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Q.(a) State and explain Kohlrausch's law of independent migration of ions.

(b) Define Order of a reaction. Illustrate your answer with an example. Define molecularity of a reaction. Illustrate with an example.
Telangana TsbieTelangana Board of Intermediate Education 2022Subjective· 8mImportance★★★★★
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Kohlrausch's law lets us calculate Λ°m for any electrolyte, even weak ones, from ionic contributions; order (experimental, can be fractional) and molecularity (theoretical, always a whole number) are two distinct ways of characterizing a reaction's kinetics.

  1. Kohlrausch's Law of Independent Migration of Ions The law states that the limiting molar conductivity of an electrolyte (i.e., its molar conductivity at infinite dilution, Λm∘\Lambda_m^{\circ}) can be expressed as the sum of the individual contributions of its constituent cation and anion. Each ion migrates independently of its co-ion and makes a definite, fixed contribution to the total molar conductivity of the electrolyte, regardless of the nature of the other ion it is associated with. Λm∘=u+λ+∘+u−λ−∘\Lambda_m^{\circ} = u_+ \lambda_+^{\circ} + u_- \lambda_-^{\circ} where ν+\nu_+, ν−\nu_- are the number of cations and anions per formula unit, and λ+∘\lambda_+^{\circ}, λ−∘\lambda_-^{\circ} are their limiting ionic molar conductivities. This law is especially useful for calculating Λm∘\Lambda_m^{\circ} of weak electrolytes (e.g., acetic acid), which cannot be obtained by extrapolation of the conductivity-vs-concentration graph (since weak electrolytes do not have a linear relationship near infinite dilution).
  2. Order of a reaction The order of a reaction is the sum of the powers (exponents) to which the concentration terms of the reactants are raised in the experimentally-determined rate law expression. It is determined experimentally and can be zero, a positive/negative integer, or even a fraction. Example: for the reaction 2NO(g)+O2(g)→2NO2(g)2NO(g) + O_2(g) \rightarrow 2NO_2(g), if the experimental rate law is Rate=k[NO]2[O2]Rate = k[NO]^2[O_2], the order with respect to NO is 2, with respect to O2 is 1, and the overall order of the reaction is 2 + 1 = 3. Molecularity of a reaction …

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