Q.Calculate Λm0 for CaCl2 and MgSO4 from the data given in Table 3.4.
(The relevant limiting molar conductivities are: λ0(Ca2+)=119.0, λ0(Cl−)=76.3, λ0(Mg2+)=106.0 and λ0(SO42−)=160.0 S cm2 mol−1.)
Concept understanding — Molar Conductivity
From Resistance to Conductance: Flipping the Idea
You already know resistance (R) — it tells you how much a material opposes the flow of current. A high resistance means the wire fights the current; a low resistance means it lets current through easily.
Now flip that thought. Instead of asking "how much does it resist?", ask "how easily does it let current flow?" That's exactly what conductance measures.
Conductance (G) is the reciprocal of resistance:
G=R1
Unit: siemens (S) — named after Werner von Siemens. 1 S = 1 A/V (ampere per volt).
If a wire has R=10 Ω, its conductance is G=0.1 S. If R=0.5 Ω, G=2 S — it conducts twice as well.
Ohm's Law in Conductance Form
You know V=IR. Rearranging:
I=RV=GV
So current = conductance × voltage. A high-conductance material draws a large current for the same voltage — it's a "good conductor."
Now, Conductivity: The Material's Intrinsic Property
Resistance depends on two things: the material itself (its "resistivity" ρ) and the geometry (length L, cross-sectional area A):
R=ρAL
Conductance also depends on geometry. A thicker wire (larger A) or a shorter wire (smaller L) has higher conductance. To isolate the material's inherent ability to conduct, we define conductivity (σ):
σ=ρ1
And for a uniform wire:
G=σLA
Conductivity is the reciprocal of resistivity. It tells you how well the material itself conducts, independent of shape and size.
- Unit: siemens per metre (S/m).
- High σ → good conductor (copper: ≈5.8×107 S/m).
- Low σ → poor conductor / insulator (glass: ≈10−12 S/m).
Don't confuse conductance (property of a specific object, depends on geometry) with conductivity (property of the material, independent of geometry). A short thick copper wire has high conductance; a long thin copper wire has lower conductance — but both have the same conductivity.
The Big Picture in One Table
| Quantity | Symbol | Definition | Depends on | Unit |
|---|---|---|---|---|
| Resistance | R | V/I | Material + geometry | Ω |
| Resistivity | ρ | RA/L | Material only | Ω⋅m |
| Conductance | G | 1/R | Material + geometry | S |
| Conductivity | σ | 1/ρ | Material only | S/m |
Intuitive Analogy
Think of a water pipe:
- Resistance = how hard it is to push water through (narrow, long pipe).
- Conductance = how easily water flows (wide, short pipe).
- Resistivity = the "roughness" of the pipe's inner surface (material property).
- Conductivity = the "smoothness" of the pipe's inner surface (material property).
A copper pipe is smooth (high conductivity). A rubber hose is rough (low conductivity). But a short, fat rubber hose might still have decent conductance — because geometry can compensate for poor material.
Key Takeaway for Exams
- G=R1 and σ=ρ1.
- G=σLA for a uniform conductor.
- Conductivity is an intrinsic material property; conductance is an extrinsic property of a specific object.
- In circuits, you'll often use conductance when dealing with parallel resistors (total conductance = sum of individual conductances).
You now have the complete picture: from resistance to conductance, from resistivity to conductivity — and the clean relationship between them.
Molar conductivity is a quantitative cornerstone of the NCERT/CBSE Class 12 Chemistry Electrochemistry chapter, and ‘molar conductivity formula’ or ‘molar conductivity vs concentration’ are recurring important-question types in board exams as well as JEE Main and NEET chemistry. This concept also sets up Kohlrausch's law, a common follow-on topic in the same unit.
Why this formula?
Conductance and Conductivity: Why the Formulas Hold
Let's build this from first principles — understanding the why before the what.
1. The Core Idea: How Easily Does Current Flow?
Think of a conductor (like a copper wire). When you apply a voltage across it, electrons drift through the material. Two questions arise:
- How much current flows for a given voltage? → This is conductance (G).
- How well does the material itself allow current? → This is conductivity (σ).
The key distinction: Conductance depends on the size and shape of the object. Conductivity is an intrinsic property of the material.
2. Ohm's Law in Terms of Conductance
You know Ohm's law:
V=IR
But we can rewrite it as:
I=RV
Define conductance G as the reciprocal of resistance:
G=R1
So:
I=GV
Why this makes sense:
- A larger G means more current for the same voltage — the conductor "conducts" better.
- G has units of siemens (S) = A/V.
3. From Resistance to Conductivity: The Geometry Factor
Resistance of a uniform conductor depends on:
- Length L (longer → more resistance)
- Cross-sectional area A (thicker → less resistance)
- Material property ρ (resistivity)
The formula:
R=ρAL
Now, conductivity σ is the reciprocal of resistivity:
σ=ρ1
So:
R=σ1⋅AL
Why this form?
- If you double the length, electrons have to travel twice as far, colliding more → resistance doubles.
- If you double the area, there's twice as many "lanes" for electrons → resistance halves.
4. The Key Formula: Conductance in Terms of Conductivity
Since G=1/R, we get:
G=σLA
This is the central relationship. Let's see why it holds:
- σ tells you how well the material conducts (intrinsic).
- A/L tells you how the geometry amplifies or reduces that.
Intuition:
- A fat, short wire (A large, L small) has high conductance.
- A thin, long wire (A small, L large) has low conductance.
- A material with high σ (like copper) gives higher G than one with low σ (like iron), for the same shape.
5. Microscopic Derivation (Why σ Exists)
At the microscopic level, conductivity arises from electron motion:
σ=neμ
Where:
- n = number of free electrons per unit volume
- e = electron charge
- μ = electron mobility (how fast they drift per unit electric field)
Why this works:
- More free electrons (n large) → more charge carriers → higher conductivity.
