The conductivity of sodium chloride at 298 K has been determined at different concentrations and the results are given below:
| 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 |
Calculate Λm for all concentrations and draw a plot between Λm and c1/2. Find the value of Λm0.
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🔒 Start your 14-day free trial to unlock the full solution →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). …
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 …
Concept: Molar Conductivity
Molar conductivity Λm is defined as Λm=cκ, where κ is the conductivity in S m−1 and c is the concentration in mol m−3. For strong electrolytes like NaCl, Λm varies linearly with c at low concentrations, and the intercept at c=0 gives the limiting molar conductivity Λm0.
Step 1: Convert units
Concentration in M (mol L−1) must be converted to mol m−3:
1 M=1000 mol m−3.
So c values: 1, 10, 20, 50, 100 mol m−3.
Step 2: Calculate Λm for each concentration
Using Λm=cκ (with κ in S m−1 and c in mol m−3), and noting κ is given as 102×κ, so actual κ=(table value)×10−2 S m−1.
| c (mol m−3) | κ (S m−1) | Λm (S m2 mol−1) |
|---|---|---|
| 1 | 1.237×10−2 | 1.237×10−2 |
| 10 | 11.85×10−2 | 1.185×10−2 |
| 20 | 23.15×10−2 | 1.158×10−2 |
| 50 | 55.53×10−2 | 1.111×10−2 |
| 100 | 106.74×10−2 | 1.067×10−2 |
Step 3: Plot Λm vs c
c values: 1, 3.162, 4.472, 7.071, 10 (in mol m−3). …
Molar conductivity Λm is calculated from κ and concentration using Λm=κ/c, then plotted against c to extrapolate to infinite dilution. The intercept gives Λm0≈126.5 S cm2 mol−1.
The key idea here is that molar conductivity Λm measures how well a solution conducts electricity per mole of electrolyte. As concentration decreases, ions move more freely because interionic attractions weaken. By plotting Λm against c and extrapolating to zero concentration, we find Λm0 — the conductivity at infinite dilution where ions are completely independent.
For strong electrolytes like NaCl, the Debye-Hückel-Onsager theory predicts a linear relationship between Λm and c at low concentrations. This linearity lets us extrapolate reliably.
1. Convert units and calculate Λm for each concentration
Molar conductivity is defined as:
Λm=cκ
where κ is in S m−1 and c is in mol m−3. But the table gives κ as 102×κ in S m−1, so actual κ=(table value)×10−2 S m−1.
Also, concentration is given in M (mol/L), which is mol dm−3. To convert to mol m−3, multiply by 1000:
c (mol m−3)=c (M)×1000
Let's compute for each row:
For c=0.001 M:
- c=0.001×1000=1.0 mol m−3
- κ=1.237×10−2=0.01237 S m−1
- Λm=1.00.01237=0.01237 S m2 mol−1
But molar conductivity is usually expressed in S cm2 mol−1. Since 1 S m2=104 S cm2:
Λm=0.01237×104=123.7 S cm2 mol−1
Similarly for c=0.010 M:
- c=10 mol m−3
- κ=11.85×10−2=0.1185 S m−1
- Λm=100.1185=0.01185 S m2 mol−1=118.5 S cm2 mol−1
For c=0.020 M:
- c=20 mol m−3
- κ=23.15×10−2=0.2315 S m−1
- Λm=200.2315=0.011575 S m2 mol−1=115.75 S cm2 mol−1
For c=0.050 M:
- c=50 mol m−3
- κ=55.53×10−2=0.5553 S m−1
- Λm=500.5553=0.011106 S m2 mol−1=111.06 S cm2 mol−1
For c=0.100 M:
- c=100 mol m−3
- κ=106.74×10−2=1.0674 S m−1
- Λm=1001.0674=0.010674 S m2 mol−1=106.74 S cm2 mol−1
2. Tabulate Λm and c
| c (M) | c (M1/2) | Λm (S cm2 mol−1) |
|---|---|---|
| 0.001 | 0.03162 | 123.7 |
| 0.010 | 0.1000 | 118.5 |
| 0.020 | 0.1414 | 115.75 |
| 0.050 | 0.2236 | 111.06 |
| 0.100 | 0.3162 | 106.74 |
3. Plot and extrapolate …
Method: Kohlrausch’s Law & Extrapolation Method
This method uses the relationship between molar conductivity (Λm) and concentration (c) for strong electrolytes, followed by graphical extrapolation to infinite dilution.
