dilution of Calculate the molar conductance at infinite dilption f
respectively, all in units of cm ,nol' ohm. [Ans. A° 272 crn mofl a/mi]
NH40H at 25°C. ,nol U' solution of KC! with CdCl2 as
29. A moving boundary experiment was carried out with 0.01
was passed through a tube of cross sectional area 030
indicator electrolyte. A current of 5.21 mA
cm for 60 seconds when the boundary moved a distance of 4.16 cm. Calculate the transport - =numbers
0.82271
of the ions.[Ans. tK+ = 0. 1772,
slution of AgNO3 using two Pt electrodes it was
30. In an electrolysis experiment with a 0.1 mol U'
found that a fall of concentration of 0.5124 x 10 g occurred in the anodic solution in 120 seconds
deposited in a copper coulometer placed in series was
afterpassing a small current. The mass of Cu ions.
found to be 0.03879g. Calculate the transport numbers of Ag and NO3[Ans. = 0.42, tNO = 0.58]
tAg