Q.Determine the osmotic pressure of a solution prepared by dissolving 25 mg of K2SO4 in 2 litre of water at 25∘C, assuming that it is completely dissociated.
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Osmotic Pressure and Molar Mass: From Intuition to Formula
Imagine you have a glass of pure water, and you carefully place a tea bag into it. After a while, the water turns brown. The tea molecules have moved from the bag into the water. That's simple diffusion. But now imagine a different setup: you have a U-shaped tube with a special membrane at the bottom that only lets water molecules pass through — not larger molecules like sugar. On one side you put pure water, on the other side you put a sugar solution. What happens?
Water will spontaneously move from the pure water side into the sugar solution side, pushing the liquid level higher on the sugar side. That rising column of liquid is a direct physical effect — it's osmotic pressure trying to equalise concentrations. The taller the column gets, the more hydrostatic pressure it exerts back. Eventually, that back-pressure exactly balances the "pull" of the sugar, and the system stops.
That balancing pressure — the pressure you would need to apply to the solution side to prevent the water from moving — is the osmotic pressure (Π).
The Intuition Behind Molar Mass from Osmotic Pressure
Here's the key insight: the osmotic pressure depends only on the number of solute particles in a given volume of solution, not on what those particles are. A big protein molecule and a tiny sugar molecule, if present in the same number per litre, produce the same osmotic pressure.
This is incredibly useful. If you dissolve an unknown substance (say, a polymer or a protein) in water and measure the osmotic pressure, you can work backwards to find how many moles of it are present. And if you know the mass you dissolved, you can calculate the molar mass:
Molar mass=number of molesmass of solute (g)
So osmotic pressure becomes a direct window into the molecular weight of substances that are too large or too fragile to vaporise (like proteins, polymers, or enzymes).
The Precise Statement
For dilute solutions, osmotic pressure follows a law that looks exactly like the ideal gas law:
ΠV=nRT
where:
- Π = osmotic pressure (in atm or Pa)
- V = volume of solution (in L or m³)
- n = number of moles of solute
- R = ideal gas constant (0.0821 L·atm·mol⁻¹·K⁻¹ or 8.314 J·mol⁻¹·K⁻¹)
- T = absolute temperature (in K)
This is the van't Hoff equation for osmotic pressure. It tells you that osmotic pressure is directly proportional to the molar concentration of the solute:
Π=VnRT=cRT
where c is the molar concentration (mol/L).
From Osmotic Pressure to Molar Mass
If you dissolve a known mass w (in grams) of an unknown substance in a volume V of solvent, and measure the osmotic pressure Π at temperature T, you can find the molar mass M as follows:
- From ΠV=nRT, we get n=RTΠV
- But n=Mw (mass divided by molar mass)
- Equating: Mw=RTΠV
- Rearranging:
M=ΠVwRT
This is the working formula. Every quantity on the right is measurable in the lab.
Why This Method is Special
Osmotic pressure measurements are extraordinarily sensitive. For a substance with a very large molar mass (say, 100,000 g/mol), the freezing point depression or boiling point elevation would be too tiny to measure accurately. But osmotic pressure can still give a measurable reading because it's a colligative property that depends only on particle count, and the effect is large even at low concentrations.
Osmotic pressure is the most sensitive colligative property for determining molar masses of macromolecules. It can detect concentrations as low as 10−4 M, which is 100–1000 times more sensitive than freezing point depression.
A Worked Example
Problem: 0.50 g of a protein is dissolved in enough water to make 100 mL of solution at 25°C. The osmotic pressure is measured as 0.012 atm. Find the molar mass of the protein.
Solution:
Given: …
Why this formula?
Great — let’s build a clear, concept-first understanding of Osmotic Pressure and its link to Molar Mass.
1. What is Osmotic Pressure?
Osmotic pressure (Π) is the minimum pressure that must be applied to a solution to prevent the net flow of solvent into it through a semipermeable membrane.
Think of it as the “push” needed to stop the solvent from diluting the solution.
2. The Key Formula
The central equation is:
Π=iCRT
Where:
- Π = osmotic pressure (atm or Pa)
- i = van’t Hoff factor (number of particles per formula unit)
- C = molar concentration (mol/L or mol/m³)
- R = universal gas constant
- T = absolute temperature (K)
For non-electrolytes (like glucose, urea), i=1, so:
Π=CRT
3. Why does this formula hold? — The Reasoning
Step 1: Analogy to Ideal Gas Law
The van’t Hoff equation for osmotic pressure is structurally identical to the ideal gas law:
PV=nRT⇒P=VnRT=CRT
Why? Because solute particles in a dilute solution behave like gas molecules — they are far apart, move randomly, and exert a “pressure” on the membrane.
