Q.In comparison to a 0.01 M solution of glucose, the depression in freezing point of a 0.01 M MgCl2 solution is _____________.
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🔒 Start your 14-day free trial to unlock the full solution →Concept understanding — VanT Hoff Factor Association
The Intuition: What Happens When Particles Stick Together?
Imagine you're counting people in a room. You see 100 chairs, each with one person. That's 100 individuals. Now imagine those same 100 people decide to pair up — every two people hold hands and become a "couple." Suddenly, the number of independent moving units in the room drops from 100 to 50.
That's exactly what association does in a solution. When solute particles (molecules or ions) associate, they clump together into larger clusters. The number of independent particles floating around decreases. And since colligative properties (freezing point depression, boiling point elevation, osmotic pressure) depend only on the number of particles — not their identity — the observed effect becomes smaller than expected.
Association is the opposite of dissociation. In dissociation, one particle breaks into many (e.g., NaCl → Na⁺ + Cl⁻). In association, many particles combine into one (e.g., two acetic acid molecules dimerise).
The Van't Hoff Factor: The Correction Number
The Van't Hoff factor, denoted by i, is defined as:
i=Number of particles if no association occurredActual number of particles in solution after association
For a non-electrolyte that does not associate or dissociate, i=1.
For association, i<1 — because the actual particle count is less than what you started with.
A Concrete Example: Acetic Acid in Benzene
Acetic acid (CH3COOH) in benzene forms dimers — two molecules stick together via hydrogen bonding:
2CH3COOH⇌(CH3COOH)2
Suppose you dissolve 100 molecules of acetic acid. If no association occurred, you'd have 100 particles. But if all of them dimerise, you get only 50 dimers. So:
i=10050=0.5
In reality, association is never 100% complete — it's an equilibrium. So i lies between 0.5 and 1.
A common mistake: thinking i can be negative. It cannot. For association, 0<i<1. For dissociation, i>1. For no change, i=1.
The General Formula for Association
Let’s say n molecules of a solute associate to form one associated particle:
nA⇌An
Let α be the degree of association — the fraction of original molecules that have associated.
- Initially: 1 mole of A (i.e., N molecules)
- Moles that associate: α
- Moles that remain as single A: 1−α
- Moles of associated particles formed: nα (because n molecules make 1 associated unit)
Total moles after association:
(1−α)+nα
The Van't Hoff factor is:
i=Initial molesTotal moles after association=1(1−α)+nα=1−α+nα
Simplify:
i=1−α(1−n1)
For the common case of dimerisation (n=2):
i=1−α(1−21)=1−2α
So if α=0.6 (60% association), then i=1−0.3=0.7.
How Association Affects Colligative Properties
All colligative properties are multiplied by i:
| Property | Formula without association | Formula with association |
|---|---|---|
| Relative lowering of vapour pressure | p∘p∘−p=xB | p∘p∘−p=i⋅xB |
| Elevation in boiling point | ΔTb=Kb⋅m | ΔTb=i⋅Kb⋅m |
Why this formula?
Van't Hoff Factor for Association: Why the Formula Holds
The Van't Hoff factor (i) for association describes how solute particles combine in solution, reducing the effective number of particles. Let's build the reasoning step-by-step.
1. The Core Idea: What Changes?
When a solute associates (e.g., two acetic acid molecules dimerize in benzene), the number of particles in solution decreases. The Van't Hoff factor is defined as:
i=Number of particles if no associationActual number of particles in solution
For association, i<1.
2. Setting Up the Association Process
Consider a solute that associates to form n molecules per aggregate (e.g., n=2 for dimerization). Let:
- Initial moles of solute = 1 mole (for simplicity)
- Degree of association = α (fraction of solute that associates)
What happens to the particles?
- Moles that associate = α (these combine into aggregates)
- Moles that remain free = 1−α
Each associated group of n molecules becomes 1 aggregate particle. So:
- Number of aggregates formed = nα
- Number of free molecules = 1−α
3. Total Particles After Association
Total moles of particles in solution:
Total=free(1−α)+aggregatesnα
If no association (α=0), total = 1 mole of particles.
4. The Van't Hoff Factor Formula
By definition:
i=Total particles if no associationTotal particles after association=1(1−α)+nα
Thus:
i=1−α+nα
5. Why This Makes Physical Sense
- If α=0 (no association): i=1 — particles behave independently.
- If α=1 (complete association): i=n1 — all molecules form n-mers, so particle count drops by factor n. …
The depression in freezing point, a colligative property, depends on the number of solute particles in the solution. The key idea here is the van 't Hoff factor (i), which accounts for the effective number of particles produced by a solute in solution.
