Q.Calculate the molar conductivity of AgI at zero concentration if the molar conductivities of NaI, AgNO3 and NaNO3 at zero concentration are respectively, 126.9, 133.4 and 121.5 Ω−1 cm2 mol−1.
Concept understanding — Kohlrausch's Law
Kohlrausch's law of independent migration of ions states that at infinite dilution, each ion migrates independently of its co-ion and contributes a fixed share to the total molar conductivity regardless of what the other ion is: Λ0=n+λ+0+n−λ−0, where λ+0 and λ−0 are the limiting ionic (molar) conductivities of the cation and anion and n+, n− their numbers in the formula. This lets Λ0 of any strong electrolyte be built directly from tabulated ionic conductivities, and — its more important use — lets Λ0 of a WEAK electrolyte be obtained (even though it cannot be found by extrapolation) from the Λ0 values of related strong electrolytes whose common-ion contributions cancel algebraically, e.g. Λ0(CH3COOH)=Λ0(HCl)+Λ0(CH3COONa)−Λ0(NaCl). Once Λ0 is known, the degree of dissociation of a weak electrolyte at any concentration c follows as α=Λc/Λ0, and its dissociation constant from Ostwald's dilution law, Ka=α2c/(1−α) — a purely electrical route to a thermodynamic equilibrium constant.
"Kohlrausch's law formula and applications" and "Kohlrausch law class 12 important questions" are frequently searched around the Electrochemistry chapter of the NCERT/CBSE Class 12 Chemistry curriculum, since finding a weak electrolyte's limiting molar conductivity is a staple JEE Main and NEET numerical. The worked route from Λ0 to degree of dissociation to Ka via Ostwald's dilution law, as shown here, is exactly the multi-step calculation competitive exams like to chain together in a single question.
By Kohlrausch's law of independent migration of ions, Λ0(AgI)=Λ0(NaI)+Λ0(AgNO3)−Λ0(NaNO3) -- the Na+ and NO3− contributions cancel.
Λ0(AgI)=126.9+133.4−121.5=138.8 Ω−1 cm2 mol−1 -- digit-for-digit the textbook's printed final.
Λ0(AgI)=Λ0(NaI)+Λ0(AgNO3)−Λ0(NaNO3)=126.9+133.4−121.5=138.8 Ω−1 cm2 mol−1.
Step 1. According to Kohlrausch's law, at zero concentration each electrolyte's molar conductivity is the sum of independent ionic contributions:
i. Λ0(NaI)=λNa+0+λI−0 = 126.9
ii. Λ0(AgNO3)=λAg+0+λNO3−0 = 133.4
iii. Λ0(NaNO3)=λNa+0+λNO3−0 = 121.5 (all in Ω−1 cm2 mol−1)
Step 2. Eq. (i) + eq. (ii) - eq. (iii) cancels λNa+0 and λNO3−0, leaving exactly λAg+0+λI−0=Λ0(AgI).
Step 3. Λ0(AgI)=126.9+133.4−121.5=138.8 Ω−1 cm2 mol−1.
Λ0(AgI) = 138.8 Ω−1 cm2 mol−1 -- digit-for-digit the textbook's printed final. (The book's solution heading spells the law "Kohrausch" -- its own spelling; the law is Kohlrausch's.)
Combine the three given electrolytes so the unwanted ions cancel: Lambda0(AgI) = Lambda0(NaI) + Lambda0(AgNO3) - Lambda0(NaNO3), by Kohlrausch's law of independent ionic migration.
- Subtracting the wrong electrolyte: only subtracting Lambda0(NaNO3) removes BOTH spectator ions (Na+ and NO3-) at once.
- Averaging the three values instead of using the add-add-subtract combination.
- Thinking the law applies at any concentration -- independent migration holds at zero concentration (infinite dilution) only.
- CBSE 2026Set SEM43 marksQ.i) What is fuel cell? ii) At 298 K the molar conductances of KCl and LiCl at infinite dilution are Λ°M(KCl) = 149.9 and Λ°M(LiCl) = 115.0 ohm^-1 cm^2 mol^-1. Calculate the value of [Λ°M(KNO3) - Λ°M(LiNO3)].
›Reveal solutionSolution
A fuel cell continuously turns a fuel + oxidant into electricity; and by Kohlrausch's law of independent ionic migration the common nitrate ion cancels, so Lambda(KNO3) - Lambda(LiNO3) equals Lambda(KCl) - Lambda(LiCl) = 34.9 ohm^-1 cm^2 mol^-1.