- Higher mobility (μ large) → electrons move faster for the same push → higher conductivity.
This explains why metals (high n) are good conductors, and why heating reduces σ (more collisions → lower μ).
6. Summary: The Logical Chain
| Step | Concept | Formula | Why |
|---|---|---|---|
| 1 | Ohm's law | V=IR | Voltage drives current against resistance |
| 2 | Conductance | G=1/R | Measures ease of flow |
| 3 | Resistivity | R=ρL/A | Geometry + material |
| 4 | Conductivity | σ=1/ρ | Material's intrinsic ability |
| 5 | Key result | G=σLA | Combines material + geometry |
Final takeaway:
Conductance G is not just a number — it's the product of how good the material is (σ) and how the shape helps (A/L). This is why a thick copper wire conducts far better than a thin iron wire of the same length.
Concept: Molar Conductivity — Kohlrausch’s law of independent migration of ions states that the limiting molar conductivity of an electrolyte is the sum of the limiting molar conductivities of its constituent ions, each multiplied by its stoichiometric coefficient.
Step 1: For CaCl2
CaCl2 dissociates as Ca2++2Cl−.
Using Kohlrausch’s law:
Λm0(CaCl2)=λ0(Ca2+)+2λ0(Cl−)
Step 2: Substitute values
Λm0(CaCl2)=119.0+2(76.3)=119.0+152.6=271.6 S cm2 mol−1
Step 3: For MgSO4
MgSO4 dissociates as Mg2++SO42−.
Λm0(MgSO4)=λ0(Mg2+)+λ0(SO42−)=106.0+160.0=266.0 S cm2 mol−1
The limiting molar conductivity is 271.6 S cm2 mol−1 for CaCl2 and 266.0 S cm2 mol−1 for MgSO4.
Kohlrausch's law of independent migration of ions lets us add the limiting molar conductivities of the individual ions, weighted by their stoichiometric coefficients, to get the limiting molar conductivity of the whole salt. For CaCl2: Λm0=119.0+2(76.3)=271.6 S cm2 mol−1. For MgSO4: Λm0=106.0+160.0=266.0 S cm2 mol−1.
The printed question cites "Table 3.4" — a leftover from NCERT's pre-rationalization numbering, when Electrochemistry was Unit 3; it refers to the same ionic limiting molar conductivities as today's Table 2.4 in the current textbook, which the values below are taken from.
The key idea is that at infinite dilution, ions behave completely independently — they don't interact with each other. So the total conductivity of a salt solution is simply the sum of the contributions from each type of ion, each multiplied by how many of that ion appear in the formula unit.
This is Kohlrausch's law of independent migration. It's a powerful shortcut: you don't need to measure every salt directly. Once you know the limiting molar conductivity of a few key ions, you can predict Λm0 for any salt made from them.
Let's apply it.
- For CaCl2 One formula unit gives one Ca2+ ion and two Cl− ions. So:
Λm0(CaCl2)=λ0(Ca2+)+2⋅λ0(Cl−)
Plug in the numbers:
Λm0=119.0+2(76.3)=119.0+152.6=271.6 S cm2 mol−1
- For MgSO4 One formula unit gives one Mg2+ and one SO42− ion. So:
Λm0(MgSO4)=λ0(Mg2+)+λ0(SO42−)
Substituting:
Λm0=106.0+160.0=266.0 S cm2 mol−1
A common mistake is to forget the stoichiometric coefficient. For CaCl2, students sometimes add only one Cl− contribution. Always check the formula: CaCl2 means two chlorides per calcium.
Notice that MgSO4 has a lower Λm0 than CaCl2 even though SO42− has a much higher λ0 than Cl−. Why? Because CaCl2 has three ions per formula unit, while MgSO4 has only two. The number of charge carriers matters.
The limiting molar conductivities are Λm0(CaCl2)=271.6 S cm2 mol−1 and Λm0(MgSO4)=266.0 S cm2 mol−1.
Method: Kohlrausch’s Law of Independent Migration of Ions
This law states that at infinite dilution, each ion contributes a fixed amount to the total molar conductivity of an electrolyte, independent of the other ion present.
Steps
- Recall the formula For any electrolyte AxBy:
Λm0=x⋅λ0(Ay+)+y⋅λ0(Bx−)
where x and y are the number of cations and anions per formula unit.
- For CaCl2
- CaCl2 dissociates as: Ca2++2Cl−
- So x=1, y=2
- Using given values:
Λm0(CaCl2)=1×λ0(Ca2+)+2×λ0(Cl−)
=1(119.0)+2(76.3)
=119.0+152.6
271.6 S cm2 mol−1
- For MgSO4
- MgSO4 dissociates as: Mg2++SO42−
- So x=1, y=1
- Using given values:
Λm0(MgSO4)=1×λ0(Mg2+)+1×λ0(SO42−)
=106.0+160.0
266.0 S cm2 mol−1
Key Concept Check
- Why does this work? At infinite dilution, ions are so far apart that they don’t interact — each ion’s conductivity is purely its own property.
- Units note: All values are in S cm2 mol−1 — always include units in your final answer for exams.
Common Mistakes Students Make with Molar Conductivity (and How to Avoid Them)
Mistake 1: Forgetting to Multiply by Stoichiometric Coefficients
The error:
Students often directly add the given ionic conductivities without considering the number of ions in the formula unit. For example, for CaCl2, they write:
Λm0=λ0(Ca2+)+λ0(Cl−)
This is wrong because CaCl2 has two chloride ions.
How to avoid:
Always write the dissociation equation first:
CaCl2→Ca2++2Cl−
Then apply Kohlrausch’s law correctly:
Λm0=ν+λ+0+ν−λ−0
where ν is the number of ions of each type.
