Q.Calculate the osmotic pressure in pascals exerted by a solution prepared by dissolving 1.0 g of polymer of molar mass 185,000 in 450 mL of water at 37∘C.
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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? …
The key idea is that osmotic pressure (Π) for a dilute solution follows van't Hoff's law: Π=iCRT, and for a non-electrolyte polymer, i=1.
Step 1: Find the molar concentration C.
Mass of polymer = 1.0 g, molar mass M=185,000 g/mol.
Moles of polymer = 185,0001.0=5.405×10−6 mol.
Volume of solution = 450 mL = 0.450 L.
C=0.4505.405×10−6=1.201×10−5 mol/L.
Step 2: Convert to SI units.
C in mol/m3: 1.201×10−5 mol/L = 1.201×10−2 mol/m3 (since 1 L = 10−3 m3).
Temperature T=37∘C = 310 K. …
Osmotic pressure depends only on the number of solute particles, not their identity. Using Π=iCRT (with i=1 for a non-electrolyte polymer), the pressure is about 31.0 Pa.
Why osmotic pressure works for molar mass
Osmotic pressure is a colligative property - it depends solely on the concentration of solute particles, not on their chemical nature. For a non-electrolyte like a polymer, each molecule contributes one particle, so i=1. This makes osmotic pressure ideal for finding the molar mass of large molecules: even a tiny mass of polymer gives a measurable pressure, whereas boiling point elevation or freezing point depression would be too small to detect.
The governing equation is:
Π=iCRT=VnRT=MVwRT
where Π is osmotic pressure (Pa), w is mass of solute (g), M is molar mass (g/mol), V is volume of solution (m3), R is the gas constant, and T is absolute temperature (K).
Step-by-step calculation
1. Convert temperature to Kelvin
T=37+273=310 K
2. Use SI gas constant
R=8.314 J mol−1K−1=8.314 Pa m3 mol−1K−1
3. Convert volume to cubic metres
V=450×10−6=4.50×10−4 m3 …
Method: Osmotic Pressure Formula (van't Hoff Equation)
This method uses the direct relationship between osmotic pressure and molar concentration for non-electrolyte solutions.
Steps
- Identify the formula The van't Hoff equation for osmotic pressure is:
Π=iCRT
For a non-electrolyte polymer, i=1, so:
Π=CRT
- Convert temperature to Kelvin
T=37∘C+273=310 K
- Calculate the molar concentration (C)
- Moles of polymer:
n=molar massmass=185,000 g/mol1.0 g=5.405×10−6 mol
- Volume in litres:
V=450 mL=0.450 L
- Molarity:
C=Vn=0.4505.405×10−6=1.201×10−5 mol/L
- Use the value of R in SI units For pressure in pascals (Pa), use:
R=8.314 J mol−1K−1=8.314 Pa m3mol−1K−1
Note: 1 L=10−3 m3, so C in mol/m3 is: …
Let’s first solve it correctly, then list the common mistakes and how to avoid each.
✓ Correct Solution (for reference)
Given:
- Mass of polymer, w=1.0 g
- Molar mass, M=185,000 g mol−1
- Volume of solution, V=450 mL=0.450 L
- Temperature, T=37∘C=37+273=310 K
- Gas constant, R=0.0821 L atm mol−1K−1 (for atm) or R=8.314 J mol−1K−1 (for Pa)
Step 1: Number of moles
n=Mw=185,0001.0=5.405×10−6 mol
Step 2: Molarity
C=V(L)n=0.4505.405×10−6=1.201×10−5 mol L−1
Step 3: Osmotic pressure (in Pa)
Use Π=CRT with R=8.314 J mol−1K−1 and C in mol m−3.
Convert molarity to mol m−3:
1 mol L−1=1000 mol m−3
So,
C=1.201×10−5×1000=1.201×10−2 mol m−3
Now,
Π=(1.201×10−2)×(8.314)×(310)
Π=1.201×10−2×2577.34≈30.95 Pa
Final answer: 30.95 Pa (approximately 31 Pa)
✗ Common Mistakes & How to Avoid Them
1. Forgetting to convert temperature to Kelvin
- Mistake: Using T=37∘C directly in Π=CRT.
- Why it’s wrong: The gas constant R has units per Kelvin — using Celsius gives a completely wrong (and meaningless) result.
- How to avoid: Always add 273 to Celsius: T(K)=T(∘C)+273. For 37°C, it’s 310 K.
2. Using wrong units for volume
- Mistake: Plugging V=450 mL directly into C=n/V without converting to litres.
- Why it’s wrong: Molarity is moles per litre, not per mL.
- How to avoid: Convert mL to L by dividing by 1000: 450 mL=0.450 L.
3. Confusing molar mass with molecular mass in g/mol
- Mistake: Treating 185,000 as the mass of one molecule (in amu) and then using it incorrectly.
- Why it’s wrong: Molar mass is already in g/mol — no further conversion needed.
- How to avoid: Remember: molar mass (g/mol) = molecular mass (amu) numerically. Just use it directly in n=w/M.
4. Using the wrong value of R for the required unit of pressure
- Mistake: Using R=0.0821 L atm mol−1K−1 and then reporting pressure in pascals without converting.
- Why it’s wrong: That R gives pressure in atm, not Pa.
- How to avoid:
- If answer needed in Pa, use R=8.314 J mol−1K−1 and ensure concentration is in mol m−3.
- If you use R=0.0821, convert atm to Pa: 1 atm=101325 Pa.
5. Forgetting to convert molarity to mol m−3 when using R=8.314
- Mistake: Plugging C in mol L−1 directly into Π=CRT with R=8.314. …
- 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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