Contents:

❖ Kohlrausch’s Law
❖ Applications of Kohlrausch's Law
• Calculation of Ionic Conductance
• Calculation of ^ ° for Weak Electrolytes
• Calculation of ^°for Sparingly Soluble Salts
• Determination of the Solubility of Sparingly Soluble Salt
• Determination of the Degree of Dissociation of Weak Electrolyte
• Calculation of the ionic product of water
Physical Chemistry

Kohlrausch’s Law
The molar conductance of an electrolyte at infinite dilution is equal to the sum of the ionic molar
conductanes of the component ions.

Explanation:

Kohlrausch examined the molar conductances of different electrolytes and discovered that the difference
in ^° for pairs of electrolytes having a common ion is always approximately constant. For example (in
units of ohm-I m2 mol-I)

(^°)KCl = 0.014986 (^°)KI = 0.015038 (^°)NaBr=0.012851 (^°)KBr=0.015192

(^°)NaCl=0.012645 (^°)NaI = 0.012694 (^°)NaCl=0.012645 (^°)KCl
=0.014986
Difference
Δ=0.002341 Δ = 0.002344 Δ = 0.000206 Δ =0.000206

The difference between the ^° of potassium and sodium having a common anion is independent of the
anion and similar results are obtained with pairs of salts having cation in common. From these
observations, Kohlrausch enunciated a generalisation which is known as the Kohlrausch’s 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.”

This law may be expressed mathematically as:

^° = 𝝀+° + 𝝀−°
Where 𝝀+ −
° 𝒂𝒏𝒅 𝝀° are the ionic molar conductances of the cations and anions respectively at infinite
dilution.

Applications of Kohlrausch's Law

1. Calculation of Ionic Conductance:
Each ion has the same constant value of 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

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𝝀+
° ∝ 𝒖+ 𝒐𝒓 𝝀+
° = 𝒌𝒖+ .......................................(1)

And
𝝀−
° ∝ 𝒖− 𝒐𝒓 𝝀−
° = 𝒌𝒖− ..............................................(2)

^° = 𝝀+° + 𝝀−° = 𝒌𝒖+ + 𝒌𝒖− = 𝒌( 𝒖+ + 𝒖− ).............(3)

Dividing Eq.(1) by Eq. (3), we get

𝝀+
° 𝒌𝒖+ 𝒖+
= = = 𝑡+
^° 𝒌( 𝒖+ + 𝒖− ) 𝒖+ + 𝒖_

Similarly

𝝀_° 𝒌𝒖_ 𝒖_
= = = 𝑡_
^° 𝒌( 𝒖+ + 𝒖− ) 𝒖+ + 𝒖_

Here 𝑡+ and 𝑡_ are the transport numbers of the cation and the anion respectively at infinite dilution. Ion
transport number is the fraction of the total electrical current carried in an electrolyte by a
given ionic species. The above expressions are very useful for determining the ionic conductances at
infinite dilution from the values of the transport number of ions and ^° values of the strong electrolytes.

Molar Ionic conductances at infinite dilution at 25°C

Cation λ+ Anion λ-
H+ 0.034982 OH- 0.019850
Na+ 0.00509 Cl- 0.00755
K+ 0.00745 Br- 0.007840
Ag+ 0.00635 I- 0.007680
𝑁𝐻4+ 0.00745 CH3COO- 0.004090
½ Ca2+ 0.00595 N𝑂3− 0.007144
½ Ba2+ 0.006364 ½ S𝑂42− 0.007980

2. Calculation of ^° for Weak Electrolytes:

It has already been pointed out that direct determination (graphical method) of the molar conductance of a
weak electrolyte at infinite dilution is not possible. These conductances however, can be determined with
the help of the Kohlrausch's law. ^° values for all mineral acids and salts (strong electrolytes) can be

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determined experimentally by graphical extrapolation method. Thus ^° for weak electrolytes can be
calculated from the ^° values of mineral acid and salts which are strong electrolytes. For example, ^° for
acetic acid can be calculated from the molar Conductance values of three strong electrolytes, namely, HCI,
NaC1 and CH3COONa as follows:

(^°)HAc = (^°)NaAc + (^°)HCl - (^°)NaCl

= λ°(Na+) + λ°(Ac-) + λ°(H+) + λ°(Cl-) - λ°(Na+) - λ°(Cl-)

= λ°(H+) + λ°(Ac-)

