Conductance of electrolytic solutions:

esistance: R
1.
It is the measure of obstruction to the flow of current. It is
measured in ohm ()
2.
It can be measured with the help of a Wheatstone bridge
3. The electrical resistance of any object is directly proportional to its
length, l and inversely proportional to its area of cross section, A. That
is,

The constant of proportionality, (Greek, rho), is called resistivity

(specific resistance).

Resistivity (specific resistance)

1. It is defined as the resistance of a conductor of one metre long
having area of cross section equal to One m2
=
2. Its SI unit is ohm metre ( m)

Conductance (G)
1. It is a measure of the ease with which current flows through a
conductor.
2. It is the inverse of resistance

3. The SI unit of conductance is siemens S .It can also be written as

ohm1 (also known as mho) or

Conductivity (specific conductance) (Greek, kappa):

It is the inverse of resistivity

Conductivity may be defined as the conductance of a material when it is 1 m long and its area of
cross section is 1 m2.

Conductance of one centimeter cube of a solution of an electrolyte

The conductivity of a solution at any given concentration is the conductance of one

unit volume of solution kept between two platinum electrodes with unit area of
cross section and at a distance of unit length. This is clear from the equation:
=

G=Conductance=1/R
G*=Cell constant =l/A
K=conductivity
= Resistivity

The SI unit of conductivity is S m1 but quite often, is expressed in S cm1

Conductivity depends on the following factors:

(i)The nature of the material (ii) temperature and (iii) pressure at which the measurements are
made.
(i)The nature of the material:Materials are classified into conductors, insulators and
semiconductors depending on the magnitude of their conductivity.
Conductors:

The substances which allow the passage of electric current are called conductors.
Eg. Metals and their alloys, certainnon-metals like carbon-black, graphite and some
organic `
polymers are also electronically conducting.

Insulators:

The substances which do not allow the passage of electric current are called Insulators.
Substances like glass, ceramics, rubber, wood, wax etc.,

Semiconductors:

Substances having conductivity between conductors and insulators are called

semiconductors and are important electronic materials. eg. Silicon doped silicon and
gallium arsenide.

Superconductors:

Materials having zero resistivity or infinite conductivity are called superconductors.

Earlier, only metals and their alloys at very low temperatures (0 to15 K) were known to
behave as
superconductors, but nowadays a number of ceramic materials and mixed
oxides are also known to
show superconductivity at temperatures as high as 150
K.eg. YBaCu3O7(92K)
Types of conductors:
(a)Metallic (or) electronic conductance (b) electrolytic (or) ionic conductance
Sl.No.
Metallic conduction
1
It is carried by the movement of electrons
It involves no change in the chemical
2
properties of the conductor
3
4

It does not involve the transfer of any

matter
It decreases with increase in temperature

Electrolytic conduction
It is carried by the movement of ions
It involves the decomposition of the
electrolyte as a result of the chemical
reaction
It involves the transfer of matter as ions
It increases with increase in temperature

Give reason why metallic conduction decreases with increase in temperature where as
electrolytic conduction increases with increase in temperature
Metallic conduction decreases with increase in temperature because the kernel starts vibrating
which produce hindrance in the flow of electrons. electrolytic conduction increases with increase

in temperature On increasing the temperature, the dissociation increases and hence conduction
increases.
Measurement of the Conductivity of Ionic Solutions:
Accurate measurement of an unknown resistance can be performed on a Wheatstone bridge.
two problems for measuring the resistance of an ionic solution

Firstly, passing direct current (DC) changes the composition of the solution.
Secondly, a solution cannot be connected to the bridge like a metallic wire or other solid
conductor.

Solution

The first difficulty is resolved by using an alternating current (AC) source of power.
The second problem is solved by using a specially designed vessel called conductivity
cell.

Two different types of conductivity cells.

Conductivity cell

Basically it consists of two platinum electrodes coated with platinum black (finely
divided metallic Pt is deposited on the electrodes electrochemically).

These have area of cross section equal to A and are separated by distance l. Therefore,
solution confined between these electrodes is a column of length l and area of cross
section A.

The Resistance of such a column of solution is then given by the equation:

cell constant G*:The quantity l/A

It depends on the distance between the electrodes and their area of Cross-section and has
the dimension of length1 and can be calculated if we know l and A.

is called cell constant G*.

Measurement of the Conductivity of Ionic Solutions

Step1: Measurement of cell constant:
Measurement of l and A is not only inconvenient but also unreliable.
The cell constant is usually determined by measuring the resistance of the cell containing
a solution of KCl whose conductivity is already known.
The cell constant, G*, is then given by the equation:

Step2:The set up for the measurement of the resistance

Take electrolytic solution in conductivity cell
Construct Wheatstone bridge by taking two resistances R3 and R4,
a variable resistance R1 and the conductivity cell having the unknown
resistance R2
Change the resistance of variable resistance(R1) till the bridge is balanced

when no current passes through the detector.

