418 A TEXT BOOK OF PHYSICAL CHEMISTRY

11.10 KOHLRAUSCH'S LAW

Kohlrausch examined the molar conductances of different

electrolytes and

discovered that the difference in A o for pairs of electrolytes

having a common ion is
always approximately constant. For example (in units of ohm-I m2
mol-I)
- 0.014986 ( AO)KI = 0.015038 ;
A
( o)NaBr0.012851 , = 0.015192

= 0.012645 ( A
o)Na1 —- 0.012694; ( A
o)NaCl0.012645 ; (
A
O)KCI - - 0.014986
(Ao)NaC1

0.000206
A = 0.000206
Difference; A = 0.002341 = 0.002344
infinite dilution.
The difference between the Ao of potassium and sodium having a
Applicatidns of
Kohlrausch's Law common anion is
1 . Calculation
independent Ionic andEach
of anion
of the ion results
similar has theare
same constant Soluti(
obtained
Conductance:
with pairs of salts having value
cation of
in common. From these
observations, Kohlrausch enunciated a generalisation which
is known as the Kohlrauschts law of independent migration
of ions. This law states, At
infinite dilution, when all the inter-ionic effects
disappear, each ion migrates independent of its co-ion, and
contributes to the total molar conductance of electrolyte,
a definite share which depends only on its nature and not
at all on the other ion with which it is associated.
expressed 1
mathematically as: o (12)
where X and X are the ionic molar conductances of the eations
and anions respectively at Ixa
m
 In simple words, this law states, the molar conductance of an
electrolyte at infinite dilution1 is equal to the sum of the
ionic molar conductanes of the component ions. This law may bei

conductance at an infinite 'dilution at a given temperature,

no matter of which electrolyte it
forms a part. It is directly proportional to the speed of the ion.

If u+ and u_ are the velocities of cations and anions respectively

at infinite dilution, then

or
oku+

and Xoor

O
ku+ + ku_k(u++
u_)
Dividing Eq. (13) by Eq. (15), we get

ku+ o k(u+ + u_) t+

Similarly,