- Glucose is a non-electrolyte and does not dissociate in solution, so its van 't Hoff factor iglucose=1.
- Magnesium chloride (MgCl2) is a strong electrolyte and dissociates completely into one Mg2+ ion and two Cl− ions, yielding a total of three particles per formula unit. Thus, its van 't Hoff factor iMgCl2=3.
- The depression in freezing point (ΔTf) is given by the formula ΔTf=iKfm, where Kf is the cryoscopic constant (same for a given solvent) and m is the molality (which is proportional to molarity for dilute solutions). …
The depression in freezing point depends on the number of solute particles. MgCl2 dissociates into three ions, while glucose does not dissociate, leading to about three times the depression in freezing point for MgCl2 compared to glucose at the same concentration.
Colligative properties are fascinating because they depend solely on the number of solute particles in a solution, not on their chemical identity. Depression in freezing point is one such property. When a solute is added to a solvent, it interferes with the solvent's ability to form a crystal lattice, thus lowering the freezing point. The more particles present, the greater this interference, and the larger the depression in freezing point.
The Van't Hoff factor, denoted by i, is crucial here. It accounts for the effective number of particles produced when a solute dissolves.
- For non-electrolytes (like glucose), which do not dissociate into ions, i=1. One molecule dissolved yields one particle.
- For electrolytes (like MgCl2), which dissociate into ions, i is approximately equal to the number of ions produced per formula unit, assuming complete dissociation.
Let's apply this understanding to the given problem.
-
Recall the formula for Depression in Freezing Point.
The depression in freezing point (ΔTf) is directly proportional to the molality (m) of the solution and the Van't Hoff factor (i).
ΔTf=iKfm
where Kf is the cryoscopic constant (molal depression constant) of the solvent. For a given solvent (water, in this case), Kf is constant.
Both solutions are 0.01 M. For dilute aqueous solutions, molarity (M) is a good approximation for molality (m) because the density of water is close to 1 g/mL, meaning 1 L of solution is approximately 1 kg of solvent. Therefore, we can consider the molality (m) to be the same for both solutions.
Since Kf and m are the same for both solutions, the ratio of their freezing point depressions will simply be the ratio of their Van't Hoff factors.
-
Determine the Van't Hoff factor for Glucose.
Glucose (C6H12O6) is a non-electrolyte. When dissolved in water, it does not dissociate into ions. Each glucose molecule remains intact.
Therefore, for glucose, the Van't Hoff factor iglucose=1.
The depression in freezing point for the glucose solution is:
ΔTf,glucose=1×Kf×0.01
-
Determine the Van't Hoff factor for MgCl2.
Magnesium chloride (MgCl2) is an ionic compound and a strong electrolyte. When dissolved in water, it dissociates completely into its constituent ions.
The dissociation reaction is: …
Concept: Colligative Properties — Depression in Freezing Point
The depression in freezing point depends on the number of particles in solution, not the nature of the solute. This is given by:
ΔTf=i⋅Kf⋅m
where:
- i = van’t Hoff factor (number of particles per formula unit)
- Kf = cryoscopic constant (solvent-dependent)
- m = molality (here, same concentration for both)
Method: Van’t Hoff Factor Comparison
Steps
-
Identify the van’t Hoff factor (i) for each solute
- Glucose (C6H12O6): non-electrolyte → i=1
- MgCl2: dissociates as MgCl2→Mg2++2Cl− → i=3
-
Write the freezing point depression for each
- For glucose: ΔTf(glucose)=1⋅Kf⋅0.01
- For MgCl2: ΔTf(MgCl2)=3⋅Kf⋅0.01 …
Common Mistakes & How to Avoid Them
Mistake 1: Forgetting that MgCl2 dissociates into ions
Many students treat MgCl2 like glucose — a non-electrolyte — and assume both solutions have the same number of particles.
Why it's wrong:
Glucose (C6H12O6) does not dissociate in water. MgCl2 dissociates completely:
MgCl2→Mg2++2Cl−
This gives 3 ions per formula unit.
How to avoid:
Always check if the solute is ionic or covalent. Ionic compounds dissociate; covalent (like glucose, urea) do not.
Mistake 2: Counting the wrong number of particles
Some students think MgCl2 gives only 2 ions (forgetting the Cl− is doubled).
Why it's wrong:
The dissociation is:
1 Mg2++2 Cl−=3 particles total
How to avoid:
Write the dissociation equation explicitly. Count the ions carefully — subscript numbers matter.
Mistake 3: Confusing depression in freezing point with boiling point elevation
Students sometimes mix up the formula or the van't Hoff factor application.