- In a gas: particles hit the container walls → pressure.
- In a solution: solute particles cannot cross the membrane, but they collide with it → osmotic pressure.
So, the formula Π=CRT is not a coincidence — it’s a direct analogy.
Step 2: The van’t Hoff Factor i
For electrolytes (e.g., NaCl), one formula unit dissociates into multiple ions:
- NaCl → Na⁺ + Cl⁻ → i=2
- CaCl₂ → Ca²⁺ + 2Cl⁻ → i=3
Each ion acts as an independent particle, so the effective concentration increases by factor i:
Π=iCRT
Step 3: Linking to Molar Mass
We usually know mass of solute (w) and volume of solution (V). Molar concentration is:
C=Vn=Vw/M
where M = molar mass (g/mol).
Substitute into the osmotic pressure equation:
Π=i⋅MVw⋅RT
Rearrange to solve for molar mass:
M=ΠViwRT
This is the key formula used in experiments to find molar mass from osmotic pressure.
4. Why is this method special? …
Concept: Osmotic Pressure with Dissociation
Osmotic pressure depends on the total number of particles in solution. When an ionic compound dissociates, we must account for all ions produced.
Step 1: Find moles of K2SO4.
Molar mass of K2SO4=2(39)+32+4(16)=174 g/mol
n=17425×10−3=1.437×10−4 mol
Step 2: Account for complete dissociation.
K2SO4→2K++SO42−
Each formula unit produces 3 ions, so the van't Hoff factor i=3.
Total moles of particles: ntotal=3×1.437×10−4=4.311×10−4 mol
Step 3: Apply the osmotic pressure formula. …
Osmotic pressure depends on the total particle concentration after dissociation. K2SO4 splits into three ions, tripling the effective molar concentration. The osmotic pressure is 5.27×10−3 atm.
Why osmotic pressure depends on particle count
Osmotic pressure measures the "push" exerted by solute particles trying to equalize concentration across a semipermeable membrane. The van 't Hoff equation tells us that osmotic pressure π behaves like an ideal gas:
π=CRT
where C is the molar concentration of particles, R is the gas constant, and T is absolute temperature.
The crucial insight: when an ionic compound dissolves and dissociates, each formula unit breaks into multiple ions. Each ion contributes independently to the osmotic pressure. So we need to account for the van 't Hoff factor i, the number of particles produced per formula unit:
π=iCRT
For K2SO4, complete dissociation gives:
K2SO4⟶2K++SO42−
That's three particles from one formula unit, so i=3.
Step-by-step calculation
1. Convert mass to moles
The molar mass of K2SO4 is:
M=2(39)+32+4(16)=78+32+64=174 g/mol
Given mass is 25 mg=0.025 g, so:
n=1740.025=1.437×10−4 mol
2. Find the molar concentration of the solute
Volume is 2 L, so:
C=21.437×10−4=7.18×10−5 mol/L
3. Account for dissociation
Since K2SO4 produces i=3 particles per formula unit, the effective particle concentration is:
Cparticles=i×C=3×7.18×10−5=2.154×10−4 mol/L …
Method: Van't Hoff Equation for Electrolyte Solutions
This problem uses the Van't Hoff equation modified for electrolytes, accounting for complete dissociation.
Step 1: Write the Van't Hoff equation
For an electrolyte solution, osmotic pressure (π) is:
π=i⋅C⋅R⋅T
Where:
- i = Van't Hoff factor (number of ions per formula unit)
- C = molar concentration (mol/L)
- R = gas constant (0.0821 L⋅atm⋅mol−1K−1)
- T = absolute temperature (K)
Step 2: Determine the Van't Hoff factor (i)
K2SO4 dissociates completely as:
K2SO4→2K++SO42−
So i=3 (2 potassium ions + 1 sulfate ion).
Step 3: Calculate moles of K2SO4
Molar mass of K2SO4:
- K=39.1×2=78.2
- S=32.1
- O=16.0×4=64.0
- Total = 174.3 g/mol
Mass given = 25 mg=0.025 g
Moles=174.30.025=1.434×10−4 mol
Step 4: Calculate molar concentration (C)
Volume = 2 L
C=21.434×10−4=7.17×10−5 mol/L
Step 5: Convert temperature to Kelvin …
Common Mistakes & How to Avoid Them
Mistake 1: Forgetting the van't Hoff Factor (i)
The error: Students calculate osmotic pressure using π=CRT directly, ignoring dissociation. For K2SO4, which dissociates completely:
K2SO4→2K++SO42−
This gives 3 ions per formula unit, so i=3.
