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Kohlrausch law
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Debye Huckel-Onsager equation:
ΛCm = Λ0m − A C
Where
A = constant depending upon the type of the electrolyte (NaCl, BaCl2, MgSO4 are called 1–1, 2–1
and 2–2 electrolytes respectively depending upon the charges on cation and anion. For a given
solvent and temperature, all electrolytes of a particular type have the same value for the constant
A), the nature of the solvent and the temperature,
Λ0m = molar conductivity at infinite dilution or limiting molar conductivity
Λ0m is the maximum value for Λm for a given electrolyte.
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Thus, if Λ m is plotted against C, a linear graph is obtained for low concentrations (with slope =
– A) but it is not linear for higher concentrations
Simplified Chemistry (Simple Approach for difficult Concepts) Contact Sharma Sir 9826259230
Simplified Chemistry (Simple Approach for difficult Concepts) Contact Sharma Sir 9826259230
Kohlrausch law of independent migration of ions:
The limiting molar conductivity of an electrolyte (i.e. molar conductivity at infinite dilution) is
the sum of the limiting ionic conductivities of the cation and the anion each multiplied with the
number of ions present in one formula. unit of the electrolyte.
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Kohlrausch law of independent migration of ions:
“At time infinite dilution, the molar conductivity of an electrolyte can be expressed as the sum of
the contributions from its individual ions” i.e.

Λ∞ 0 0 y+ 0 x–
m Or Λ m AxBy = X Λ m A + Y Λ m B

Where;
Λ0m = limiting molar conductivity; & Λ∞
m = molar conductivity at infinite dilution,

X = the number of cations “Ay+” & Y = the number of anions “Bx –”.
 Simplified Chemistry (Simple Approach for difficult Concepts) Contact Sharma Sir 9826259230
Applications of Kohlrausch law:
1. Determination of 𝚲∞
𝐦 for weak electrolytes:
 Simplified Chemistry (Simple Approach for difficult Concepts) Contact Sharma Sir 9826259230
2. Determination of the degree of ionization of a weak electrolyte:

ΛC
m
∝=
Λ∞
m

Where,
ΛCm = molar conductivity of a weak electrolyte at concentration C
Λ∞
m = molar conductivity of a electrolyte at infinite dilution.

∝ = degree of ionization.
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3. Determination of the ionization constant of a weak electrolyte:
C ∝2
K=
(1− ∝)

Where
K = the ionization constant of the weak electrolyte,
C = Molarity or Concentration of weak electrolyte.
∝ = degree of ionization
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4. Determination of the solubility of a sparingly soluble salt:
1000 x κ
S=
Λ∞
m

Where;
S = solubility of a sparingly soluble salt,
κ = the conductivity of the salt,
Simplified Chemistry (Simple Approach for difficult Concepts) Contact Sharma Sir 9826259230
Simplified Chemistry (Simple Approach for difficult Concepts) Contact Sharma Sir 9826259230
Simplified Chemistry (Simple Approach for difficult Concepts) Contact Sharma Sir 9826259230
Simplified Chemistry (Simple Approach for difficult Concepts) Contact Sharma Sir 9826259230
Simplified Chemistry (Simple Approach for difficult Concepts) Contact Sharma Sir 9826259230
Simplified Chemistry (Simple Approach for difficult Concepts) Contact Sharma Sir 9826259230
Simplified Chemistry (Simple Approach for difficult Concepts) Contact Sharma Sir 9826259230
Simplified Chemistry (Simple Approach for difficult Concepts) Contact Sharma Sir 9826259230
Simplified Chemistry (Simple Approach for difficult Concepts) Contact Sharma Sir 9826259230
Simplified Chemistry (Simple Approach for difficult Concepts) Contact Sharma Sir 9826259230
Simplified Chemistry (Simple Approach for difficult Concepts) Contact Sharma Sir 9826259230
Simplified Chemistry (Simple Approach for difficult Concepts) Contact Sharma Sir 9826259230

NCERT &
NCERT Exemplar
Questions
Simplified Chemistry (Simple Approach for difficult Concepts) Contact Sharma Sir 9826259230
Example 3.6: The molar conductivity of KCl solutions at different concentrations at 298 K are
given below:
C (mol L–1) Λ𝑜𝑚 (S cm2 mol–1)
0.000198 148.61
0.000309 148.29
0.000521 147.81
0.000989 147.09
Show that a plot between Λ 𝑚 and c½ is a straight line. Determine the values of Λ𝑜𝑚 and A for KCl.
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Example 3.7: Calculate Λ𝑜𝑚 for CaCl2 and MgSO4 from the data given
Λ𝑜𝑚 Ca2+ = 119.0 S cm2 mol–1 Λ𝑜𝑚 Cl– = 76.3 S cm2 mol–1
Λ𝑜𝑚 Mg2+ = 106.0 S cm2 mol–1 Λ𝑜𝑚 SO42– = 160 S cm2 mol–1
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Example 3.8: Λ𝑜𝑚 for NaCl, HCl and NaAc are 126.4, 425.9 and 91.0 S cm2 mol–1 respectively.
Calculate Λ𝑜𝑚 for Hac
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Example 3.9: The conductivity of 0.001028 mol L –1 acetic acid is 4.95 × 10–5 S cm –1. Calculate
its dissociation constant if Λ𝑜𝑚 for acetic acid is 390.5 S cm2 mol–1.
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NCERT Exercise
3.10 The conductivity of sodium chloride at 298 K has been determined at different
concentrations and the results are given below:
Concentration/M 0.001 0.010 0.020 0.050 0.100
102 × κ/S m–1 1.237 11.85 23.15 55.53 106.74
Calculate Λm for all concentrations and draw a plot between Λm and c½. Find the value of Λmo.
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3.11 Conductivity of 0.00241 M acetic acid is 7.896 × 10–5 S/cm. Calculate its molar conductivity
and if Λmo for acetic acid is 390.5 S cm2 mol–1, what is its dissociation constant?
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NCERT EXAMPLAR
16. Λom (NH4OH) is equal to ______________.
(i) Λom (NH4OH) + Λom (NH4Cl) – Λom (HCl)
(ii) Λom (NH4Cl) + Λom (NaOH) – Λom (NaCl)
(iii) Λom (NH4Cl) + Λom (NaCl) – Λom (NaOH)
(iv) Λom (NaOH) + Λom (NaCl) – Λom (NH4Cl)

Ans = (ii)
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NCERT EXAMPLAR
22*. Λom H2O is equal to _______________.
(i) Λom (HCl) + Λom (NaOH) – Λom (NaCl)
(ii) Λom (HNO3) + Λom (NaNO3) – Λom (NaOH)
(iii) Λom (HNO3) + Λom (NaOH) – Λom (NaNO3)
(iv) Λom (NH4OH) + Λom (HCl) – Λom (NH4Cl)

Ans = (i & iv)

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53. Match the items of Column I and Column II.
Column I Column II
(i) k (a) I × t
(ii) Λm (b) ΛmൗΛo
m

(iii) ∝ k
(c)
C
(iv) Q G∗
(d)
R

Ans = (i) ~ (d) (ii) ~ (c) (iii) ~ (b) (iv) ~ (a)