Q.In an aqueous solution how does specific conductivity of electrolytes change with addition of water?
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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 …
The key idea is that specific conductivity (κ) measures the conductance of a 1 cm3 column of solution. Adding water dilutes the solution.
- Dilution reduces ion concentration — fewer charge carriers per unit volume.
- However, dilution also increases ion mobility because interionic attractions weaken, allowing ions to move faster.
- For strong electrolytes, the decrease in concentration dominates, so κ decreases steadily as water is added. …
Specific conductivity (κ) of an electrolyte solution decreases when water is added, because dilution reduces the number of charge carriers per unit volume, even though the ions themselves become more mobile.
Why this happens — the core idea
Specific conductivity (κ) measures how well a fixed volume of solution conducts electricity. It depends on two things: how many ions are packed into that volume, and how fast each ion can move. When you add water, you're literally spreading the same number of ions over a larger volume. The concentration drops, so the ion density drops — and κ falls.
But here's the twist: as the solution gets more dilute, ions have more room to move and less interionic attraction to slow them down. Their individual mobility actually increases. So why doesn't κ go up? Because the drop in the number of ions per unit volume is far more dramatic than the gain in mobility. The net effect is a decrease.
A common mistake is to confuse specific conductivity (κ) with molar conductivity (Λₘ). Molar conductivity increases on dilution because it accounts for the number of ions per mole — but specific conductivity, which is a bulk property of the solution, always decreases.
Step-by-step reasoning
- Define specific conductivity (κ) It is the conductance of a 1 cm cube of solution, measured in S cm⁻¹. It depends directly on the concentration of ions (c) and their mobility (u):
κ=∑ici∣zi∣Fui
where F is Faraday's constant and zi is the charge number. The key point: κ is proportional to concentration of ions.
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What happens when water is added?
Adding water dilutes the solution. The number of moles of electrolyte stays the same, but the volume increases. So the concentration c (mol L⁻¹) decreases.
-
Effect on ion density
Fewer ions per unit volume means fewer charge carriers available to conduct electricity through a fixed cross-section. This directly reduces κ.
-
Effect on ion mobility
In a concentrated solution, ions are crowded and experience strong interionic attractions, which slows them down. On dilution, these attractions weaken, and ions move more freely. So mobility u increases slightly.
-
Which effect dominates? …
Method: Dilution Effect Analysis (Kohlrausch's Approach)
This method explains how specific conductivity (κ) changes when water is added to an electrolyte solution.
Step 1 – Understand the two opposing factors
When water is added:
- Number of ions per unit volume decreases (dilution)
- Ionic mobility increases (ions are farther apart, less interionic attraction)
Step 2 – Recall the definition
Specific conductivity (κ) is the conductance of a 1 cm × 1 cm column of solution. It depends on:
- Concentration of ions
- Mobility of ions
Step 3 – Apply the dilution logic
- Initially, at high concentration, κ is high because many ions are present.
- On adding water, the drop in ion concentration dominates over the increase in mobility.
- So κ decreases steadily with dilution.
Step 4 – State the final trend …
Here are the most common mistakes students make when asked about the effect of adding water on specific conductivity (κ), along with the correct reasoning and how to avoid each.
Mistake 1: Confusing Specific Conductivity with Molar Conductivity
The error:
Students often say “conductivity increases because dilution increases dissociation.” This is wrong for specific conductivity (κ), but correct for molar conductivity (Λₘ).
Why it’s wrong:
- Specific conductivity (κ) is the conductance of a 1 cm × 1 cm column of solution.
- Adding water dilutes the number of ions per unit volume.
- Even though each ion moves faster (due to less interionic attraction), the drop in ion concentration dominates → κ decreases.
How to avoid:
- Memorise the key distinction:
- κ (specific) → decreases with dilution.
- Λₘ (molar) → increases with dilution (for weak electrolytes, sharply).
- Write the definition before answering:
κ=ρ1⋅R1(conductance per unit volume)
Dilution → fewer charge carriers per cm³ → κ ↓.