Correct calculation:
Λm0(CaCl2)=1×119.0+2×76.3=119.0+152.6=271.6 S cm2 mol−1
Mistake 2: Confusing the Formula for 1:1 vs 2:2 Electrolytes
The error:
For MgSO4, students sometimes incorrectly multiply both ions by 2, thinking "both are divalent so double everything."
How to avoid:
Remember: stoichiometry matters, not just charge. MgSO4 dissociates as:
MgSO4→Mg2++SO42−
There is one magnesium ion and one sulfate ion. So:
Λm0(MgSO4)=1×106.0+1×160.0=266.0 S cm2 mol−1
Key insight: Charge tells you the mobility (given in the table), but the count of ions tells you the multiplier.
Mistake 3: Mixing Up Units or Omitting Them
The error:
Students write numbers without units, or confuse S cm2 mol−1 with S m2 mol−1.
How to avoid:
- Always attach units to your final answer.
- In NCERT/board exams, the standard unit is S cm2 mol−1.
- If conversion is needed: 1 S cm2 mol−1=10−4 S m2 mol−1.
Correct final answers with units:
- Λm0(CaCl2)=271.6 S cm2 mol−1
- Λm0(MgSO4)=266.0 S cm2 mol−1
Mistake 4: Using the Wrong Table Values
The error:
Students accidentally swap values (e.g., using λ0(Mg2+) for Ca2+) or misread the table.
How to avoid:
- Label each value as you copy it from the table.
- Double-check: Ca2+=119.0, Cl−=76.3, Mg2+=106.0, SO42−=160.0.
- Cross-check with periodic trends: Ca2+ has higher conductivity than Mg2+ (larger ion, less hydration), so 119>106 makes sense.
Quick Checklist to Avoid All Mistakes
| Step | Action |
|---|---|
| 1 | Write the dissociation equation |
| 2 | Count the number of each ion (ν+ and ν−) |
| 3 | Apply: Λm0=ν+λ+0+ν−λ−0 |
| 4 | Use correct values from the table |
| 5 | Attach units: S cm2 mol−1 |
Final correct answers for reference:
Λm0(CaCl2)=271.6 S cm2 mol−1
Λm0(MgSO4)=266.0 S cm2 mol−1
Showing the 12 most recent of 20 on this concept.
- COMEDK 2026Set 2026-A1 markMCQQ.Resistance of 0.2 M solution of an electrolyte is 50Ω. The conductivity of the solution is 1.3Sm−1. If the resistance of 0.4 M solution of the same electrolyte is 260Ω, its molar conductivity is: (A) 6.25×10−3Sm2 mol−1 (B) 62.5×10−4Sm2 mol−1 (C) 6.25×10−4Sm2 mol−1 (D) 625×10−4Sm2 mol−1
›Reveal solutionSolution
The key is to first find the cell constant from the 0.2 M data, then use it to find the conductivity of the 0.4 M solution, and finally compute its molar conductivity. The result matches option (C).
Concept and intuition
Molar conductivity (Λm) is the conductivity of a solution divided by its molar concentration: Λm=cκ. But we cannot directly measure conductivity — we measure resistance R of a solution in a cell with a fixed geometry. The cell constant G∗ (units m⁻¹) relates conductivity κ to measured conductance 1/R:
κ=G∗⋅R1
So the plan: use the first solution’s known κ and R to find G∗, then use that G∗ with the second solution’s R to find its κ, and finally compute Λm for the second solution.
Step-by-step solution
- Find the cell constant from the 0.2 M data For the 0.2 M solution:
κ1=1.3 Sm−1,R1=50 Ω
Using κ=G∗/R:
G∗=κ1⋅R1=1.3×50=65 m−1
This cell constant is fixed for the same conductivity cell.
- Find the conductivity of the 0.4 M solution For the 0.4 M solution: R2=260 Ω.
κ2=R2G∗=26065=0.25 Sm−1
- Compute the molar conductivity of the 0.4 M solution Molar conductivity Λm is defined as:
Λm=cκ
where c is concentration in mol/m³.
Given c=0.4 M=0.4 mol/L=0.4×103 mol/m3=400 mol/m3.
Λm=400 molm−30.25 Sm−1=6.25×10−4 Sm2mol−1
TipAlways convert concentration from M (mol/L) to mol/m³ by multiplying by 1000 — a common slip is to forget this factor, which would give an answer 1000 times too large.
- Match with the options The value 6.25×10−4 Sm2mol−1 corresponds exactly to option (C).
Watch outOption (A) is 6.25×10−3 — that’s what you’d get if you mistakenly used c=0.4 mol/m3 (i.e., forgot the 1000 factor). Option (B) and (D) are just powers-of-ten variations of the same mistake.
✓Final answerThe correct option is (C).
ANSWER: C
- COMEDK 2026Set 2026-M1 markMCQQ.Identify the correct mathematical expression which represents the variation in molar conductivity of a weak acid having concentration C and ionisation constant Ka ( λm∞= molar conductivity at infinite dilution, λm= molar conductivity at concentration C ) (A) Ka=λm2C/λm∞(λm∞−λm) (B) Ka=λmλm∞−(λm∞)2+λm2C (C) λm+λm∞+KaC21=0 (D) Ka=λm2C/λm∞(λm∞+λm)
›Reveal solutionSolution
The key idea is to combine Ostwald’s dilution law with the relation between molar conductivity and degree of dissociation. The correct expression is option (A).
We start from the fundamental relationship for a weak electrolyte: the degree of dissociation α is given by the ratio of molar conductivity at concentration C to that at infinite dilution:
α=λm∞λm
This works because λm increases with dissociation, and at infinite dilution the electrolyte is fully dissociated.
