Variation of conductivity with concentration

of electrolytes increases with dilution.

The variation is different for strong and weak electrolytes.
Strong Electrolytes
It is given according to the equation

are the molar conductance at a given concentration and at infinite dilution

(respectively). b is a constant depending on the viscosity of the solvent. The graph shows
that decreases as the concentration increases.

fig 5.6
This is because at higher concentration there is greater inter ionic attraction which

retards the motion of the ions as conductance falls is that conductance at

infinite dilution where the ions are far apart and there is no inter-ionic attraction. This
can be obtained by extrapolation of the graph to zero concentration.
Weak electrolytes
A weak electrolyte dissociates to a much lesser extent so its conductance is lower than
that of a strong electrolyte at the same concentration.
fig 5.7
The very large increase at infinite dilution is because the ionization increases and so the
number of ions in solution increases.

The value of cannot be obtained by extrapolation as can be seen on the

graph. It is obtained by applying Kohlrausch's law.

values for strong electrolytes is larger than weak electrolytes for the same
concentration. Increase for strong electrolyte is quite small as compared to that for
weak electrolyte.

Summary
The conductivity and molar conductivity of an electrolyte change with the concentration of the
electrolyte.
As concentration decreases, conductivity decreases for both strong and weak electrolytes.
But molar conductivity increases as concentration decreases. The variation is different for strong
electrolytes and weak electrolytes.
Limiting molar conductivity:
This is the conductivity of a solution as its electrolyte concentration approaches zero. Limiting
molar conductivity is given the symbol Λ0m.
The molar conductivity of strong electrolytes is weakly dependent on concentration.
A graph of molar conductivity against the square root of concentration:
The y intercept is the limiting molar concentration. The slope of the resulting line is the
Kohlrausch coefficient, which depends on the specific salt.
The Kohlrausch coefficient depends on the cation and anion charges of the ions formed by the
electrolyte.
The molar conductivity of a weak electrolyte depends greatly on the concentration of the
solution. This is because weak electrolytes have a low degree of dissociation as concentration
increases.
Since the relationship isn't linear, we can't determine the limiting molar conductivity by
extrapolating back to zero concentration. At infinite dilution, the electrolyte dissociates
completely, but the conductivity is so low that it can't be measured directly. Instead, we can use
Kohlrausch's law to find the limiting molar concentration.

Degree of dissociation α:
α for a weak electrolyte
Degree of Dissociation α = Am(Molar Conductivity)/A°m(Limiting Molar Conductivity)
If the molar conductivity and the limiting molar conductivity known, then the dissociation
constants for weak electrolytes at a given concentration can be find.
Videos

1.Chemistry Electrochemistry part 22 (Molar Electrolytic conductivity variation) CBSE class 12 XII

2.Effect of
Concentration on Conductivity of Solutions

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-The conductance is the property of the conductor (metallic as well as electrolytic) which facilitates
the flow of electricity through it. It is equal to the reciprocal of resistance i.e.,

Units of conductance : .
Specific Conductance or Conductivity
The resistance of any conductor varies directly as its length (l) and inversely as its cross-sectional
area (A), i.e.,
Mathematically

Where ρ is called the specific resistance.

l/A is known as cell constant.
If l = 1 cm and A = 1 cm2, then
R=ρ
The specific resistance is, thus defined as the resistance of one centimeter cube of a conductor.

The reciprocal of specific resistance is termed the specific conductance or it is the conductance
of one centimeter cube of a conductor.
It is denoted by the symbo (kappa)l .
Thus,

Where kappa → the specific conductance

Specific conductance is also called conductivity.

Further,

or Specific conductance = Conductance × cell constant

In the case of electrolytic solutions, the specific conductance is defined as the conductance of a
solution of definite dilution enclosed in a cell having two electrodes of unit area separated by one
centimeter apart.

Unit of specific conductance:

Equivalent Conductance
One of the factors on which the conductance of an electrolytic solution depends is the concentration
of the solution.

In order to obtain comparable results for different electrolytes, it is necessary to take equivalent
conductance's.
Equivalent conductance is defined as the conductance of all the ions produced by one gram
equivalent of an electrolyte in a given solution.

It is denoted by A.

To understand the manning of equivalent conductance, imagine a rectangular

trough with two opposite sides made of metallic conductor (acting as
electrodes) exactly 1 cm apart, If 1 cm3 (1 mL) solution containing 1 gram
equivalent of an electrolyte is places in this container is measured.
According to definitions,
Conductance = Specific conductance (K) = Equivalent conductance ( )
If the solution is diluted to say (9 cm3) (9 mL), the conductance of the solution will be the same but
specific conductance becomes 1/9th as it contains nine cubes.
The conductance is also equal to the equivalent because the solution still has 1 g equivalent of the
electrolyte.

Equivalent conductance ( ) = 9 × k

In general,

=k×V

where V is the volume in mL containing 1 g equivalent of the electrolyte.

In case, if the concentration of the solution is c gram equivalent per litre, then the volume containing 1 g equivalent o
So equivalent conductance
= k × 1000/c
= k × 1000/N
where N = normality
Unit of equivalent conductance:

Molar Conductance
The molar conductance is defined as the conductance of all the ions produced by ionization of 1 g
mole of an electrolyte when present in V mL of solution. It is denoted by .