Mistake 2: Forgetting the “Weak vs Strong” Electrolyte Difference
The error:
Students treat all electrolytes the same — saying “κ always decreases linearly.”
Why it’s wrong:
- For strong electrolytes (e.g., NaCl, HCl): κ decreases smoothly as dilution increases.
- For weak electrolytes (e.g., CH₃COOH): κ decreases very sharply at first because dilution also increases dissociation (Le Chatelier’s principle), but the net effect is still a decrease — just not linear.
How to avoid:
- Draw a rough graph in your mind:
- Strong: κ vs concentration → nearly straight line.
- Weak: κ drops steeply at low dilution, then flattens.
- Remember: κ always decreases — the rate differs, not the direction.
Mistake 3: Saying “Conductivity Increases Because More Ions Are Produced”
The error:
Students think that adding water increases the total number of ions (true for weak electrolytes) and therefore κ increases.
Why it’s wrong:
- Yes, for weak electrolytes, dilution shifts equilibrium to produce more ions per molecule.
- But the volume increases even more.
- Ion concentration (ions per cm³) still falls → κ falls.
How to avoid:
- Use the concentration argument:
κ∝(number of ions per unit volume)
Dilution → volume ↑ → concentration ↓ → κ ↓.
- The increase in dissociation cannot compensate for the volume increase.
Mistake 4: Mixing Up “Conductance” and “Conductivity”
The error:
Students treat conductance (G) and specific conductivity (κ) as the same.
Why it’s wrong:
- Conductance G=R1 depends on cell geometry.
- Specific conductivity κ=G×Al is intensive — independent of cell size.
- Adding water changes both, but the question asks about κ (intensive property).
How to avoid: …
Showing the 12 most recent of 15 on this concept.
- TG EAPCET 2026Set eng-2026-05-09-AN1 markMCQQ.KMnO4 oxidizes M2+ to M4+ in acid medium. 500 mL of 0.02 M M2+ solution requires 500 mL of x M MnO4− solution for complete oxidation. The value of x is (A) 16×10−3 (B) 8×10−3 (C) 4×10−3 (D) 2×10−3
›Reveal solutionSolution
This problem involves a redox titration where the gram equivalents of the oxidizing agent (KMnO4) and the reducing agent (M2+) are equal at the equivalence point. By determining the n-factors for both species and using the given concentrations and volumes, we find the unknown molarity x to be 8×10−3 M.
When a redox reaction reaches its equivalence point in a titration, it means that the amount of oxidizing agent added is stoichiometrically exactly enough to react with all of the reducing agent present. In terms of chemical quantities, this is most conveniently expressed using gram equivalents.
The concept of gram equivalents simplifies calculations in redox titrations because it accounts for the number of electrons transferred per mole of reactant. Instead of balancing the full redox equation, we can simply equate the gram equivalents of the oxidant and reductant.
At the equivalence point of a titration:
Gram equivalents of oxidant=Gram equivalents of reductant
Where Gram equivalents=Moles×n-factor
And Moles=Molarity×Volume (in L)
So, (Molarity×n-factor×Volume)oxidant=(Molarity×n-factor×Volume)reductant
The 'n-factor' (or valence factor) for a redox species is the number of electrons gained or lost per mole of the substance in the reaction.
-
Determine the n-factor for M2+:
The problem states that M2+ is oxidized to M4+. This means the oxidation state of M changes from +2 to +4.
The half-reaction for M2+ is:
M2+→M4++2e−
Since 2 electrons are lost per mole of M2+, its n-factor is 2.
-
Determine the n-factor for MnO4− (from KMnO4) in acid medium:
In KMnO4, the oxidation state of manganese (Mn) is +7 (since K is +1 and each O is -2, so 1+Mn+4(−2)=0⇒Mn=+7).
In acid medium, MnO4− is a strong oxidizing agent and is typically reduced to Mn2+ ions.
The half-reaction for MnO4− in acid medium is:
MnO4−+8H++5e−→Mn2++4H2O
Since 5 electrons are gained per mole of MnO4−, its n-factor is 5.