For a weak acid HA dissociating as:
HA⇌H++A−
Ostwald’s dilution law gives the ionization constant:
Ka=1−αCα2
Now substitute α=λm/λm∞:
Ka=1−λm∞λmC(λm∞λm)2=(λm∞−λm)/λm∞Cλm2/(λm∞)2=λm∞(λm∞−λm)Cλm2
This matches option (A) exactly.
Watch outA common mistake is to forget the denominator (1−α) or to misplace the λm∞ factor. Always check that the units and limiting behavior make sense: as C→0, λm→λm∞ and the expression should blow up (since Ka is constant but the formula must handle the limit carefully).
TipYou can quickly eliminate options by testing a simple case: if λm is very small (weak acid, low dissociation), then Ka≈Cλm2/(λm∞)2, which is plausible. Option (A) gives that; option (D) would give a smaller value because of the plus sign, which is wrong.
✓Final answerThe correct option is (A).
ANSWER: A
- COMEDK 2026Set 2026-M1 markMCQQ.Two statements, one Assertion and the other Reason are given. Choose the right option. Assertion: The Molar conductivity of KCl increases very slowly with dilution and approaches a limiting value when dilution is infinite. Reason: In case of KCl there is an increase in the number of ions on dilution due to complete ionisation at infinite dilution. (A) Both Assertion and Reason are correct and Reason is the correct explanation of Assertion (B) Both Assertion and Reason are correct but Reason is not the correct explanation of Assertion (C) Assertion is incorrect but Reason is correct (D) Assertion is correct but Reason is incorrect
›Reveal solutionSolution
Molar conductivity increases with dilution due to reduced ion-ion interactions, not because more ions are formed — KCl is already fully dissociated. The Assertion is correct, but the Reason is wrong.
The key concept here is Kohlrausch’s law and the distinction between strong and weak electrolytes. KCl is a strong electrolyte — it dissociates completely in water at all dilutions. So the number of ions per formula unit does not increase as you dilute it; it’s already 100% ionised.
The Assertion says molar conductivity of KCl increases slowly with dilution and approaches a limiting value. That is true. But why does it increase? Not because more ions appear — they were already there. The increase happens because ion-ion interactions weaken as the solution gets more dilute. Ions move more freely, so conductivity per mole (molar conductivity) rises. At infinite dilution, ions are independent and molar conductivity reaches its maximum, the limiting molar conductivity Λm∞.
The Reason claims that dilution causes an increase in the number of ions due to complete ionisation at infinite dilution. That is false for KCl — it is already completely ionised even at moderate concentrations. The number of ions per mole of KCl does not change with dilution. So the Reason is incorrect.
Let’s walk through it step by step.
-
Identify the electrolyte type. KCl is a salt of a strong acid (HCl) and a strong base (KOH). In water, it dissociates fully: KCl→K++Cl−. This is true at any dilution — there is no undissociated KCl present. So the degree of ionisation α=1 always.
-
Understand molar conductivity. Molar conductivity Λm is defined as Λm=cκ, where κ is conductivity and c is concentration. For a strong electrolyte, Λm increases as c decreases, but the increase is gradual and follows the Kohlrausch square-root law: Λm=Λm∞−Ac. The limiting value Λm∞ is approached as c→0.
-
Why does Λm increase? At higher concentrations, ions are close together and their mutual electrostatic attractions (ion-ion interactions) slow them down. Dilution separates the ions, reducing these interactions, so each ion moves faster under the applied field. The number of charge carriers per mole is constant — it’s always 2 moles of ions per mole of KCl — but their mobility increases. That’s the sole reason for the rise in Λm.
-
Evaluate the Reason. The Reason says: “there is an increase in the number of ions on dilution due to complete ionisation at infinite dilution.” This is a double error. First, the number of ions does not increase — it’s fixed. Second, complete ionisation is not something that happens at infinite dilution; it was already complete. So the Reason is factually wrong.
Watch outA common mistake is to confuse strong and weak electrolytes. For a weak electrolyte like acetic acid, dilution does increase the degree of ionisation, so the number of ions rises sharply — that’s why its molar conductivity increases steeply. But KCl is strong; its ionisation is already 100%. The Reason given would be correct for a weak electrolyte, but not for KCl.
-
Check the Assertion. “The Molar conductivity of KCl increases very slowly with dilution and approaches a limiting value when dilution is infinite.” This is exactly what Kohlrausch’s law predicts for a strong electrolyte. The increase is slow (linear in c) and it approaches Λm∞. So the Assertion is correct.
-
Determine the relationship. Since the Assertion is correct and the Reason is incorrect, the Reason cannot be the correct explanation — in fact, it’s not even a correct statement. The correct option is therefore (D).
✓Final answerThe correct option is (D): Assertion is correct but Reason is incorrect.
-
- KCET 2026Set D31 markMCQQ.Λmo(NH4OH) is equal to (A) Λmo(NH4OH) + Λmo(NH4Cl) - Λmo(HCl) (B) Λmo(NH4Cl) + Λmo(NaOH) - Λmo(NaCl) (C) Λmo(NH4Cl) + Λmo(NaCl) - Λmo(NaOH) (D) Λmo(NaOH) + Λmo(NaCl) - Λmo(NH4Cl)
›Reveal solutionSolution
Apply Kohlrausch's law of independent ionic migration: combine strong electrolytes sharing NH4+ and OH− so the extra ions (Na+, Cl−) cancel out.
