Chemistry Notes, Chapter 11: Graham’s Law of Effusion

Background:
The ratio of the rates of effusion of two gases is equal to the square root of the
inverse ratio of their molar masses or densities.

The effusion rate of a gas is inversely proportional to the square root of its molar
mass.

What this means is, the larger the gas particle, the slower it will effuse at a given
temperature and pressure.

Mathematically, this can be represented as:

Rate of effusion of gas A = √Molar Mass of gas B = √density of gas B

Rate of effusion of gas B √Molar Mass of gas A √density of gas A

Explanation and Discussion:

Let us first consider why gases effuse. Containers can have small holes or pores in
them. Although these openings are microscopic, they are larger than the gas
molecules. Randomly, the gas molecules move around the inside of the container
until they impact something. This can be another molecule or the side of the
container. A gas can also, instead of hitting the side of the container, pass through
one of those openings by chance. This is effusion: a random movement of a as
molecule through the container's wall. A common example of this is a balloon filled
with helium: first it is buoyant and floats in the air, but in a few days it hangs
toward the ground or floats a few inches above the ground (if at all). The helium has
escaped through the small holes in the balloon.

With Graham's Law, you can find the effusion rates for two gases, the molar mass
of a gas, or the density of a gas. This ratio of effusion rates follows the pattern that
the gas with the lesser molar mass or density has a greater rate of effusion.

Calculations using Graham's Law

Let's compare the rate of effusion of two common gases, Nitrogen and Oxygen. N2,
Nitrogen, has a molar mass of 28.0 g. O2, Oxygen, has a molar mass of 32.0 g.
Therefore, to find the ratio, the equation would be:
 Rate of effusion of N2 = √32.0 g/mol
Rate of effusion of O2 = √28.0 g/mol

This works out to:

Rate of effusion of N2 = 1.069044968

Rate of effusion of O2

Adjusting to the appropriate significant figures, we find that the rate is 1.07. This
tells us that N2 is 1.07 times as fast as O2. It is faster, but not by much.

Let's try to find a molar mass. Let's use gas A and B. A is 0.68 times as fast as B.
The molar mass of B is 17.0 g/mol. What is the molar mass of A?

First, we set up the equation. Plugging in the values to our formula, we get:

0.68 = √17.0 g/mol

√Molar Mass of gas A

Squaring both sides gets:

0.4624 = 17.0 g/mol

Molar Mass of gas A

Then, to get the unknown alone, we exchange the extremes of our proportion:

Molar mass of gas A = 17.0 g/mol

0.4624

Which simplifies to:

Molar mass of gas A = 36.7647 g

Which, when adjusted to the correct significant digits, is 36.8 g/mol. Plugging this
in to our formula would check the answer. (If you are interested in which gases
were used, A is HCl and B is NH3).