-
Calculate the gram equivalents of M2+:
Given:
Volume of M2+ solution (VM2+) = 500 mL = 0.5 L
Molarity of M2+ solution (MM2+) = 0.02 M
n-factor of M2+ (nM2+) = 2
Gram equivalents of M2+ = MM2+×VM2+×nM2+
Gram equivalents of M2+ = 0.02 M×0.5 L×2=0.02
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Set up the equivalence condition for MnO4−:
At the equivalence point, the gram equivalents of MnO4− must be equal to the gram equivalents of M2+. …
-
- TG EAPCET 2026Set eng-2026-05-09-FN1 markMCQQ.The solubility of BaCO3 (molar mass 197 g mol−1) is 1.4×10−3 g∣100mL. The solubility product constant of BaCO3 is x×10−9 mol2 L−2. The value of x is (nearest integer) (A) 4.0 (B) 5.0 (C) 6.0 (D) 4.8
›Reveal solutionSolution
The solubility product is found by converting the given mass solubility to molar solubility, then squaring it (since BaCO₃ dissociates 1:1). The calculated value is 5.0×10−9, so the nearest integer is 5, corresponding to option (B).
The key idea is that for a sparingly soluble salt like BaCO₃, the solubility product Ksp is directly related to its molar solubility. Because BaCO₃ dissociates into one Ba²⁺ and one CO₃²⁻ ion, Ksp=s2, where s is the molar solubility. The trick is to carefully convert the given solubility in grams per 100 mL into moles per liter.
- Convert the given solubility to grams per liter. The solubility is 1.4×10−3 g per 100 mL. Since 1 L = 1000 mL, multiply by 10:
Solubility in g/L=1.4×10−3×10=1.4×10−2 g/L.
- Convert grams per liter to molar solubility (mol/L). Molar mass of BaCO₃ = 197 g/mol. So:
s=197 g/mol1.4×10−2 g/L=1971.4×10−2 mol/L.
Compute: 1.4/197≈0.0071066, so:
s≈7.1066×10−5 mol/L.
- Write the dissociation equilibrium and Ksp expression.
BaCO3(s)⇌Ba2+(aq)+CO32−(aq)
At equilibrium: [Ba2+]=s and [CO32−]=s.
Hence:
Ksp=s×s=s2.
- Calculate Ksp. Ksp=(7.1066×10−5)2=5.050×10−9 mol2 L−2. …
- TG EAPCET 2026Set eng-2026-05-10-FN1 markMCQQ.The wavelength of electron in the third orbit of hydrogen atom is 6πa0. The kinetic energy of electron (in J) is equal to (Where, K=π2a02meh2, a0 = radius of first orbit of hydrogen, me = mass of electron, h = Planck's constant) (A) 36K (B) 108K (C) 72K (D) 18K
›Reveal solutionSolution
De Broglie momentum p=h/λ gives KE=2mep2=72K.
For the n=3 orbit the de Broglie wavelength is λ=6πa0 (consistent with the quantisation 2πr3=3λ, since r3=9a0).
Momentum of the electron:
p=λh=6πa0h.
Kinetic energy: …
- TG EAPCET 2026Set eng-2026-05-10-FN1 markMCQQ.For a first order reaction, rate constants at 50∘C and 100∘C are 1.5×107 s−1 and 4.5×107 s−1 respectively. What is the approximate activation energy of the reaction (in kJmol−1)? \ (log3=0.48) (R=8.3 Jmol−1K−1) (A) 22 (B) 28 (C) 38 (D) 44
›Reveal solutionSolution
Use the two-point form of the Arrhenius equation to relate the rate constants at two temperatures. The activation energy comes out to approximately 22 kJ/mol.
The Arrhenius equation tells us how the rate constant k depends on temperature T and activation energy Ea:
k=Ae−Ea/RT
When you have rate constants at two different temperatures, the pre-exponential factor A cancels out if you take the ratio. That gives the two-point form:
lnk1k2=REa(T11−T21)
This is the direct route to Ea without needing A.
-
Convert temperatures to Kelvin.