Under these conditions: R1/R2 = R3/R4

Unknown resistance

Step3.
Once the cell constant and the resistance of the solution in the cell is determined, the
conductivity of the solution is given by the equation:

Molar conductivity m (Greek, lambda)

It is defined as the conducting power of all the ions produced by dissolving one mole of
an electrolyte in solution
Molar conductivity :conductance of the one mole of electrolytic solution kept between
the electrodes of a conductivity cell at unit distance and having large area of cross
section
Molar conductivity of a solution at a given concentration is the conductance of the
volume V of solution containing one mole of electrolyte kept between two electrodes with
large area of cross section A and distance of unit length
m=
C

m = x1000
M

m = xV

If is expressed in Sm-1 and Conc. is in mol m-3 then the unit of m is Sm2 mol-1

If is expressed in Scm-1 and M is the molarity (mol L-1) then the unit of m is Scm2
mol-1

Variation of conductivity (k)with concentration (weak and strong electrolyte)

Conductivity always decreases with decrease in concentration(On dilution) both, for weak and
strong electrolytes.
Reason: the number of ions per unit volume that carry the current in a solution decreases on
dilution.
Variation of molar conductivity with concentration
It increases with decrease in concentration(On dilution) of the electrolyte.
Reason: This is because the total volume, V, of solution containing one mole of electrolyte
increases on dilution. That increases the mobility of ions by minimizing inter-ionic attractions
and increase in extent of ionization (Decrease in on dilution of a solution is more than
compensated by increase in its volume.).
The variation in molar conductivity with concentration is different for strong and weak
electrolytes.
This can be studied by plotting graph between molar conductivity and concentration (C,)
Limiting molar conductivity: It is the molar conductivity at infinite dilution i.e.
(when concentrationapproaches zero)
limiting molar conductivity and can be represented by the equation the ion:
m= m-AC
If we plot m against C, we obtain a straight line with intercept m slope A
For strong electrolyte

For weak electrolyte

At high concentration

Strong
electrolytes
are
completely ionised in solution
at all concentrations.
In concentrated solution there
are
strong
inter
ionic
attraction. This decreases the
speed of ions and mobility

Weak electrolytes are partially

ionised in solution and give less
number of ions and strong inter
ionic attraction. This decreases
the speed of ions and mobility

On decreases in
concentration (dilution)

On dilution the ions move

apart due to the decrease in
inter ionic attractions and
their mobility (speed of ion)
increases with dilution. Molar

Extent of ionization increases there by increases

number of ions as well as the decrease in inter
ionic attractions increase the mobility (speed of
ion) with dilution. Molar conductivity increases
steeply

GRAPH

conductivity increases slowly

Calculating
limiting molar
conductivity 0 m:

It can obtained from the

graph plotted between m
and C. .

The
curve
obtained
is
straight line with negative
slope.

Since
m
increases
steeply(parallel to y-axis) on
dilution m cannot be obtained
by extrapolation of m to zero
concentration.

At infinite dilution electrolyte

dissociates completely (=1),

but at such low concentration

the conductivity of the solution
is so low that it cannot be
measured accurately.

m for weak electrolytes is obtained by

using Kohlrausch law of independent
migration of ions.

When extrapolation of m to
zero concentration intercept
gives 0 m

Important summery :
For strong electrolytes
A. Effect of decreasing concentration or dilution on molar conductivity
m increases slowly with dilution( decreasing concentration)
Reason:
Strong electrolytes are completely ionised in solution at all concentrations. In
concentrated solution there are strong inter ionic attraction. This decreases the speed of
ions and mobilityOn dilution the ions move apart due to the decrease in inter ionic
attractions and their mobility increases with dilution.
B. Limiting molar conductivity
When the concentration of the solution become very, very low , inter ionic attraction
become negligible and molar conductivity approaches the limiting value called limiting
molar conductivity and can be represented by the equatring the ion:
m= m-AC
If we plot m against C, we obtain a straight line with intercept m slope A.

C. Measuring the limiting molar conductivity 0 m:

It can obtained from the graph plotted between m and C. .the curve obtained is

straight line with negative slope. When extrapolation of m to zero concentration

intercept gives 0 m
For Weak electrolytes:
D. Effect of decreasing concentration or dilution on molar conductivity
Weak electrolytes (like acetic acid )have lower degree of dissociation at higher

concentrations. Therefore the molar conductivity is low as compared to strong

electrolyte.

On dilution it increases steeply, especially near lower concentrations. However it does

not reach a limiting value
Reason: on dilution the degree of dissociation and consequently the number of ions in
total volume of solution that contains 1 mol of electrolyte as well as its mobility
increases.
E. m cannot be obtained by extrapolation of graph of weak electrolytes

Since m increases steeply on dilution m cannot be obtained by extrapolation of m to zero

concentration.
At infinite dilution electrolyte dissociates completely (=1), but at such low concentration
the conductivity of the solution is so low that it cannot be measured accurately.

F. How to find m for weak electrolytes

m for weak electrolytes is obtained by using Kohlrausch law of independent
migration of ions.
Kohlrausch law of independent migration of ions.
The law states that limiting molar conductivity of an electrolyte can be represented as the
sum of the individual contributions of the anion and cation of the electrolyte.

The law states that limiting molar conductivity of an electrolyte is equal to the sum of the
molar conductivities of the anion and cation of the electrolyte at infinite dilution.
Applications of Kohlrausch law:
1. To calculate m for any electrolyte from the o of individual ions.
(i) For strong electrolytes like NaCl,
NaCl = Na+ + Cl(ii) For weak electrolytes like acetic acid it can be be obtained by the knowledge of
limiting molar conductivity of some strong electrolytes.
CH3COOH = CH3COONa + NaCl _ HCl
NH4OH = NH4Cl + NaOH _ NaCl
2. To calculate the degree of dissociation of weak electrolyte :

At any concentration c, the degree of dissociation is defined as the ratio of molar

conductivity m at the specific Concentration c to limiting molar conductivity, m
3. To determine the value of the dissociation constant for weak electrolyte (ka)

Table 3.4: Limiting Molar Conductivity for some ions in water at 298K

1
2

8
9

Suggest a way to determine the mvalue of water.