Why it's wrong:
The formula for depression in freezing point is:
ΔTf=i⋅Kf⋅m
where i = van't Hoff factor (number of particles per formula unit).
- For glucose: i=1
- For MgCl2: i=3
How to avoid:
Memorise the formula clearly. For colligative properties, always ask: "How many particles does this solute produce in solution?"
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Showing the 12 most recent of 14 on this concept.
- AP EAPCET 2026Set ap-2026-05-19-FN1 markMCQQ.At T(K), 0.004 M Na2SO4 solution is isotonic with 0.01M glucose solution. The degree of dissociation of Na2SO4 is (A) 80% (B) 50% (C) 25% (D) 75%
›Reveal solutionSolution
Tests isotonicity via the van't Hoff factor for a dissociating electrolyte; the degree of dissociation of Na2SO4 works out to 75%.
Concept and Intuition
Two solutions are isotonic when they exert the same osmotic pressure — i.e. the same effective particle concentration. For an electrolyte that partially dissociates, the effective concentration is boosted by the van't Hoff factor i=1+(n−1)α, where n is the number of ions produced per formula unit and α is the degree of dissociation. A non-electrolyte like glucose has i=1 always.
Step-by-Step Solution
- Glucose is a non-electrolyte: effective concentration =1×0.01=0.01 M.
- Isotonic condition: iNa2SO4×CNa2SO4=Cglucose, so i×0.004=0.01⇒i=2.5. …
- AP EAPCET 2026Set ap-2026-05-19-AN1 markMCQQ.The van't Hoff factor of 0.01 m K2SO4 solution is 2.70. The percentage of undissociated K2SO4 at this concentration is (A) 85 (B) 35 (C) 25 (D) 15
›Reveal solutionSolution
Van't Hoff factor 2.70 for K2SO4 (n=3 ions) gives α=0.85, so 15% remains undissociated.
Concept and Intuition
The van't Hoff factor i measures how many effective particles a formula unit produces upon dissociation, relative to 1 (if it stayed intact). For a salt that dissociates into n ions with degree of dissociation α, i=1+(n−1)α; solving for α tells you what fraction actually ionised, and 1−α is the undissociated fraction.
Step-by-Step Solution
- K2SO4→2K++SO42−, so n=3 ions per formula unit.
- i=1+(n−1)α⇒2.70=1+(3−1)α=1+2α. …
- AP EAPCET 2026Set eng-2026-05-18-AN1 markMCQQ.What mass (in g) of glycerol is required to produce the same anti-freezing effect in 1.0 L of water as that of 20 g of NaCl in 1.0 L of water? (molar mass of glycerol = 92 g mol−1, assume NaCl is 97% dissociated) (A) 52.96 (B) 61.96 (C) 41.91 (D) 72.96
›Reveal solutionSolution
Equal anti-freeze effect requires equal effective (van't Hoff-corrected) molality; NaCl's dissociation must be accounted for via i, then glycerol (non-electrolyte) is matched to that effective concentration.
Concept and Intuition
Freezing-point depression is a colligative property: ΔTf=iKfm. For two solutions in the same solvent to show the same depression, their effective particle concentrations (i× molality) must be equal — not their nominal concentrations. An electrolyte like NaCl contributes more particles per mole than a non-electrolyte like glycerol because it dissociates.
Step-by-Step Solution
- NaCl is 97% dissociated into Na++Cl− (ν=2), so the van't Hoff factor is
i=1+α(ν−1)=1+0.97(2−1)=1.97
- Moles of NaCl in 1.0 L water: nNaCl=58.520=0.3419 mol (molar mass Na=23, Cl=35.5).
- Effective moles (particles) contributed by NaCl: i×n=1.97×0.3419=0.6735 mol. …
- AP EAPCET 2025Set ap-2025-05-20-AN1 markMCQQ.The osmotic pressure of 0.01 molar solution of an electrolyte is found to be 0.65 bar at 27∘C. The van't Hoff factor of the electrolyte is (R=0.083barLK−1mol−1) (A) 2.610 (B) 1.610 (C) 2.305 (D) 1.805
›Reveal solutionSolution
Rearranging the van't Hoff osmotic-pressure equation for i and plugging in the numbers gives i≈2.610.
Concept and Intuition
For an electrolyte solution, the observed osmotic pressure exceeds the "ideal" (non-dissociating) prediction because the solute dissociates into more particles. This is captured by the van't Hoff factor i:
π=icRT
where c is the molar concentration, R the gas constant, and T the absolute temperature. i>1 signals dissociation (more particles than formula units), i<1 signals association.