T1=50∘C=323 K
T2=100∘C=373 K
-
Write the ratio of rate constants.
k1=1.5×107 s−1, k2=4.5×107 s−1
k1k2=1.5×1074.5×107=3
- Use the two-point Arrhenius equation in log base 10 form. Since the problem gives log3 (base 10), convert the natural log: lnx=2.303logx.
logk1k2=2.303REa(T11−T21)
Plug in log3=0.48:
0.48=2.303×8.3Ea(3231−3731)
- Compute the temperature difference term.
3231−3731=323×373373−323=12047950
Approximate 323×373≈120500 (close enough for an estimate).
So the term is roughly 12050050=24101.
- Solve for Ea.
0.48=2.303×8.3Ea×24101
Ea=0.48×2.303×8.3×2410 …
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- TG EAPCET 2025Set eng-2025-05-03-AN1 markMCQQ.The molar conductivity of acetic acid solution at infinite dilution is 390 S cm2 mol−1. What is the molar conductivity of 0.01 M acetic acid solution (in S cm2 mol−1)? (Given: Ka(CH3COOH)=1.8×10−5, assume 1−α=1) (A) 10.64 (B) 16.54 (C) 51.64 (D) 15.64
›Reveal solutionSolution
The key idea is to use the degree of dissociation α from the acid dissociation constant Ka, then apply Kohlrausch’s law to find molar conductivity at a given concentration. The final molar conductivity is approximately 16.54 S cm2 mol−1, which corresponds to option (B).
We are given the molar conductivity at infinite dilution, Λm∞=390 S cm2 mol−1, for acetic acid. For a weak electrolyte like acetic acid, the molar conductivity at a finite concentration is related to Λm∞ by Λm=αΛm∞, where α is the degree of dissociation. So the problem reduces to finding α for a 0.01 M solution using the given Ka.
Why this works:
For weak acids, the conductivity is proportional to the number of ions present. At infinite dilution, the acid is fully dissociated (α=1). At any finite concentration, only a fraction α dissociates, so the molar conductivity scales linearly with α. The value of α is obtained from the equilibrium expression for Ka.
Step-by-step solution:
- Write the dissociation equilibrium For acetic acid:
CH3COOH⇌CH3COO−+H+
Initial concentration: c=0.01 M.
At equilibrium:
[CH3COOH]=c(1−α),[CH3COO−]=cα,[H+]=cα
- Apply the acid dissociation constant expression
Ka=[CH3COOH][H+][CH3COO−]=c(1−α)(cα)(cα)=1−αcα2
Given Ka=1.8×10−5 and c=0.01 M.
- Simplify using the assumption 1−α≈1 The problem explicitly says “assume 1−α=1”. This is valid because α is very small for a weak acid at this concentration. Then:
Ka≈cα2
So:
α=cKa=0.011.8×10−5=1.8×10−3=0.0018
- Calculate α
- TG EAPCET 2025Set eng-2025-05-03-FN1 markMCQQ.The molar conductivity of acetic acid solution at infinite dilution is 390 S cm2 mol−1. What is the molar conductivity of 0.01 M acetic acid solution (in S cm2 mol−1)? (Given: Ka (CH3COOH)=1.8×10−5, assume 1−α=1) (A) 15.64 (B) 51.64 (C) 16.54 (D) 10.64
›Reveal solutionSolution
Using the Ostwald dilution law and the relationship between molar conductivity and degree of dissociation, the molar conductivity of 0.01 M acetic acid is found to be approximately 16.54 S cm² mol⁻¹, corresponding to option (C).
Concept & Intuition
Acetic acid is a weak electrolyte — it does not fully dissociate in solution. Its molar conductivity at a given concentration is less than at infinite dilution because fewer ions are present. The degree of dissociation α is related to the acid dissociation constant Ka via Ostwald’s dilution law. Once α is known, the molar conductivity Λm is simply α×Λm∞, assuming that ionic mobilities are constant (which is reasonable at low concentrations). The problem also tells us to assume 1−α≈1, which simplifies the calculation.
Step-by-step solution
- Write the relationship between molar conductivity and degree of dissociation For a weak electrolyte, the molar conductivity at a given concentration is:
Λm=αΛm∞
where Λm∞=390 S cm2 mol−1 is the molar conductivity at infinite dilution.