Step 1 — Express each electrolyte's limiting conductivity in terms of ions
Λmo(NH4Cl)=λNH4+o+λCl−o
Λmo(NaOH)=λNa+o+λOH−o
Λmo(NaCl)=λNa+o+λCl−o
Step 2 — Combine to isolate NH4+ and OH−
Adding the first two and subtracting the third:
Λmo(NH4Cl)+Λmo(NaOH)−Λmo(NaCl)=(λNH4+o+λCl−o)+(λNa+o+λOH−o)−(λNa+o+λCl−o)
The λNa+o and λCl−o terms cancel, leaving:
=λNH4+o+λOH−o=Λmo(NH4OH)
Step 3 — Conclusion
This is exactly the standard textbook application of Kohlrausch's law for a weak base like NH4OH, matching option (B).
✓Final answerThe correct option is (B) — Λmo(NH4Cl) + Λmo(NaOH) − Λmo(NaCl).
- COMEDK 2025Set 2025-A1 markMCQQ.Two statements, one Assertion and the other Reason are given. Choose the correct option. Assertion: For strong electrolytes the plot of Molar conductivity versus Concentration gives a straight line with slope equal to +A and intercept equal to λm Reason: For strong electrolytes, λm increases slowly with dilution due to increase in the distance between the ions and increase in ionic mobility (A) Assertion is correct but Reason is incorrect. (B) Both Assertion and Reason are incorrect. (C) Assertion is incorrect but Reason is correct. (D) Both Assertion and Reason are correct.
›Reveal solutionSolution
The assertion incorrectly states the slope is positive (+A) when it is actually negative for strong electrolytes; the reason correctly describes the trend but misattributes it to "slow increase" rather than a small, gradual decrease. The correct option is (C).
The key concept here is Kohlrausch’s law for strong electrolytes. For strong electrolytes (fully dissociated salts like NaCl, KCl), molar conductivity Λm decreases linearly with the square root of concentration c, not increases. The slope is negative because as concentration increases, ion-ion interactions impede mobility. The reason, while describing the correct physical trend (conductivity changes with dilution), gets the direction wrong—it says "increases slowly" when in fact it decreases slightly with increasing concentration.
Let’s break it down step by step.
-
Understand the Assertion
The assertion says: For strong electrolytes, the plot of Molar conductivity versus Concentration gives a straight line with slope equal to +A and intercept equal to λm.
- Kohlrausch’s empirical law states: Λm=Λm0−Ac, where Λm0 is the limiting molar conductivity (intercept) and A is a positive constant.
- This is a straight line when Λm is plotted against c, not against c directly. The slope is −A (negative), not +A.
- Therefore, the assertion is incorrect because it gives the wrong sign for the slope and implies a plot against c (not c).
-
Understand the Reason
The reason says: For strong electrolytes, λm increases slowly with dilution due to increase in the distance between the ions and increase in ionic mobility.
- As we dilute a strong electrolyte, the distance between ions increases, reducing interionic attractions. This does increase ionic mobility, so Λm increases.
- However, the phrase "increases slowly" is misleading: for strong electrolytes, Λm increases sharply at low concentrations and then approaches a constant Λm0; the change is not "slow" in the sense of a small slope. More importantly, the reason correctly identifies the cause (greater distance → less hindrance → higher mobility), but it misstates the rate as "slow".
- Despite this wording issue, the core physical idea is correct: dilution increases molar conductivity for strong electrolytes. So the reason is essentially correct in its causal explanation.
-
Evaluate the options
- (A) Assertion correct, Reason incorrect → No, assertion is wrong.
- (B) Both incorrect → No, reason is largely correct.
- (C) Assertion incorrect, Reason correct → This matches our analysis.
- (D) Both correct → No, assertion is wrong.
Watch outA common mistake is to think the slope is positive because conductivity increases with dilution. But the graph is Λm vs. c (or c), and as concentration decreases (dilution), Λm rises — so the slope with respect to increasing c is negative.
TipRemember the Kohlrausch equation: Λm=Λm0−Ac. The intercept is Λm0, and the slope is −A. Always check the variable on the x-axis — it’s c, not c.
✓Final answerThe correct option is (C).
ANSWER: C
-
- COMEDK 2025Set 2025-E1 markMCQQ.When 0.1 mol L−1 of KCl was filled in a Conductivity cell the resistance was 80 ohms at 298 K . (Conductivity of 0.1 M KCl at 298 K is 1.29 S m−1. The same cell when filled with an unknown electrolyte of concentration 0.025 M , had a resistance of 92 ohms. What is the Molar conductivity of the electrolyte at the given concentration? (A) 220.6 S cm2 mol−1 (B) 0.2206 S cm2 mol−1 (C) 448 S cm2 mol−1 (D) 0.449 S cm2 mol−1
›Reveal solutionSolution
The key is to first find the cell constant from the known KCl data, then use it to get the conductivity of the unknown solution, and finally compute its molar conductivity. The result is 0.448Sm2mol−1, which matches option (C) when converted to Scm2mol−1.
Concept & Intuition
Conductivity cells have a fixed geometry — the distance between electrodes and their area — captured by the cell constant G∗=Aℓ (units: m−1).
We cannot measure ℓ and A directly, but we can find G∗ using a standard solution of known conductivity.
Once we know G∗, any unknown solution’s conductivity is simply κ=G∗/R.
Then molar conductivity Λm=cκ (with careful unit conversion) gives the answer.
Step-by-step
- Find the cell constant from the KCl data For the KCl solution:
κKCl=1.29Sm−1,RKCl=80Ω
The cell constant is:
G∗=κKCl×RKCl=1.29×80=103.2m−1
- Use the cell constant to find the conductivity of the unknown For the unknown solution:
Runknown=92Ω
κunknown=RunknownG∗=92103.2≈1.12174Sm−1
- Convert concentration to SI units The concentration is 0.025M=0.025molL−1. Since 1L=10−3m3:
c=0.025molL−1=0.025×103molm−3=25molm−3
- Compute molar conductivity in SI units
Λm=cκunknown=251.12174=0.0448696Sm2mol−1
- Convert to the units used in the options Options are in Scm2mol−1.
