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Questions
State Kohlrausch’s law of independent migration of ions.
State the following:
Kohlrausch law of independent migration of ions.
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Solution
Kohlrausch’s law states that the molar conductivity of an electrolyte at infinite dilution is the same as the sum of the anions' and cations' limited molar conductivities.
`∧_m^° = v_+ λ_+^° + v_- λ_-^°`
Here `λ_+^°` and `λ_-^°` are limiting molar conductivities of cations and anions.
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Resistance of conductivity cell filled with 0.1 M KCl solution is 100 ohms. If the resistance of the same cell when filled with 0.02 M KCl solution is 520 ohms, calculate the conductivity and molar conductivity of 0.02 M KCl solution. [Given: Conductivity of 0.1 M KCl solution is 1.29 S m-1 .]
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The conductivity of 0.20 mol L−1 solution of KCl is 2.48 × 10−2 S cm−1. Calculate its molar conductivity and degree of dissociation (α). Given λ0 (K+) = 73.5 S cm2 mol−1 and λ0 (C1−) = 76.5 S cm2 mol−1.
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| 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 |
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In the plot of molar conductivity (∧m) vs square root of concentration (c1/2), following curves are obtained for two electrolytes A and B:

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Conductivity always decreases with decrease in concentration both, for weak and strong electrolytes because of the fact that ____________.
\[\ce{\Lambda^0_m(NH4OH)}\] is equal to ______.
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(i) \[\ce{Λ^0_m_{(HCl)} + \ce{Λ^0_m_{(NaOH)} - \ce{Λ^0_m_{(NaCl)}}}}\]
(ii) \[\ce{Λ^0_m_{(HNO_3)} + \ce{Λ^0_m_{(NaNO_3)} - \ce{Λ^0_m_{(NaOH)}}}}\]
(iii) \[\ce{Λ^0_{(HNO_3)} + \ce{Λ^0_m_{(NaOH)} - \ce{Λ^0_m_{(NaNO_3)}}}}\]
(iv) \[\ce{Λ^0_m_{(NH_4OH)} + \ce{Λ^0_m_{(HCl)} - \ce{Λ^0_m_{(NH_4Cl)}}}}\]
When acidulated water (dil.H2SO4 solution) is electrolysed, will the pH of the solution be affected? Justify your answer.
Why on dilution the m Λm of \[\ce{CH3COOH}\] increases very fast, while that of \[\ce{CH3COONa}\] increases gradually?
Match the items of Column I and Column II on the basis of data given below:
`E_("F"_2//"F"^-)^Θ` = 2.87 V, `"E"_(("Li"^(+))//("Li"^-))^Θ` = − 3.5V, `"E"_(("Au"^(3+))//("Au"))^Θ` = 1.4 V, `"E"_(("Br"_(2))//("Br"^-))^Θ` = 1.09 V
| Column I | Column II |
| (i) F2 | (a) metal is the strongest reducing agent |
| (ii) Li | (b) metal ion which is the weakest oxidising agent |
| (iii) Au3+ | (c) non metal which is the best oxidising agent |
| (iv) Br– | (d) unreactive metal |
| (v) Au | (e) anion that can be oxidised by Au3+ |
| (vi) Li+ | (f) anion which is the weakest reducing agent |
| (vii) F– | (g) metal ion which is an oxidising agent |
Assertion: `"E"_("Ag"^+ //"Ag")` increases with increase in concentration of Ag+ ions.
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Choose the right option for your answer.
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\[\begin{array}{cc}
\end{array}\]\[\begin{bmatrix}
\ce{\Lambda^{\circ}_{H^+} = 350 S cm^2 mol^{-1}}\\
\ce{\Lambda^{\circ}_{CH_3COO^-} = 50 S cm^2 mol^{-1}}
\end{bmatrix}\]
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Statements I: The limiting molar conductivity of KCl (strong electrolyte) is higher compared to that of CH3COOH (weak electrolyte).
Statement II: Molar conductivity decreases with decrease in concentration of electrolyte.
In the light of the above statements, choose the most appropriate answer from the options given below:
The following questions are case-based questions. Read the passage carefully and answer the questions that follow:
| Rahul set up an experiment to find the resistance of aqueous KCl solution for different concentrations at 298 K using a conductivity cell connected to a Wheatstone bridge. He fed the Wheatstone bridge with a.c. power in the audio frequency range 550 to 5000 cycles per second. Once the resistance was calculated from the null point, he also calculated the conductivity K and molar conductivity ∧m and recorded his readings in tabular form. |
| S. No. | Conc. (M) |
k S cm−1 | ∧m S cm2 mol−1 |
| 1. | 1.00 | 111.3 × 10−3 | 111.3 |
| 2. | 0.10 | 12.9 × 10−3 | 129.0 |
| 3. | 0.01 | 1.41 × 10−3 | 141.0 |
Answer the following questions:
(a) Why does conductivity decrease with dilution? (1)
(b) If `∧_"m"^0` of KCl is 150.0 S cm2 mol−1, calculate the degree of dissociation of 0.01 M KCI. (1)
(c) If Rahul had used HCl instead of KCl then would you expect the ∧m values to be more or less than those per KCl for a given concentration? Justify. (2)
OR
(c) Amit a classmate of Rahul repeated the same experiment with CH3COOH solution instead of KCl solution. Give one point that would be similar and one that would be different in his observations as compared to Rahul. (2)
Which of the following solutions will have the highest conductivity at 298 K?
The resistance of a conductivity cell with a 0.1 M KCl solution is 200 ohm. When the same cell is filled with a 0.02 M NaCl solution, the resistance is 1100 ohm. If the conductivity of 0.1 M KCl solution is 0.0129 ohm-1 cm-1, calculate the cell constant and molar conductivity of 0.02 M NaCl solution.
The solution of two electrolytes A and B are diluted. ^m of B increases 1.5 times while that of A increases 25 times. Which of the two is a strong electrolyte? Give a reason.
Discuss the variation of conductivity and molar conductivity with concentration.