- Express α using the acid dissociation constant For acetic acid:
CH3COOH⇌CH3COO−+H+
Initial concentration: c=0.01 M.
At equilibrium: [H+]=[CH3COO−]=cα, [CH3COOH]=c(1−α).
The dissociation constant is:
Ka=c(1−α)(cα)(cα)=1−αcα2
- Apply the approximation 1−α≈1 Since acetic acid is weak, α is very small, so:
Ka≈cα2
This gives:
α=cKa
- Plug in the numbers α=0.011.8×10−5=1.8×10−3=0.0018 …
- TG EAPCET 2024Set eng-2024-05-09-FN1 markMCQQ.Identify the correct statements from the following A) At 298 K, the potential of hydrogen electrode placed in a solution of pH = 10, is −0.59 V B) The limiting molar conductivity of Ca2+ and Cl− is 119 and 76 S cm2 mol−1 respectively. The limiting molar conductivity of CaCl2 is 195 S cm2 mol−1 C) The correct relationship between Kc and Ecell⊖ is Ecell⊖=nF2.303RTlogKc (A) A, B, C (B) A, B only (C) A, C only (D) B, C only
›Reveal solutionSolution
The key idea is to check each statement using standard electrochemistry and conductivity relations: statement A uses the Nernst equation for a hydrogen electrode at pH 10, statement B applies Kohlrausch’s law of independent migration of ions, and statement C relates the standard cell potential to the equilibrium constant. Only statements A and C are correct, so the answer is option (C).
Concept and Intuition
We need to verify three independent statements.
- For A: The hydrogen electrode potential depends on [H+], which is given by pH. The Nernst equation directly gives the potential vs. SHE.
- For B: Limiting molar conductivity of a salt is the sum of the limiting molar conductivities of its ions, each multiplied by the number of ions per formula unit.
- For C: The relationship between Ecell⊖ and Kc is a standard thermodynamic equation derived from ΔG⊖=−nFEcell⊖=−RTlnKc.
Let’s examine each step by step.
- Statement A: Hydrogen electrode at pH = 10 at 298 K The hydrogen electrode reaction is 2H++2e−→H2. Under standard conditions (1 atm H2, [H+]=1 M), E⊖=0 V. For non-standard conditions, the Nernst equation at 298 K is:
E=E⊖−n0.059log[H+]21
Here n=2, so:
E=0−20.059log[H+]21=−0.059×log[H+]1=−0.059×pH
At pH = 10: E=−0.059×10=−0.59 V.
TipA common mistake is forgetting that the Nernst equation for the hydrogen electrode simplifies directly to E=−0.059×pH at 298 K.
So statement A is correct.
- Statement B: Limiting molar conductivity of CaCl2 Kohlrausch’s law: Λm∞(CaCl2)=λ∞(Ca2+)+2⋅λ∞(Cl−) Given: λ∞(Ca2+)=119 S cm2 mol−1, λ∞(Cl−)=76 S cm2 mol−1. Then: Λm∞(CaCl2)=119+2×76=119+152=271 S cm2 mol−1. …
- TG EAPCET 2024Set eng-2024-05-10-FN1 markMCQQ.The molar conductivity of 0.02 M solution of an electrolyte is 124×10−4 S m2 mol−1. What is the resistance of the same solution (in ohms), kept in a cell of cell constant 129 m−1? (A) 390 (B) 130 (C) 260 (D) 520
›Reveal solutionSolution
The key is to relate molar conductivity, concentration, and cell constant to resistance via conductivity. The resistance is found to be 520 Ω, so the correct option is (D).
We are given:
- Molar conductivity, Λm=124×10−4S m2mol−1
- Concentration, c=0.02M=0.02mol/L=20mol m−3 (since 1 M = 1000 mol/m³)
- Cell constant, G∗=129m−1
We need the resistance R in ohms.
Concept and intuition:
Molar conductivity Λm is the conductivity per mole of electrolyte. Conductivity κ (in S/m) is related to Λm by κ=Λm×c. Then, resistance is found from the cell constant: R=κG∗. This is a direct chain: molar conductivity → conductivity → resistance.
