Q.(a) State and explain Kohlrausch's law of independent migration of ions.
You're viewing a preview — the full solution, concept, methods & PYQ mapping are locked.
Start your 14-day free trial to unlock the full solution →(a) Kohlrausch's law: molar conductivity at infinite dilution = sum of ionic contributions. (b) Molecularity (number of colliding species in an elementary step, always a whole number, theoretical) differs from order (sum of powers in the experimental rate law, found by experiment, can be fractional/zero); e.g. bimolecular 2HI -> H2 + I2, trimolecular 2NO + O2 -> 2NO2.
(a) Kohlrausch's law of independent migration of ions:
Statement: At infinite dilution, when dissociation of an electrolyte is complete, each ion migrates independently of the co-ion and contributes a definite share to the total molar conductivity of the electrolyte, irrespective of the nature of the other ion with which it is associated. Therefore the limiting molar conductivity of an electrolyte is the sum of the individual limiting molar conductivities of its cation and anion.
Mathematically, for an electrolyte giving nu+ cations and nu- anions:
lambda_m(0) = (nu+) lambda(0,+) + (nu-) lambda(0,-)
where lambda(0,+) and lambda(0,-) are the limiting molar conductivities of the cation and anion respectively.
Example: lambda_m(0)[NaCl] = lambda(0)[Na+] + lambda(0)[Cl-].
Applications: (i) calculation of limiting molar conductivity of weak electrolytes (e.g. CH3COOH) which cannot be obtained by extrapolation; (ii) calculation of the degree of dissociation and dissociation constant of a weak electrolyte; (iii) determination of solubility of sparingly soluble salts.
(b) Molecularity vs order:
Molecularity of a reaction is the number of reacting species (atoms, ions or molecules) that must collide simultaneously in an elementary (single-step) reaction to bring about the chemical change.
Differences from order:
- Molecularity is a theoretical concept defined only for an elementary reaction; order is an experimental quantity determined from the rate law.
- Molecularity is always a whole number (1, 2, 3...) and cannot be zero or fractional; order can be zero, fractional or integral. …
Unlock everything free for 14 days
- Full step-by-step solutions
- Concept-first explanations
- Methods, shortcuts & mistakes
- PYQ mapping + timed mock tests
Full access for 14 days. No credit card required.