Step-by-Step Solution
- Given: π=0.65 bar, c=0.01 mol/L, R=0.083 bar·L·K⁻¹·mol⁻¹, T=27+273=300 K.
- Compute the "ideal" osmotic pressure term: cRT=(0.01)(0.083)(300)=0.249 bar. …
- AP EAPCET 2025Set ap-2025-05-20-FN1 markMCQQ.0.25 moles of CH2FCOOH was dissolved in 0.5 kg of water. The depression in freezing point of resultant solution was observed as 1∘C. What is the van't Hoff factor? (Kf=1.86 K kg mol−1) (A) 0.93 (B) 1.07 (C) 1.25 (D) 1.50
›Reveal solutionSolution
Using the freezing-point depression formula with the van't Hoff factor gives i≈1.07, indicating the acid is a weak electrolyte that partially ionises.
Concept and Intuition
Colligative properties like freezing-point depression depend on the total number of solute particles in solution. For a solute that partially dissociates (like a weak acid), the van't Hoff factor i (ratio of actual particles to formula units) is slightly greater than 1, capturing that partial ionisation.
Step-by-Step Solution
- Molality: m=mass of solvent (kg)nsolute=0.5kg0.25mol=0.5mol/kg.
- Freezing point depression formula: ΔTf=iKfm. …
- AP EAPCET 2025Set eng-2025-05-26-AN1 markMCQQ.The van't Hoff factor for 0.5 m aqueous CH2FCOOH solution is 1.075. What is the experimentally observed ΔTf (in K) for this solution ? (Kf=1.86 K kg mol−1) (A) 1.156 (B) 1.075 (C) 1.0 (D) 0.95
›Reveal solutionSolution
The van't Hoff factor scales the ideal (non-dissociating) freezing-point depression up to the experimentally observed value: ΔTf(obs)=iKfm, giving ≈1.0 K.
Concept and Intuition
For a weak electrolyte like fluoroacetic acid (CH2FCOOH), partial dissociation produces slightly more particles than the un-ionised molality alone would suggest. The van't Hoff factor i>1 captures this extra particle count, and the observed colligative property is the ideal formula multiplied by i.
Step-by-Step Solution
- Formula: ΔTf(observed)=i×Kf×m.
- Plug in values: i=1.075, Kf=1.86 K kg mol−1, m=0.5 mol kg−1.
- First compute the ideal part: Kf×m=1.86×0.5=0.93 K. …
- AP EAPCET 2024Set eng-2024-05-19-AN1 markMCQQ.The ΔTb value for 0.01 m KCl solution is 0.01 K. What is the Van't Hoff factor? (Kb for water = 0.52 Kkgmol−1) (A) 1.92 (B) 1.72 (C) 0.96 (D) 0.86
›Reveal solutionSolution
This tests the van't Hoff factor calculation from an observed elevation in boiling point of an electrolyte solution. The answer is (A) 1.92.
Concept and Intuition
The van't Hoff factor i accounts for the actual number of particles a solute produces in solution relative to the ideal (undissociated) case. For a strong electrolyte like KCl, which fully dissociates into 2 ions, the ideal i would be 2, but incomplete dissociation or ion-pairing effects can make the observed value slightly less than the ideal -- hence i close to but below 2 for a dilute solution is physically reasonable.
Step-by-Step Solution
- Colligative property formula for boiling point elevation with a van't Hoff factor: ΔTb=i⋅Kb⋅m.
- Rearranging: i=Kb⋅mΔTb. …
- AP EAPCET 2023Set ap-2023-05-23-AN1 markMCQQ.In a freezing point experiment, aqueous acetic acid solution gave ΔTf (observed) = 0.02 K. Calculated ΔTf for same solution was found to be 0.018 K. What is the van't Hoff factor of acetic acid? (A) 109 (B) 101 (C) 910 (D) 110
›Reveal solutionSolution
The van't Hoff factor is simply the ratio of the observed to the theoretical (undissociated, i=1) colligative property; here i=0.02/0.018=10/9.
Concept and Intuition
The van't Hoff factor i measures how far a real solute's colligative behaviour deviates from the "ideal" (non-electrolyte, non-associating) prediction. i>1 signals dissociation (more particles than expected — e.g. acetic acid partially ionising into H+ and CH3COO−), while i<1 signals association (fewer effective particles, e.g. dimerisation in benzene).
Step-by-Step Solution
- "Calculated" ΔTf = the theoretical value assuming the solute behaves as intact, non-dissociated molecules (i=1): given as 0.018 K.
- "Observed" ΔTf = the actually measured value in the experiment: given as 0.02 K.