-
Convert concentration to SI units.
Molarity is mol/L, but conductivity uses mol/m³.
0.02mol/L=0.02×1000=20mol/m3.
-
Find conductivity κ.
κ=Λm×c=(124×10−4)×20
Compute:
124×10−4=0.0124
0.0124×20=0.248S/m.
- Use the cell constant to find resistance. The cell constant G∗=arealength and relates conductivity and resistance:
R=κG∗
So,
- TG EAPCET 2023Set eng-2023-05-12-AN1 markMCQQ.At 300 K, the conductivity of 0.01 mol dm−3 aqueous solution of acetic acid is 19.5×10−5 mho cm−1 and limiting molar conductivity of acetic acid at the same temperature is 390 mho cm2 mol−1. The degree of dissociation of acetic acid is (A) 5.0×10−5 (B) 5.0×10−2 (C) 2.5×10−5 (D) 7.5×10−2
›Reveal solutionSolution
The degree of dissociation α is the ratio of molar conductivity at a given concentration to the limiting molar conductivity. Using κ=19.5×10−5 mho cm−1, c=0.01 mol dm−3, and Λm∘=390 mho cm2 mol−1, we find α=5.0×10−2, which corresponds to option (B).
Concept and intuition:
For a weak electrolyte like acetic acid, the molar conductivity Λm increases as the solution is diluted, approaching a limiting value Λm∘ at infinite dilution. The degree of dissociation α tells us what fraction of the acid molecules have actually ionized. Kohlrausch’s law and the relation α=Λm/Λm∘ let us extract α directly from conductivity measurements — no equilibrium constants needed, just a ratio.
Step-by-step solution:
- Convert concentration to consistent units. The concentration is given as 0.01 mol dm−3. Since 1 dm3=1000 cm3, we have
c=0.01 mol dm−3=0.01 mol per 1000 cm3=1.0×10−5 mol cm−3.
This conversion is essential because conductivity κ is in mho cm−1 and molar conductivity will be in mho cm2 mol−1.
- Compute the molar conductivity Λm of the solution. Molar conductivity is defined as
Λm=cκ,
where κ is the measured conductivity and c is the concentration in mol cm−3.
Substituting:
Λm=1.0×10−5 mol cm−319.5×10−5 mho cm−1=19.5 mho cm2 mol−1.
- Recall the relation between degree of dissociation and molar conductivities. For a weak electrolyte, the degree of dissociation α is given by
α=Λm∘Λm,
where Λm∘ is the limiting molar conductivity (at infinite dilution). This holds because at infinite dilution the electrolyte is fully dissociated, so the ratio tells us the fraction dissociated at the given concentration. …
- TG EAPCET 2023Set eng-2023-05-13-FN1 markMCQQ.The conductivity of a solution of concentration 0.1 mol L−1 of a weak monobasic acid (HA) (in Scm−1) is (Given ∧m0=400 Scm2 mol−1 and degree of dissociation (α) of HA =0.02) (A) 32×10−4 (B) 16×10−4 (C) 4×10−4 (D) 8×10−4
›Reveal solutionSolution
The conductivity κ is found from κ=αcΛm0. With α=0.02, c=0.1 molL−1, and Λm0=400 Scm2mol−1, we get κ=8×10−4 Scm−1, so the correct option is (D).
The key idea is that for a weak electrolyte, the molar conductivity at a given concentration is Λm=αΛm0, because only the dissociated fraction contributes to conduction. Conductivity κ is then κ=Λm×c (with careful unit handling). This avoids needing the full Kohlrausch law — just use the degree of dissociation directly.
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Understand the relationship
Molar conductivity Λm is defined as κ/c, where κ is conductivity (in Scm−1) and c is concentration (in molcm−3). For a weak acid, Λm=αΛm0, because only the fraction α of molecules has dissociated into ions, each with the limiting molar conductivity Λm0.