Step 1: Calculate Λm for each concentration
Formula:
Λm=cκ
Where:
- κ = conductivity (in S m−1)
- c = concentration (in mol m−3)
Important: Convert concentration from M (mol L−1) to mol m−3:
c (mol m−3)=c (M)×1000
Step 2: Perform the calculations
For 0.001 M:
- c=0.001×1000=1 mol m−3
- κ=1.237×10−2 S m−1
- Λm=11.237×10−2=1.237×10−2 S m2 mol−1
Similarly for all concentrations:
| c (M) | c (mol m−3) | κ (S m−1) | Λm (S m2 mol−1) |
|---|---|---|---|
| 0.001 | 1 | 1.237×10−2 | 1.237×10−2 |
| 0.010 | 10 | 11.85×10−2 | 1.185×10−2 |
| 0.020 | 20 | 23.15×10−2 | 1.158×10−2 |
| 0.050 | 50 | 55.53×10−2 | 1.111×10−2 |
| 0.100 | 100 | 106.74×10−2 | 1.067×10−2 |
Step 3: Calculate c values
| c (M) | c (M1/2) |
|---|---|
| 0.001 | 0.0316 |
| 0.010 | 0.1000 |
| 0.020 | 0.1414 |
| 0.050 | 0.2236 |
| 0.100 | 0.3162 |
Step 4: Plot Λm vs c
- X-axis: c (in M1/2)
- Y-axis: Λm (in S m2 mol−1) …
Common Mistakes & How to Avoid Them
Mistake 1: Mishandling the "102×κ" Table Header
The error: Students read the table value (e.g., 1.237) as κ itself, instead of realising the header says 102×κ, so the actual conductivity is the table value ×10−2.
Why it happens: Tables in NCERT-style problems often report a scaled quantity to keep the numbers tidy, and it's easy to skip past the header notation under time pressure.
How to avoid:
- Always read the column header literally: if it says 102×κ / S m−1, then κ=(table value)×10−2 S m−1.
- For c=0.001 M: table value is 1.237, so κ=1.237×10−2 S m−1, not 1.237 S m−1.
Mistake 2: Forgetting to Convert Concentration from mol L⁻¹ to mol m⁻³
The error: Dividing κ (in S m⁻¹) directly by c in mol L⁻¹ (i.e., 0.001, 0.01, etc.) without converting to SI concentration units, which gives an answer 1000× too large.
How to avoid:
- Since 1 M=1000 mol m−3, always convert first: c (mol m−3)=c (M)×1000.
- For c=0.001 M: c=1 mol m−3.
Mistake 3: Mixing S m² mol⁻¹ and S cm² mol⁻¹ Without Converting
The error: Computing Λm in SI units (S m2 mol−1, which comes out as a small number like 0.0124) and then comparing it directly against a Λm0 value quoted in S cm2 mol−1 (typically in the hundreds) without converting, making the numbers look wildly inconsistent.
How to avoid:
- Remember: 1 S m2 mol−1=104 S cm2 mol−1.
- Pick ONE unit system and stick with it for every row of the table and for the extrapolated intercept.
Mistake 4: Plotting Λm Against c Instead of c
The error: For a strong electrolyte like NaCl, students plot Λm directly against concentration c and try to extrapolate — but Kohlrausch's law says the linear relationship is with c, not c itself, so extrapolating the wrong plot gives a wrong intercept.
How to avoid:
- Always compute c for each row first.
- Plot Λm (y-axis) against c (x-axis) — only this plot is a straight line for a strong electrolyte, per Λm=Λm0−Ac.
Mistake 5: Estimating the Intercept from Only Two (Often the Closest) Data Points …
- KEAM 2026Set eng-2026-04214 marksMCQQ.The molar conductivity of a weak mono basic acid, HA at 298 K is 70 Scm2mol−1. What is the percentage ionisation of HA at 298 K? [At infinite dilution λH+=340 Scm2mol−1 and λA−=80 Scm2mol−1] (A) 8.35 % (B) 16.7 % (C) 20 % (D) 32.5 % (E) 15.3 %
›Reveal solutionSolution
α=Λm/Λm∘=70/420=16.7.
Limiting molar conductivity of HA:
Λm∘=λH+∘+λA−∘=340+80=420,Scm2mol−1.