- By definition, i=ΔTf(calculated,i=1)ΔTf(observed)=0.0180.02.
- Simplify: 0.0180.02=1820=910≈1.11. …
- AP EAPCET 2023Set eng-2023-05-15-AN1 markMCQQ.What is the van't Hoff factor of Ferric Sulphate (Assume 100% ionization) (A) 2 (B) 4 (C) 5 (D) 3
›Reveal solutionSolution
Ferric sulphate Fe2(SO4)3 dissociates completely into 2Fe3++3SO42−, five ions total, so with 100% ionization the van't Hoff factor i=5.
Concept and Intuition
The van't Hoff factor i measures the ratio of the actual number of particles in solution to the number of formula units dissolved — it captures dissociation (for electrolytes, i>1) or association (for e.g. dimerizing acids in nonpolar solvents, i<1). For a strong electrolyte assumed to ionize completely, i simply equals the total number of ions each formula unit breaks into.
Step-by-Step Solution
- Write the complete dissociation of ferric sulphate: Fe2(SO4)3→2Fe3++3SO42−.
- Count the total ions produced per formula unit: 2 (Fe3+)+3 (SO42−)=5 ions.
- Since 100% ionization is assumed (given in the question), the van't Hoff factor equals this ion count exactly: i=5.
Common Mistakes …
- AP EAPCET 2023Set eng-2023-05-16-AN1 markMCQQ.When 10−3 M solution of glucose in water, freezes at -0.0186 °C, then at what temperature 10−3 M solution of NaCl will freeze? (A) 0 °C (B) 0.186 °C (C) -0.186 °C (D) -0.0372 °C
›Reveal solutionSolution
NaCl dissociates into 2 ions in water (i=2), so its freezing point depression is twice that of the non-dissociating glucose solution at the same molar concentration — giving −0.0372 °C.
Concept and Intuition
Freezing point depression depends on the total number of solute particles in solution, captured by the van't Hoff factor i: ΔTf=iKfm. Glucose is a non-electrolyte (i=1), while NaCl is a strong electrolyte that dissociates completely into Na⁺ and Cl⁻ (i=2).
Step-by-Step Solution
- From the glucose data, find Kf: ΔTf=Kf×m×iglucose, with i=1, m=10−3: 0.0186=Kf×10−3⇒Kf=18.6 K·kg/mol. …
- AP EAPCET 2022Set ap-2022-07-11-AN1 markMCQQ.Arrange the following solutions in the correct order of their osmotic pressures. (A) 0.1 M NaCl (B) 0.1 M Urea (C) 0.1 M BaCl2 (A) B > C > A (B) C > B > A (C) C > A > B (D) A > B > C
›Reveal solutionSolution
Since all three solutions are 0.1 M, osmotic pressure ranks purely by the number of particles each solute produces in solution (i), giving BaCl2>NaCl> urea.
Concept and Intuition
Osmotic pressure is a colligative property: π=iCRT. At the same molar concentration C, temperature T is fixed, so π is directly proportional to the van't Hoff factor i, which counts how many particles (ions) one formula unit produces on dissociation.
Step-by-Step Solution
- Urea (B) is a non-electrolyte: it does not dissociate, so i=1.
- NaCl (A) dissociates into Na++Cl−: i≈2.
- BaCl2 (C) dissociates into Ba2++2Cl− (3 ions): i≈3. …
- AP EAPCET 2022Set ap-2022-07-11-FN1 markMCQQ.The correct property of colloidal solutions when compared to that of true solutions is (A) Lower osmatic pressure (B) High depression in freezing point (C) High elevation in boiling point (D) High Vapour pressure
›Reveal solutionSolution
This tests the comparative colligative behaviour of colloids vs true solutions — colloids show markedly lower osmotic pressure because particle number (not mass) governs colligative properties.
Concept and Intuition
Colligative properties (osmotic pressure, boiling point elevation, freezing point depression, vapour pressure lowering) depend on the NUMBER of solute particles, not their mass. Colloidal particles, though much bigger in size/mass, are far fewer in number per unit volume compared to a true (molecular) solution of the same mass concentration. Hence colloidal solutions show much smaller colligative effects — most notably a much lower osmotic pressure than expected, which is in fact used experimentally to estimate very large (macromolecular) molar masses.
Step-by-Step Solution
- Colligative properties ∝ number of particles (moles) of solute per unit volume of solvent.
- In a colloidal dispersion, particles (aggregates/micelles) are much bigger, so far fewer particles exist per gram of dispersed substance than in a true solution of the same mass.
- Therefore, at the same mass concentration, the colloidal system exhibits a much LOWER osmotic pressure than the true solution. …
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