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Convert concentration units
Given c=0.1 molL−1. Since 1 L=1000 cm3, we have
c=0.1 molL−1=0.1×10−3 molcm−3=1.0×10−4 molcm−3.
This step is crucial because Λm0 is in Scm2mol−1, so c must be in molcm−3 for κ to come out in Scm−1.
- Compute the molar conductivity at this concentration Λm=αΛm0=0.02×400 Scm2mol−1=8 Scm2mol−1. …
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- TG EAPCET 2023Set eng-2023-05-13-FN1 markMCQQ.A polymer sample contains 3 molecules of molar mass 103, 3 molecules of molar mass 500 and 4 molecules of molar mass 200. What is its weight average molecular mass? (A) 530 (B) 737.7 (C) 834.4 (D) 821.6
›Reveal solutionSolution
The weight‑average molecular mass weights each molecule by its mass, so larger molecules contribute more heavily. For this sample, the result is approximately 737.7 g/mol, which corresponds to option (B).
The key idea is that weight‑average molecular mass (Mˉw) is not a simple arithmetic mean of the molar masses. Instead, it accounts for the fact that heavier molecules make up a larger fraction of the total mass of the sample. This is crucial in polymer chemistry because properties like viscosity and mechanical strength depend more on the mass of the larger chains.
The formula is:
Mˉw=∑niMi∑niMi2
where ni is the number of molecules of molar mass Mi. The numerator is the sum of (number × mass²), and the denominator is the total mass of the sample.
Let’s work through it step by step.
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List the data clearly
- 3 molecules of M1=1000
- 3 molecules of M2=500
- 4 molecules of M3=200
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Compute the total number of molecules (not needed for Mˉw, but good for context):
N=3+3+4=10 molecules.
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Compute the total mass of the sample (denominator):
∑niMi=(3×1000)+(3×500)+(4×200)
=3000+1500+800=5300
- Compute the sum of (number × mass²) (numerator):
∑niMi2=(3×10002)+(3×5002)+(4×2002)
=(3×1000000)+(3×250000)+(4×40000)
=3000000+750000+160000=3910000 …
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- TG EAPCET 2023Set ap-2023-05-11-AN1 markMCQQ.The molar conductances of sodium acetate, hydrochloric acid and sodium chloride are 91.0, 425.9 and 126.4 S cm2 mol−1 respectively at 25 ∘C at infinite dilution. What is the molar conductance of acetic acid at infinite dilution? (A) 390.5 S cm2 mol−1 (B) 461.3 S cm2 mol−1 (C) 643.3 S cm2 mol−1 (D) 43.5 S cm2 mol−1
›Reveal solutionSolution
Use Kohlrausch's law of independent migration of ions to combine the given molar conductances algebraically: ΛCH3COOH∘=ΛCH3COONa∘+ΛHCl∘−ΛNaCl∘=390.5 S cm2 mol−1.
The key insight is that at infinite dilution, each ion migrates independently and contributes a fixed amount to the total molar conductance, regardless of which other ion it's paired with. This is Kohlrausch's law.
For a weak electrolyte like acetic acid, we cannot measure the molar conductance at infinite dilution directly because it never fully dissociates. Instead, we construct it from strong electrolytes whose limiting conductances we can measure.
Think of it as an algebraic puzzle with ions. We want:
ΛCH3COOH∘=λCH3COO−∘+λH+∘
where λ∘ represents the limiting ionic conductance of each ion. We need to find a combination of the three given electrolytes that gives us exactly these two ions.
Building the combination:
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Identify what each electrolyte contributes:
- Sodium acetate: ΛCH3COONa∘=λCH3COO−∘+λNa+∘=91.0
- Hydrochloric acid: ΛHCl∘=λH+∘+λCl−∘=425.9
- Sodium chloride: ΛNaCl∘=λNa+∘+λCl−∘=126.4
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Construct the target combination:
We need CH3COO− and H+, but we want to eliminate Na+ and Cl−.
Start with sodium acetate (gives us CH3COO−) and add HCl (gives us H+):
ΛCH3COONa∘+ΛHCl∘=λCH3COO−∘+λNa+∘+λH+∘+λCl−∘ …
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