- Fuel cell A fuel cell is a galvanic (voltaic) cell in which the chemical energy released by the combustion-type reaction of a fuel (such as hydrogen, methane or methanol) with an oxidant (oxygen) is converted directly and continuously into electrical energy, as long as the reactants are fed in from outside. In the H2-O2 fuel cell, at the anode H2 + 2OH- -> 2H2O + 2e- and at the cathode O2 + 2H2O + 4e- -> 4OH-, giving an overall reaction 2H2 + O2 -> 2H2O. It is efficient and pollution-free.
- Using Kohlrausch's law of independent migration of ions At infinite dilution each ion contributes a fixed molar ionic conductance: Lambda(KNO3) = lambda(K+) + lambda(NO3-) Lambda(LiNO3) = lambda(Li+) + lambda(NO3-) Subtracting, the common lambda(NO3-) cancels: Lambda(KNO3) - Lambda(LiNO3) = lambda(K+) - lambda(Li+) The same difference lambda(K+) - lambda(Li+) is obtained from the chlorides (the common lambda(Cl-) cancels there too): lambda(K+) - lambda(Li+) = Lambda(KCl) - Lambda(LiCl) = 149.9 - 115.0 = 34.9 Therefore Lambda(KNO3) - Lambda(LiNO3) = 34.9 ohm^-1 cm^2 mol^-1. Alternative part (B): A lithium-ion battery is a rechargeable cell in which Li+ ions shuttle between a lithiated transition-metal-oxide cathode (e.g. LiCoO2) and a graphite anode through a non-aqueous Li-salt electrolyte during charge/discharge; it is light and gives a high energy density. (The NH4OH Kd part uses Lambda(NH4OH) = Lambda(NH4Cl) + Lambda(NaOH) - Lambda(NaCl) = 129.8 + 217.2 - 109.05 = 238.0 S cm^2 mol^-1, alpha = 9.52/238.0 = 0.04, and Kd = C.alpha^2/(1-alpha) approx 0.01 x (0.04)^2 / 0.96 approx 1.67 x 10^-5.)
✓Final answerA fuel cell converts the chemical energy of a fuel + oxidant directly into electricity. Lambda(KNO3) - Lambda(LiNO3) = Lambda(KCl) - Lambda(LiCl) = 149.9 - 115.0 = 34.9 ohm^-1 cm^2 mol^-1.
- CBSE 2023Set ANNUAL3 marksQ.(i) State the Kohlrausch's law of independent migration of ions.(ii) The specific conductance or conductivity of a 0.01 M acetic acid at 298 K is 1.65x10-4 S cm-1. Calculate molar conductivity of the solution and degree of dissociation of CH3COOH. Given that, lambda-degree(H+) = 349.1 and lambda-degree(CH3COO-) = 40.9 S cm2 mol-1. (1+2) OR(i) Write two functions of salt bridge.(ii) Write Nernst equation of the following galvanic cell and calculate emf of the cell at 298 K temperature: Cu(s) | Cu2+(0.130M) || Ag+(1.0x10-4M) | Ag(s). Given that E-degree(Cu2+/Cu) = +0.34V, E-degree(Ag+/Ag) = +0.80V. (1+2)
›Reveal solutionSolution
Kohlrausch's law lets ionic contributions to conductivity be added independently; applying it to the given data gives a degree of dissociation of about 4.2% for this dilute acetic acid solution.
- Kohlrausch's law of independent migration of ions states that at infinite dilution, each ion migrates independently of its co-ion, and the limiting molar conductivity of the electrolyte is the sum of the limiting ionic conductivities of the cation and anion: Λm∘=u+λ+∘+u−λ−∘
- Molar conductivity from specific conductance: Λm=κ×C1000=1.65×10−4×0.011000=16.5 S cm2mol−1 Limiting molar conductivity via Kohlrausch's law: Λm∘=λ∘(H+)+λ∘(CH3COO−)=349.1+40.9=390 S cm2mol−1 Degree of dissociation: α=Λm∘Λm=39016.5≈0.0423
✓Final answer- Lambda-m-degree = sum of independent limiting ionic conductivities.
- Molar conductivity ~ 16.5 S cm2 mol-1; degree of dissociation alpha ~ 0.0423 (4.23%).
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