1Sm2mol−1=104Scm2mol−1
So:
Λm=0.0448696×104=448.696Scm2mol−1≈448Scm2mol−1
TipA common mistake is forgetting to convert concentration from mol/L to mol/m³ — that would give a result 1000 times too small, leading to option (D) instead of (C).
✓Final answerThe correct option is (C).
ANSWER: C
- COMEDK 2025Set 2025-M1 markMCQQ.Arrange the following compounds in the decreasing order of the molar conductivities of their aqueous solutions. .tg {border-collapse:collapse;border-spacing:0;} .tg td{border-color:black;border-style:solid;border-width:1px;font-family:Arial, sans-serif;font-size:14px; overflow:hidden;padding:10px 5px;word-break:normal;} .tg th{border-color:black;border-style:solid;border-width:1px;font-family:Arial, sans-serif;font-size:14px; font-weight:normal;overflow:hidden;padding:10px 5px;word-break:normal;} .tg .tg-baqh{text-align:center;vertical-align:top} A B C D [Co(NH3)5Cl]Cl2 [Co(NH3)3Cl3] [Co(NH3)4Cl2]Cl [Co(NH3)6]Cl3 (A) B>C>A>D (B) D>A>C>B (C) B>A>C>D (D) A>B>D>C
›Reveal solutionSolution
Molar conductivity depends on the number of ions produced per formula unit in solution. The more ions, the higher the conductivity. The correct order is D > A > C > B, which corresponds to option (B).
The key concept here is Kohlrausch’s law of independent migration of ions: the molar conductivity of an electrolyte at infinite dilution is the sum of the conductivities of its constituent ions. For a given concentration (here, aqueous solutions at comparable dilution), the compound that dissociates into more ions will have a higher molar conductivity. So we simply count the number of ions each coordination compound releases when dissolved in water.
-
Identify the number of ions per formula unit for each compound.
Coordination compounds in water typically dissociate into the complex ion and the counter ions outside the coordination sphere. The ligands inside the brackets are tightly bound and do not dissociate.
-
A: [Co(NH3)5Cl]Cl2
The complex ion is [Co(NH3)5Cl]2+ and there are two Cl− ions outside.
→ Total ions = 1 complex cation + 2 chloride ions = 3 ions.
-
B: [Co(NH3)3Cl3]
All three chlorines are inside the coordination sphere; no counter ions outside.
→ This is a neutral complex, so it does not dissociate into ions.
→ Total ions = 0 ions (or effectively 1 molecule, but conductivity is negligible).
-
C: [Co(NH3)4Cl2]Cl
The complex ion is [Co(NH3)4Cl2]+ and one Cl− outside.
→ Total ions = 1 complex cation + 1 chloride ion = 2 ions.
-
D: [Co(NH3)6]Cl3
The complex ion is [Co(NH3)6]3+ and three Cl− outside.
→ Total ions = 1 complex cation + 3 chloride ions = 4 ions.
-
-
Arrange in decreasing order of number of ions.
More ions → higher molar conductivity.
- D: 4 ions
- A: 3 ions
- C: 2 ions
- B: 0 ions (negligible conductivity)
So the order is: D > A > C > B.
-
Match with the given options.
Option (B) is exactly D > A > C > B.
Watch outA common mistake is to forget that only ions outside the coordination sphere contribute to conductivity. For example, compound B has three chlorines, but they are all bonded inside the complex, so it does not produce free ions.
TipYou can think of the “charge on the complex” as a quick check: the number of counter ions equals the charge on the complex ion. For D, the complex is +3, so three Cl⁻; for A, +2, so two Cl⁻; for C, +1, so one Cl⁻; for B, neutral, so zero.
✓Final answerThe correct option is (B).
ANSWER: B
-
- COMEDK 2025Set 2025-M1 markMCQQ.The conductivity of 0.01 M solution of CH3COOH at 298 K is 1.65×10−4Scm−1 What is the pKa value of the acid if λ0(H+)and λ0(CH3COO)−1 are 349.1Scm2 mol−1 and 40.9Scm2 mol−1 respectively? (A) 4.73 (B) 1.87 (C) 3.47 (D) 2.95
›Reveal solutionSolution
The pKa is found by first calculating the molar conductivity and degree of dissociation from the given conductivity and limiting conductivities, then using the dissociation constant expression for a weak acid. The result is approximately 4.73, corresponding to option (A).
Concept & Intuition
This problem connects conductivity measurements to acid dissociation. For a weak acid like acetic acid, the molar conductivity at a given concentration is less than the limiting molar conductivity because the acid is only partially dissociated. The ratio of these gives the degree of dissociation (α). Once α is known, the dissociation constant Ka follows from the equilibrium expression, and then pKa=−logKa.
- Calculate the molar conductivity (Λm) of the solution. Molar conductivity is given by Λm=cκ, where κ is the conductivity and c is the concentration in mol/cm³ (since units must match). Here, κ=1.65×10−4Scm−1 and c=0.01molL−1=0.01×10−3molcm−3=10−5molcm−3.
Λm=10−51.65×10−4=16.5Scm2mol−1
- Find the limiting molar conductivity (Λm0) of acetic acid. Using Kohlrausch’s law:
Λm0(CH3COOH)=λ0(H+)+λ0(CH3COO−)
Given λ0(H+)=349.1 and λ0(CH3COO−)=40.9 (both in Scm2mol−1):
Λm0=349.1+40.9=390.0Scm2mol−1
- Determine the degree of dissociation (α). For a weak electrolyte, α=Λm0Λm.
