Q.Calculate the mass of ascorbic acid (Vitamin C, C6H8O6) to be dissolved in 75 g of acetic acid to lower its melting point by 1.5∘C. Kf=3.9 K kg mol−1.
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🔒 Start your 14-day free trial to unlock the full solution →Concept understanding — Colligative Properties Association
Colligative Properties: The Intuition First
Imagine you're at a party. The room is full of people dancing — that's your solvent molecules, moving freely. Now, someone brings in a few heavy, slow-moving guests who just stand in one spot — those are your solute particles. They don't dance, they don't interact much, they just take up space.
What happens? The dancers now have less room to move. They bump into the standing guests more often. The whole atmosphere changes — the dancers can't move as freely, they can't escape the room as easily, and the overall "energy" of the party shifts.
That's the core idea of colligative properties. When you add a non-volatile solute (like salt) to a solvent (like water), the solute particles don't do anything special — they just exist in the solution. But their mere presence changes four measurable properties of the solvent:
- Vapour pressure decreases
- Boiling point increases
- Freezing point decreases
- Osmotic pressure increases
The key insight: these changes depend only on the number of solute particles, not on what kind of particles they are. One molecule of sugar and one ion of salt (if they don't dissociate) affect these properties identically — provided they're the same number of particles.
This is why "colligative" comes from the Latin colligatus meaning "bound together" — the properties are bound to the quantity of solute, not its identity.
The Precise Statement
Colligative properties are properties of a solution that depend solely on the ratio of the number of solute particles to the number of solvent molecules in a given solution, and not on the chemical nature of the solute.
Mathematically, for a dilute solution of a non-volatile, non-electrolyte solute:
ΔP=P0⋅x2
ΔTb=Kb⋅m
ΔTf=Kf⋅m
Π=i⋅MRT
Where:
- ΔP = lowering of vapour pressure
- P0 = vapour pressure of pure solvent
- x2 = mole fraction of solute
- ΔTb = elevation in boiling point
- Kb = ebullioscopic constant (depends only on solvent)
- m = molality of solution
- ΔTf = depression in freezing point
- Kf = cryoscopic constant (depends only on solvent)
- Π = osmotic pressure
- i = van't Hoff factor (accounts for dissociation/association)
- M = molarity
- R = gas constant
- T = absolute temperature
The Crucial Distinction: Association vs. Dissociation
Now, here's where the association part comes in — and it's the twist that catches most students.
The formulas above assume the solute particles remain as individual, independent particles. But in reality:
- Dissociation: Some solutes break apart into smaller particles (e.g., NaCl → Na⁺ + Cl⁻). This increases the number of particles, so the colligative effect is larger than expected.
- Association: Some solutes clump together into larger particles (e.g., acetic acid in benzene forms dimers: 2 CH₃COOH → (CH₃COOH)₂). This decreases the number of particles, so the colligative effect is smaller than expected.
A common mistake: students think "association" means the solute interacts with the solvent. No — association means solute particles bind to each other, reducing the effective particle count. Solvent-solute interactions affect non-colligative properties like solubility.
The van't Hoff Factor i
To account for these real-world effects, we introduce the van't Hoff factor:
i=Number of formula units dissolvedActual number of particles in solution
For a non-electrolyte that doesn't associate or dissociate: i=1
For dissociation (e.g., NaCl): i>1 (ideally 2 for NaCl)
For association (e.g., acetic acid dimerizing): i<1
The corrected formulas become:
ΔTb=i⋅Kb⋅m
ΔTf=i⋅Kf⋅m
Π=i⋅MRT
A Concrete Example
Consider acetic acid (CH₃COOH) dissolved in benzene. In benzene, acetic acid molecules form hydrogen-bonded dimers:
2CH3COOH⇌(CH3COOH)2
If you dissolve 1 mole of acetic acid, you might end up with only 0.6 moles of particles (0.4 moles of dimers + 0.2 moles of monomers). So i=0.6. …
Why this formula?
Colligative Properties & Association: Why the Formula Holds
Let's build this from first principles — understanding why association changes colligative properties, not just memorizing the formula.
The Core Idea: What Are Colligative Properties?
Colligative properties depend only on the number of solute particles in solution, not on their chemical identity. The four key ones are:
- Vapor pressure lowering
- Boiling point elevation
- Freezing point depression
- Osmotic pressure
When a solute associates (e.g., two molecules dimerize), the effective number of particles decreases. This is the entire reason the formula changes.
The van't Hoff Factor: The Bridge
We define the van't Hoff factor i as:
i=number of formula units dissolvedactual number of particles in solution
For a non-electrolyte that does not associate, i=1.
For association, i<1.
Example: Dimerization of Benzoic Acid in Benzene
Benzoic acid (C6H5COOH) forms dimers in benzene:
2C6H5COOH⇌(C6H5COOH)2
If we dissolve n moles of monomer, but only n/2 moles of dimer exist, then:
i=nn/2=0.5
Deriving the Modified Formula
Step 1: Start with the Normal Colligative Formula
For freezing point depression (the most common exam case):
ΔTf=Kf⋅m
where m is the molality of the solute (moles per kg solvent).