= 0.035 + 0.00408

= 0.03908 ohm-I m2 mol-I

3. Calculation of ^°for Sparingly Soluble Salts:

^° for sparingly soluble salts (e.g., AgCl, PbS04) can be determined by adding the molar
ionic conductances of the constituent ions. Thus for AgCl

^° (AgCl) = λ°(Ag+) + λ°(Cl-)

= 0.00635 + 0.00755
= 0.0149 ohm-I m2 mol-I

4. Determination of the Solubility of Sparingly Soluble Salt:

The solubility of sparingly soluble salts such as AgCl, PbS0 4 is very small and cannot be
easily determined by a chemical method. However, their solubilities can be determined
from the measurements of their conductance values of their solutions. A saturated solution
of the sparingly soluble salt is prepared in the conductivity water of known specific
conductance K(for H2O). Then the specific conductance of the saturated solution is
measured. From this is subtracted the conductivity of the water itself, so that the specific
conductance of the salt alone k(salt), in solution is found out.
k(salt) = k(solution) - k(H2O)
From K(salt), the molar conductance is obtained by using the following equation.
10−3
^𝑚 = 𝐾(𝑠𝑎𝑙𝑡)
𝑐

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where c is the concentration of the salt in moles dm-3 and that is the solubility. Since the solution
is very dilute, it must be completely dissociated into ions, therefore ^𝑚 must be equal to ^° which
according to Kohlrausch’s law is the sum of the ionic conductances of the constituent ions,

^° = 𝝀+° + 𝝀−° Hence,

10−3
^𝑚 = ^° = 𝐾(𝑠𝑎𝑙𝑡)
𝑐
10−3 10−3
C= 𝐾(𝑠𝑎𝑙𝑡) = 𝐾(𝑠𝑎𝑙𝑡)
𝑐 𝝀+
° + 𝝀−
°

By looking up 𝝀+ −
° 𝒂𝒏𝒅 𝝀° values in the table of molar ionic conductances at infinite dilution, c the
solubility in mole dm-3 can be calculated from above equation from the measured specific conductance of
the saturated solution.

5. Determination of the Degree of Dissociation of Weak Electrolyte:

The degree of dissociation of an electrolyte may be defined as the fraction of the total number of molecules
of the solute present in solution as ions that are free to carry current at a given concentration and is denoted
by 𝛼. According to the Arrhenius theory of electrolytic dissociation, 𝛼 can be determined by taking the
ratio of the molar conductance of the solution Vv, at the dilution V, to the molar conductance at the infinite
dilution ^° thus

^𝑣 ^𝑣
𝛼= = +
^° 𝝀° + 𝝀−
°

Above holds good for weak electrolytes and is not applicable to strong electrolytes.

6. Calculation of the ionic product of water:

Water is a weak electrolyte and it ionizes according to the equation

H2O H+ + OH-

To find the degree of ionization 𝛼 at,say,25°C, ^𝑣 is required. Since ^𝑣 = 𝑘 × 𝑉, where V is the volume
in cubic meter containing 1 mole of water. V must be the molecular mass of water divided by the density
of water at 25°C (density of water at 25°C is 0.9971 gcm-1. Therefore,

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𝑀𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 18.016

𝑣= = = 18.0684 𝑐𝑚3
𝑑𝑒𝑛𝑠𝑖𝑡𝑦 0.9971

The specific conductance of distilled water at 25°C is 58 × 10−7 ohm-I m-1

^𝑣 = 𝑘 × 𝑉 = 58 × 10−7 × 18.0684 × 10−6 = 1.048 × 10−10 ohm-I m-2

Again, for water is the sum of the molar ionic conductance of H+ and OH- ions. Thus

^° (H20) = λ°(H+) + λ°(OH-) = 0.035 + 0.0192 = 0.0542 ohm-I m-2

^𝑣 1.048 × 10−10
𝛼= = = 1.91 × 10−9
^° 0.0542

The molality of water is given by,

1000
C= 18.016 = 55.49 mol dm-3

Hence, the ionic concentrations are

CH+ = COH- = 𝛼𝑐 = 55.49 × 1.191 × 10−9 = 1.05 × 10−7

Ionic product of H2O,

Kw = CH+ × COH- = 1.05 × 10−7 × 1.05 × 10−7

Kw = 1.1 × 10−14

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Physical Chemistry

Reference:
• A text book of Physical Chemistry by Ghulam Rasool Chaudhary
• www.wikipedia.com