α=390.016.5≈0.04231
- Write the dissociation equilibrium and find Ka. For CH3COOH⇌H++CH3COO−, initial concentration c=0.01M. At equilibrium:
[H+]=[CH3COO−]=cα,[CH3COOH]=c(1−α)
The dissociation constant:
Ka=c(1−α)(cα)(cα)=1−αcα2
Substitute values:
Ka=1−0.042310.01×(0.04231)2=0.957690.01×0.001790≈0.957691.79×10−5≈1.87×10−5
- Calculate pKa.
pKa=−logKa=−log(1.87×10−5)=5−log1.87
log1.87≈0.2718, so:
pKa≈5−0.2718=4.7282≈4.73
TipA common pitfall is forgetting to convert concentration from mol/L to mol/cm³ when using conductivity in S/cm. Here, since the units cancel correctly, using c in mol/L directly with κ in S/cm gives the same numerical result if you remember that 1L=1000cm3. Always check unit consistency.
✓Final answerThe correct option is (A).
ANSWER: A
- KCET 2024Set B-21 markMCQQ.The value of ‘A’ in the equation λm=λm0−AC is same for the pair : (A) NaCl and CaCl2 (B) CaCl2 and MgSO4 (C) NaCl and KBr (D) MgCl2 and NaCl
›Reveal solutionSolution
The slope A of the Debye–Hückel–Onsager plot is fixed by the electrolyte's charge type (1:1, 1:2, 2:2 …), so the pair with the same charge type shares the same A.
Step 1 — What the equation says.
For a strong electrolyte, molar conductivity falls with concentration as
Λm=Λm0−AC.
The C dependence comes from the ionic atmosphere (relaxation + electrophoretic effects). The Debye–Hückel–Onsager theory shows the constant A depends on:
- the nature of the solvent (dielectric constant, viscosity),
- the temperature, and
- the charge type of the electrolyte (i.e. the valencies z+, z−).
It does not depend on which particular ions of that charge type are present.
Step 2 — Classify each substance by charge type.
Electrolyte Ions Charge type NaCl Na+, Cl− 1 : 1 KBr K+, Br− 1 : 1 CaCl2 Ca2+, 2 Cl− 2 : 1 MgCl2 Mg2+, 2 Cl− 2 : 1 MgSO4 Mg2+, SO42− 2 : 2 Step 3 — Test each option.
- (A) NaCl (1:1) and CaCl2 (2:1) — different charge types ✗
- (B) CaCl2 (2:1) and MgSO4 (2:2) — different ✗
- (C) NaCl (1:1) and KBr (1:1) — same charge type ✓
- (D) MgCl2 (2:1) and NaCl (1:1) — different ✗
✓Final answerThe correct option is (C) — NaCl and KBr.
ANSWER: C
- COMEDK 2024Set 2024-A1 markMCQQ.The limiting molar conductivity of NH4OH is 238 S cm2 mol−1. At 25∘C, molar conductance of 0.1M aqueous solution of ammonium hydroxide is 9.54 S cm2 mol−1. The degree of ionisation of NH4OH at the same concentration and temperature is: (A) 4.008% (B) 40.0% (C) 2.08% (D) 32.5%
›Reveal solutionSolution
The degree of ionization is the ratio of molar conductivity at a given concentration to the limiting molar conductivity. For NH₄OH, this gives 9.54 / 238 ≈ 0.04008, which is 4.008%, so option (A) is correct.
The key idea here is Kohlrausch’s law and the concept of degree of ionization for weak electrolytes. Ammonium hydroxide (NH₄OH) is a weak base; it does not fully dissociate in water. The molar conductivity at a given concentration (Λₘ) is less than the limiting molar conductivity (Λₘ⁰) because only a fraction of the molecules are ionized. For weak electrolytes, the degree of ionization (α) is simply:
α=Λm0Λm
This works because the mobility of ions is constant at infinite dilution, and the only reason Λₘ is smaller is that fewer ions are present.
Now, let’s work through it step by step.
-
Identify the given data
- Limiting molar conductivity, Λm0=238S cm2mol−1
- Molar conductivity at 0.1 M, Λm=9.54S cm2mol−1
- Concentration = 0.1 M, temperature = 25°C
-
Recall the formula for degree of ionization
For a weak electrolyte, the degree of ionization is:
α=Λm0Λm
This is valid because at infinite dilution, the electrolyte is fully dissociated, so Λₘ⁰ represents the conductivity if all molecules were ions. At any finite concentration, the actual conductivity is proportional to the fraction dissociated.
- Plug in the numbers
α=2389.54
Calculate:
α=0.040084...
- Convert to percentage
α×100%=0.040084×100%=4.0084%
Rounded to three significant figures, this is 4.008%.
- Match with the options Option (A) is 4.008%, which matches exactly.
Watch outA common mistake is to use the Ostwald dilution formula (which involves concentration and equilibrium constant) unnecessarily. Here, the direct ratio is sufficient because the question gives both Λₘ and Λₘ⁰. Also, be careful: for strong electrolytes, this simple ratio does not give the degree of ionization (due to ion-pairing and interionic effects), but for weak electrolytes like NH₄OH, it is correct.
TipNotice that the concentration (0.1 M) is not needed for the calculation of α here — it is only given to confirm that the solution is dilute enough that the simple ratio applies. If the concentration were very high, the formula might need correction, but at 0.1 M for a weak base, it’s fine.
✓Final answerThe correct option is (A).
ANSWER: A
-
- COMEDK 2024Set 2024-E1 markMCQQ.Given below are 2 statements: Assertion and Reason. Choose the correct option. Assertion: When Molar conductivity for a strong electrolyte is plotted versus C( mol/L)1/2, a straight line is obtained with intercept equal to Molar conductivity at infinite dilution for the electrolyte and Slope equal to −A. All electrolytes of a given type have the same A value. Reason: At infinite dilution, strong electrolytes of the same type will have different number of ions due to incomplete dissociation. (A) Assertion is correct but Reason is incorrect statement. (B) Both Assertion and Reason are correct and Reason is the correct explanation of Assertion. (C) Both Assertion and Reason are incorrect statements. (D) Assertion is incorrect but Reason is correct statement.