Molar conductance μ = k ×V

where V is the volume in mL containing 1 g mole of the electrolyte. If c is the concentration of the
solution in g mole per litre, then

μ = k × 1000/c

Units of molar conductance:

Equivalent conductance = (Molar conductance)/n
where

n = (Molecular mass)/(Equivalent mass)

Measurement of Conductance
It is now known to us that when the solution of an electrolyte is taken between two parallel electrodes
of cross-sectional area 'a' and 'l' cm apart, then the specific conductance, k, should be:

Thus, knowing the values of R, l and A, the specific conductance can be measured.
 The resistance of the solution between two parallel electrodes is determined by using Wheatstone
bridge method.
 The diagram of the apparatus is shown in AB is a uniform wire and X is a sliding contact which
moves over it.

 C is the conductivity cell containing the solution of the electrolyte and S represents the source of
alternating current.

 R is the resistance box and T is a headphone to detect the flow of current.

 A suitable resistance is taken out from the resistance box and the sliding contact X is moves on
the wire to search a point of minimum sound in the headphone. At this point, the bridge is balanced.

 (Resistance of solution)/(Resistance from resistance box) =(Resistance XB)/(Resistance

XA) =(Length XB)/(Length XA)
 Resistance of solution can be used because it produce two complications.
 Change in the concentration of the solution occurs due to electrolysis which will change the
resistance.

 Polarisation at the electrodes sets in which also charges the resistance.

 An alternating current (A.C.) is used to overcome the above complications.

 The solution whose conductance is to be measured is taken in a special type of cell known as
conductivity as conductivity cell.

 The electrodes consist of platinum discs coated with finely divided platinum black and welded to
platinum wires fused in two glass tubes.
 The glass tubes contain mercury and are finely fixed in the cover of cells. Contact with the platinum
is made by dipping the copper wires of the circuit in the mercury contained in the tubes.

 As the conductivity changes with temperature, the cell is usually placed in a constant temperature
bath during the experiment.

 Cells with along paths are used for concentrated solution and cells with sort paths and large
electrodes are used for dilute solutions.
Cell Constant
Since the electrodes are not exactly 1 unit apart and may not possess a surface area of 1 square unit,
the measured resistance does not give the specific conductance of the solution. Actual measurements
of l and a being inconvenient, an indirect method is employed to determine the value of which is a
constant quantity for a particular cell and is known as cell constant.

We know that

(Specific conductance)/Conductance=l/A= cell constant

The resistance of cell, i.e., conductance is measured when filled with a standard solution (say N/10
KCl solution) at a given temperature.

The standard values of specific conductance of KCl solutions of various concentrations at different
temperature are known.

Thus, the cell constant is calculated by using the above equation. The sane cell constant applies to a
measurement with any other solution.

The determination of specific conductance of an electrolytic solution, thus, consists of two steps:

 Determination of cell constant by using a standard KCl solution of known concentration in the
conductivity cell.
 Determination of resistance of he given solution using the same cell. The reciprocal of this gives
the value of conductance.

Multiplication of conductance and cell constant gives the value of specific conductance of the solution.

In order to determine equivalent conductance or molar conductance, the concentration of the

experimental solution should be known.
In conductance measurements, the solutions are always prepared in conductivity water which has no
conductance due to dissolved impurities.

It is prepared by distilling a number of times the distilled water to which a little KMnO 4 and KOH have
been added in a hard glass distillation assembly.
Such water has very low conductance of the order of 4.3 × 10-8 ohm-1. For ordinary purposes, double
distilled water may be used.

Effect of Dilution on Equivalent Conductance

 The value of equivalent conductance increases with dilution.
 This is due to the fact that degree of ionization increases with dilution thereby increasing the total
number of ions in solution.

 Solution which contains large number of ions compared to another solution of the same
concentration at the same temperature has more conductance and is said to be stronger
electrolyte.

 The one which has relatively small number of ions is called a weak electrolyte. The number of ions
from an electrolyte depends on the degree of dissociation. The curve shows the variation of the
equivalent conductance of some electrolytes with dilution. It shows that electrolytes behave in two
ways o dilution.
 Electrolytes like KCl have high value of conductance even at low concentration and there is no rapid increase in the
dilution. Such electrolytes are termed strong electrolytes. In the case of strong electrolytes, there is a tendency for e
approach a limiting value when the concentration approaches zero. When the whole of the electrolyte has ionized, fu
not bring any change in the value of equivalent conductance. This stage is called infinite dilution. The equivalent con
oat infinite dilution and is represented by /\∞ .
Electrolytes like acetic acid have a low value at high concentration and there is a rapid increase in the value of equiv
Such electrolytes are termed weak electrolytes. There is no indication that a limiting value of equivalent conductance
the concentration approaches zero. Thus, graphically, /\∞ of weak electrolytes cannot be obtained.
 It is thus concluded that equivalent conductance of electrolytes whether strong or weak increases
with dilution and reaches to a maximum or limiting value which is termed /\∞ (equivalent
conductance at infinite dilution.) /\∞ in the case of strong electrolytes cannot be obtained by
extrapolation of the graph of equivalent conductance to zero concentration but in the case of weak
electrolytes it cannot be obtained accurately. An indirect method for obtaining /\∞ for weak
electrolyte has been given by Kohlrusch.

Question 1:
Unit of molar conductivity is

a. ohm cm-1 mol-l

b. ohm-1 mol
c. ohm-1 cm-1 mol-l
d. ohm mol-l
Question 2:
The reciprocal of resistivity is known as

a. molar conductance

b. specific conductance

c. equivalent conductance

d. permittivity
Question 3:
is the unit of

a. molar conductance

b. specific conductance

c. conductivity

d. resistivity
Question 4:
The value of equivalent conductance
a.decreases with pressure.

b. increases with pressure.

c. decreases with dilution.

d. increases with dilution.

Q.1 Q.2 Q.3

a b a