Graham's Law of Diffusion – From Intuition to Precision
Imagine you're in a room where someone opens a bottle of perfume at one end. You don't smell it instantly — it takes time for the perfume molecules to wander across the room. Now imagine the same experiment with a bottle of ammonia. You'd smell the ammonia much faster. Why? The ammonia molecules are lighter.
That's the core physical idea: lighter gas molecules move faster, on average, than heavier ones at the same temperature. Since diffusion and effusion are processes driven by molecular motion, a lighter gas will spread out (diffuse) or escape through a tiny hole (effuse) more quickly than a heavier gas.
Note
Diffusion is the mixing of gases due to random molecular motion. Effusion is the escape of a gas through a tiny hole into a vacuum. Graham's Law applies to both.
The Precise Statement
Graham's Law of Diffusion/Effusion states:
At constant temperature and pressure, the rate of diffusion or effusion of a gas is inversely proportional to the square root of its molar mass (or density).
Mathematically, for two gases A and B:
rBrA=MAMB=ρAρB
where:
r = rate of diffusion/effusion (volume or moles per unit time)
M = molar mass
ρ = density (at same T and P)
r2r1=M1M2
Why the Square Root? (The Physics)
The reason comes from kinetic molecular theory. At a given temperature, the average kinetic energy of gas molecules is the same for all gases:
21mv2=constant
Here m is the mass of one molecule and v is its speed. Rearranging:
v∝m1
Since molar mass M is proportional to molecular mass m, the average molecular speed is inversely proportional to M. And since the rate of diffusion/effusion is directly proportional to this average speed, you get Graham's Law.
Watch out
A common mistake is to invert the ratio. If gas A is lighter (MA<MB), then rA>rB. Check: MB/MA>1, so rA/rB>1 — correct. Always put the lighter gas in the numerator if you want a ratio > 1.
Worked Example
Problem: Hydrogen (M=2g/mol) and oxygen (M=32g/mol) are allowed to effuse through identical pinholes. How much faster does hydrogen effuse?
Step 1. When the perfume bottle is opened, its vapour molecules move (by random molecular motion) from the region of high concentration near the bottle to the rest of the room, where concentration is initially zero. …