›Reveal solutionSolution
The assertion is correct (Kohlrausch’s law gives a straight line for strong electrolytes, with the same slope for a given type), but the reason is false (strong electrolytes dissociate completely at infinite dilution, so the number of ions is the same for a given type). Hence the correct option is (A).
Concept and Intuition
Kohlrausch discovered that for strong electrolytes, molar conductivity Λm decreases linearly with the square root of concentration at low concentrations. This is described by Λm=Λm∞−AC, where Λm∞ is the limiting molar conductivity and A is a constant that depends only on the type of electrolyte (e.g., 1:1, 2:1, etc.) and the solvent, not on the specific ions. The reason given claims that at infinite dilution, strong electrolytes of the same type have different numbers of ions due to incomplete dissociation — but that’s wrong: strong electrolytes dissociate completely at all dilutions, and at infinite dilution they are fully dissociated, so all 1:1 electrolytes give exactly two ions per formula unit, all 2:1 give three, etc. The reason therefore does not explain the assertion and is itself false.
Step-by-step reasoning
- Understanding the assertion For a strong electrolyte, Kohlrausch’s law states:
Λm=Λm∞−AC
This is a linear equation in C. The intercept (at C=0) is Λm∞, and the slope is −A. The constant A depends on the stoichiometry (type) of the electrolyte and the solvent properties (viscosity, dielectric constant), but is the same for all electrolytes of a given type (e.g., all 1:1 electrolytes like NaCl, KCl, HCl have the same A in the same solvent). So the assertion is correct.
-
Examining the reason
The reason says: “At infinite dilution, strong electrolytes of the same type will have different number of ions due to incomplete dissociation.”
- Strong electrolytes (e.g., NaCl, KOH, HCl) dissociate completely in solution at all concentrations, including infinite dilution.
- At infinite dilution, every formula unit of a 1:1 strong electrolyte gives exactly 2 ions (one cation, one anion). For a 2:1 electrolyte (e.g., CaCl₂), it gives 3 ions. So all electrolytes of the same type yield the same number of ions.
- “Incomplete dissociation” applies to weak electrolytes, not strong ones. Hence the reason is false.
-
Connecting assertion and reason
The assertion is true and the reason is false. The reason does not explain the assertion — in fact, it contradicts the known behavior of strong electrolytes. Therefore, the correct choice is that the assertion is correct but the reason is incorrect.
Watch outA common mistake is to think that at infinite dilution, even strong electrolytes might not be fully dissociated. In reality, infinite dilution means complete dissociation for strong electrolytes; incomplete dissociation is a property of weak electrolytes.
✓Final answerThe correct option is (A).
ANSWER: A
- COMEDK 2024Set 2024-M1 markMCQQ.0.1M solution of AgNO3 is taken in a Conductivity cell and a potential difference of 40 V is applied across the ends of a column of this solution whose diameter is 4.0 cm and length of the column is 12 cm. The current used is 0.4 A. The Molar conductivity of the solution is _________. (A) 9.547 Scm2 mol−1 (B) 95.5 Scm2 mol−1 (C) 0.009546 Scm2 mol−1 (D) 954.7 Scm2 mol−1
›Reveal solutionSolution
The molar conductivity is found by first calculating the conductivity from the cell geometry and measured current/voltage, then dividing by the concentration. The result is 95.5Scm2mol−1, which corresponds to option (B).
We are given a conductivity cell with a solution of 0.1M AgNO3. A voltage of 40V is applied, producing a current of 0.4A. The column has diameter 4.0cm and length 12cm. We need the molar conductivity Λm.
Concept and intuition:
Molar conductivity is the conductivity of a solution divided by its molar concentration. Conductivity κ itself is the reciprocal of resistivity, and we can get it from the measured resistance R=V/I and the cell constant G∗=ℓ/A (length over cross-sectional area). So the plan is:
- Find resistance from Ohm’s law.
- Compute the cell constant from the given dimensions.
- Conductivity κ=cell constant/R.
- Molar conductivity Λm=κ/c (with careful unit conversion).
Let’s go step by step.
- Find the resistance of the solution column. Ohm’s law: R=V/I.
R=0.4A40V=100Ω.
- Compute the cell constant G∗. The cell constant is ℓ/A, where ℓ is the distance between electrodes (length of column) and A is the cross-sectional area. Diameter d=4.0cm, so radius r=2.0cm. Area:
A=πr2=π(2.0)2=4πcm2.
Length ℓ=12cm.
Hence:
G∗=Aℓ=4π12=π3cm−1.
- Calculate the conductivity κ. Conductivity is related to resistance by:
κ=RG∗.
So:
κ=1003/π=100π3Scm−1.
Numerically:
κ≈314.1593≈0.009549Scm−1.
- Convert concentration to proper units. Molar concentration c=0.1M=0.1molL−1. For molar conductivity in Scm2mol−1, we need concentration in molcm−3. Since 1L=1000cm3:
c=0.1molL−1=0.1×10−3molcm−3=10−4molcm−3.
- Compute molar conductivity Λm.
Λm=cκ=10−40.009549=95.49Scm2mol−1.
Rounding gives 95.5Scm2mol−1.
TipA common mistake is forgetting to convert concentration from mol/L to mol/cm³. If you use c=0.1 directly, you get a number 1000 times too large or too small. Always check units: molar conductivity in Scm2mol−1 demands κ in Scm−1 and c in molcm−3.
✓Final answerThe correct option is (B).
ANSWER: B
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