Step 2: Replace m with Effective Molality
Because only the number of particles matters, we replace m with i⋅m:
ΔTf=Kf⋅(i⋅m)
This is the general formula for any colligative property when association or dissociation occurs.
Step 3: Express i in Terms of Degree of Association
Let:
- α = degree of association (fraction of molecules that associate)
- n = number of molecules that combine to form one associated particle (e.g., n=2 for dimerization)
For a dimerization (n=2):
- Initially: 1 mole of monomer
- After association: (1−α) moles remain as monomer, and α/2 moles of dimer form
- Total particles = (1−α)+2α=1−2α
Thus:
i=11−2α=1−2α
General formula for association of n molecules:
i=1−α+nα=1−α(1−n1)
Why This Makes Physical Sense …
The problem involves the depression of the freezing point, a colligative property that depends on the number of solute particles. Ascorbic acid (C6H8O6) is a non-electrolyte, meaning its van't Hoff factor (i) is 1 as it does not dissociate or associate in solution.
ΔTf=iKfm
-
The given depression in melting point is ΔTf=1.5∘C, which is 1.5K. The cryoscopic constant Kf=3.9 K kg mol−1. We calculate the molality (m) of the solution:
m=iKfΔTf=1×3.9 K kg mol−11.5 K=0.3846 mol kg−1.
-
The mass of the solvent (acetic acid) is W1=75 g=0.075 kg. Using the definition of molality (m=mass of solvent in kgmoles of solute), the moles of ascorbic acid (n2) required are: …
Freezing-point depression ΔTf=Kfm fixes the molality; with the molar mass of ascorbic acid (176 g mol−1) and 75 g of acetic acid, the required mass is ≈5.08 g.
1. Molality from ΔTf=Kfm.
m=KfΔTf=3.91.5=0.3846 mol kg−1
2. Moles of ascorbic acid in 75 g=0.075 kg of acetic acid:
n=m×0.075=0.3846×0.075=0.02885 mol …
Method: Freezing Point Depression (Cryoscopy)
This is a direct application of Raoult’s Law for colligative properties — specifically, the depression of freezing point caused by dissolving a non-volatile solute.
Step 1 — Write the formula
The freezing point depression is given by:
ΔTf=Kf⋅m
Where:
- ΔTf = depression in freezing point (in K or °C, same magnitude)
- Kf = cryoscopic constant (in K kg mol⁻¹)
- m = molality of the solution (mol solute per kg solvent)
Step 2 — Identify given values
- ΔTf=1.5∘C (same as 1.5 K)
- Kf=3.9K kg mol−1
- Mass of solvent (acetic acid) = 75g=0.075kg
- Solute = ascorbic acid, C6H8O6
Step 3 — Calculate molality required
From ΔTf=Kf⋅m:
m=KfΔTf=3.91.5
m≈0.3846mol/kg
Step 4 — Find moles of solute needed
Molality = moles of solute per kg of solvent:
Moles of solute=m×mass of solvent (kg)
=0.3846×0.075
≈0.02885mol
Step 5 — Convert moles to mass
Molar mass of C6H8O6: …
🧠 The Core Concept First
The problem uses freezing point depression:
ΔTf=Kf⋅m
where
- ΔTf = depression in freezing point (here, 1.5 °C = 1.5 K, since the size of 1 °C = 1 K)
- Kf = cryoscopic constant (given: 3.9 K kg mol⁻¹)
- m = molality = moles of solute per kg of solvent
We need mass of solute (ascorbic acid).
✗ Common Mistake #1: Forgetting to convert solvent mass to kg
The error:
Using 75 g directly in the molality formula without converting to kg.
Why it’s wrong:
Molality is moles per kg of solvent, not per gram.
✓ How to avoid:
Always write the unit conversion explicitly:
Mass of solvent=75g=0.075kg
✗ Common Mistake #2: Using ΔTf in °C without realising it equals K
The error:
Thinking 1.5 °C needs conversion to Kelvin (e.g., adding 273).
Why it’s wrong:
A difference of 1.5 °C is exactly equal to a difference of 1.5 K. The Kelvin scale has the same “step size” as Celsius.
✓ How to avoid:
Remember: ΔT in °C = ΔT in K. Only absolute temperatures need the +273 conversion.
✗ Common Mistake #3: Incorrect molar mass of ascorbic acid (C6H8O6)
The error:
Miscounting atoms or using wrong atomic masses.
Why it’s wrong:
A wrong molar mass gives a wrong final mass.
✓ How to avoid:
Calculate step by step:
- C: 6×12=72
- H: 8×1=8
- O: 6×16=96
M=72+8+96=176g mol−1
Double-check — this is a standard value.
✗ Common Mistake #4: Mixing up the formula — using ΔTf=Kf⋅n instead of Kf⋅m
The error:
Plugging moles directly without dividing by kg of solvent.
Why it’s wrong:
Molality m=kg solventmoles, not just moles.
✓ How to avoid:
Write the full chain:
ΔTf=Kf⋅kg of solventmoles of solute
Then rearrange stepwise.
✓ Correct Solution (Quick Walkthrough)
Step 1: Find molality …
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