Degree of ionisation: …
- KEAM 2026Set pha-2026-0418F4 marksMCQQ.The limiting molar conductance for aqueous solution of CaCl2 at 298K is 271.6 S cm2 mol−1. If the limiting ionic conductance of Ca2+ ion at the same temperature is 119 S cm2 mol−1 what is the limiting ionic conductance of Cl− ion? (A) 152.6 S cm2 mol−1 (B) 76.3 S cm2 mol−1 (C) 135.8 S cm2 mol−1 (D) 228.7 S cm2 mol−1 (E) 114.35 S cm2 mol−1
›Reveal solutionSolution
Kohlrausch: Λm∘(CaCl2)=λ∘(Ca2+)+2λ∘(Cl−).
271.6=119+2λ∘(Cl−) …
- KEAM 2025Set eng-2025-04254 marksMCQQ.The molar conductivity (Λm) acetic acid is 78.1 S cm2 mol−1. Its degree of dissociation (α) is (Λm0) for acetic acid = 390.5 S cm2 mol−1 (A) 0.12 (B) 0.40 (C) 0.02 (D) 0.20 (E) 0.04
›Reveal solutionSolution
Degree of dissociation of a weak electrolyte α=Λm0Λm=390.578.1=0.20.
For a weak electrolyte such as acetic acid, the degree of dissociation is the ratio of the molar conductivity at the given concentration to the molar conductivity at infinite dilution:
α=Λm0Λm …
- KEAM 2025Set pha-2025-0424F4 marksMCQQ.The ion with the highest limiting molar conductance at 298 K is (A) H+ (B) Na+ (C) K+ (D) Ca2+ (E) Mg2+
›Reveal solutionSolution
The proton conducts by the Grotthuss (hopping) mechanism, giving H+ by far the largest limiting molar conductivity (≈350 S cm2 mol−1).
Limiting molar conductivities at 298 K (in S cm2 mol−1) are roughly:
- H+≈349.8
- K+≈73.5
- Ca2+≈119 (but per mole of charge ≈59.5)
- Na+≈50.1
- Mg2+≈106 (per mole of charge ≈53) …
- KEAM 2024Set eng-2024-06074 marksMCQQ.The conductivity of 0.02 mol L−1 KCl solution is 0.248 S m−1. Its molar conductivity is (A) 20 S m2 mol−1 (B) 1.24×10−3 S m2 mol−1 (C) 1.24×10−4 S m2 mol−1 (D) 2.48×10−2 S m2 mol−1 (E) 1.24×10−2 S m2 mol−1
›Reveal solutionSolution
Molar conductivity Λm=κ/c. With κ=0.248 S m−1 and c=0.02 mol L−1=20 mol m−3, Λm=1.24×10−2 S m2 mol−1.
Molar conductivity is related to conductivity by
Λm=cκ.
Using SI units, the concentration must be in mol m−3:
c=0.02 mol L−1=0.02×1000=20 mol m−3. …
- KEAM 2024Set eng-2024-06084 marksMCQQ.The limiting molar conductances of NaCl, HCl and CH3COONa at 300 K are 126.4, 425.9 and 91.0 S cm2 mol−1 respectively. The limiting molar conductance of acetic acid at 300 K is (A) 266 S cm2 mol−1 (B) 390.5 S cm2 mol−1 (C) 461.3 S cm2 mol−1 (D) 208 S cm2 mol−1 (E) 108 S cm2 mol−1
›Reveal solutionSolution
Kohlrausch's law of independent ion migration lets the limiting molar conductance of acetic acid be built from those of sodium acetate, HCl and NaCl: 91.0+425.9−126.4=390.5 S cm2 mol−1.
Acetic acid dissociates into CH3COO− and H+. Combining known limiting conductances:
Λm∘(CH3COOH)=Λm∘(CH3COONa)+Λm∘(HCl)−Λm∘(NaCl). …
- KEAM 2021Set eng-2021-P1-A14 marksMCQQ.The SI unit of molar conductivity is (A) S m3 mol−1 (B) S m mol−1 (C) S m mol−2 (D) S m2 mol−1 (E) S m2 mol−2
›Reveal solutionSolution
The SI unit of molar conductivity is S m2 mol−1.
Concept and Intuition
Molar conductivity is the conductivity per unit molar concentration, defined as Λm=κ/c. Its unit follows directly from the units of conductivity and concentration in SI.
Step-by-Step Solution
- Conductivity κ has SI unit S m−1.
- Concentration c in SI is mol m−3. …
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