How to avoid: Always check if the solute is ionic and whether it dissociates. For complete dissociation:
- i = number of ions produced per formula unit
- For K2SO4, i=3 (not 1)
Use the correct formula: π=iCRT
Mistake 2: Unit Confusion (mg vs g, mL vs L)
The error: Using 25 mg as 25 g, or forgetting to convert volume to litres.
How to avoid: Always convert to standard SI units before plugging into formulas:
- Mass: 25 mg = 25×10−3 g
- Volume: 2 L (already correct)
- Molar mass of K2SO4: 2(39.1)+32+4(16)=174.2 g/mol
Quick check: Write units alongside every number in your calculation.
Mistake 3: Using Wrong Temperature Scale
The error: Plugging in 25∘C directly as T without converting to Kelvin.
How to avoid: Always convert Celsius to Kelvin:
T(K)=25+273=298 K
Memory aid: "Gas constant R uses Kelvin — so must T."
Mistake 4: Incorrect Molarity Calculation
The error: Calculating moles correctly but then dividing by wrong volume or forgetting to convert mass to moles first.
Correct approach:
Moles of K2SO4=174.2 g/mol25×10−3 g=1.435×10−4 mol
Molarity C=2 L1.435×10−4 mol=7.175×10−5 M
How to avoid: Write the formula step-by-step:
C=molar mass (g/mol)×volume (L)mass (g)
Mistake 5: Forgetting the Value of R …
- JKBOSE Class 12 Annual Regular Examination 2022Set SZ5 marksQ.Define the term Osmotic pressure. Describe how molecular mass of a substance can be determined on the basis of osmotic pressure. 200 cm3 of an aqueous solution of a protein contains 1.26 g of the protein. The osmotic pressure of such solution at 300K is found to be 2.57 x 10^-3 bar. Calculate molecular mass of the protein. OR Define the following:(i) Molarity(ii) Molality(iii) Mole fraction. Concentrated nitric acid in laboratory work is 68% nitric acid by mass in aqueous solution. What should be the molarity of such a sample of the acid if the density of the solution is 1.504 gmL^-1?
›Reveal solutionSolution
Osmotic pressure pi obeys piV = nRT (a Van't Hoff-type equation), which rearranges to M = wRT/(piV); working the given numbers gives M is approximately 61,000 g/mol.
(A) Osmotic pressure and molecular mass determination
Osmotic pressure (pi) is the minimum excess pressure that must be applied on the solution side of a semipermeable membrane (separating the solution from pure solvent) to just stop the net flow (osmosis) of solvent molecules into the solution.
For a dilute solution, osmotic pressure obeys a Van't Hoff-type relation analogous to the ideal gas equation:
pi * V = n * R * T
where pi = osmotic pressure, V = volume of solution (litres), n = moles of solute, R = gas constant, T = absolute temperature.
Since n = w/M (w = mass of solute in grams, M = molar mass), this becomes:
pi * V = (w/M) * R * T
=> M = w * R * T / (pi * V)
Because osmotic pressure is measurable even for very dilute solutions (and at ordinary room temperature), this method is especially valuable for determining molar masses of macromolecules such as proteins and polymers, whose molar masses are too high to determine reliably by boiling-point elevation or freezing-point depression (whose changes would be too small to measure at such low molar concentrations).
Numerical: w = 1.26 g, V = 200 cm3 = 0.200 L, pi = 2.57x10^-3 bar, T = 300 K, R = 0.083 L bar K^-1 mol^-1.
M = wRT/(pi*V) = (1.26 x 0.083 x 300) / (2.57x10^-3 x 0.200)
Numerator = 1.26 x 0.083 x 300 = 31.37 (approx)
Denominator = 2.57x10^-3 x 0.200 = 5.14x10^-4
M = 31.37 / 5.14x10^-4 is approximately 61,040 g/mol
So the molecular mass of the protein is approximately 6.1 x 10^4 g/mol (about 61,000 g/mol) — a reasonable order of magnitude for a small protein.
OR
(B) Definitions
- Molarity (M): moles of solute dissolved per litre (dm3) of solution. Molarity = moles of solute / volume of solution in litres. Unit: mol/L.
- Molality (m): moles of solute dissolved per kilogram of solvent (NOT solution). Molality = moles of solute / mass of solvent in kg. Unit: mol/kg. Unlike molarity, molality does not change with temperature since it is mass-based, not volume-based. …
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