4756 - Week 6

GRAHAMS LAW OF DIFFUSION
In 1833, Graham, an English chemist, discovered that a less dense gas can diffuse through a medium much faster
than a denser gas and carried out an experiment to examine the relationship between the rate of diffusion of a gas
and its density.
Graham's law of diffusion states that, at a constant temperature and pressure, the rate of diffusion of a gas is
inversely proportional to the square root of its density.
From Graham's law,
1 𝐾
𝑅∝ Thus, R = √𝑝
√𝑝
Where k is a constant, R is the rate of diffusion, p (the Greek letter rho) is the density of the gas.
𝑅1 𝑝2
⸫ = √𝑝1
𝑅2
Where R1 and R2 are the rates of diffusion and p1 and p2 the densities of the two gases.
The density of a given gas is found to be directly proportional to its molecular mass. Graham's law can be
redefined as:
At constant temperature and pressure, the rate of diffusion gas is inversely proportional to the square root of
its molecular mass
𝑅1 𝑀2
= √𝑀1.
𝑅2
1
Rate is the reciprocal of time, i.e 𝑅 = 𝑡
1 1
Therefore, substituting, 𝑅1 = 𝑡1, 𝑅2 = 𝑡2
𝑅1 𝑡2
We get 𝑅2 = 𝑡1
𝑡2 𝑚2
Thus, 𝑡1 = √𝑚1
Examples:
1. If equal amounts of helium and argon are placed in
a porous container and allowed to escape, which 2. What is the molecular weight of a gas that
gas will escape faster and how much faster? diffuses 1/50 as fast as hydrogen?
Solution:
Solution:
Rate1 (R1) = unknown gas = 1
First, Set rates and get atomic weights:
Rate2 (R2) = H2 = 50
Rate1 (R1) = He = x
Remember, 1/50th of 50 is 1.
Rate2 (R2) = Ar = 1
The molecular weight, (M1), of H2 = 2.016g/mol
The atomic weight, (M1), of He = 4.00
The molecular weight, (M2) ,of the other gas = x.
The atomic weight, (M2), of Ar = 39.95
𝑅1 𝑀2 By Graham's Law, we have:
From Graham's Law = √𝑀1 50 / 1 = √(x / 2.016)
𝑅2
Substituting, we have: 50 = √(x / 2.016)

Squaring both sides, we have
x / 1 = √(39.95 / 4.00) 50 2 = x / 2.016
x = 3.16 x = 2500 X 2.016
x = 5,040 g/mol
Thus, Helium escapes faster than Ar. It does so at
3.16 times the rate of the argon.
𝐑𝐄𝐋𝐀𝐓𝐈𝐕𝐄 𝐕𝐀𝐏𝐎𝐔𝐑 𝐃𝐄𝐍𝐒𝐈𝐓𝐘 𝐎𝐅 𝐀 𝐆𝐀𝐒𝐄
The vapour density of a gas or vapour is the number of times a given volume of gas (or vapour) is heavier
than the same volume of hydrogen measured and weighed under the same temperature and pressure
𝑚𝑎𝑠𝑠 𝑜𝑓 1 𝑣𝑜𝑙 𝑜𝑓 𝑎 𝑔𝑎𝑠 𝑜𝑟 𝑣𝑎𝑝𝑜𝑢𝑟
Vapour density = 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑒𝑞𝑢𝑎𝑙 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 ℎ𝑦𝑑𝑟𝑜𝑔𝑒𝑛
Applying Avogadro’s law, it is possible to show that the vapour density of a gas is related to the relative
molecular mass of the gas.
𝑚𝑎𝑠𝑠 𝑜𝑓 1 𝑚𝑜𝑙𝑒 𝑜𝑓 𝑎 𝑔𝑎𝑠 𝑜𝑟 𝑣𝑎𝑝𝑜𝑢𝑟
V.D = 𝑚𝑎𝑠𝑠 𝑜𝑓 1 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒 𝑜𝑓 ℎ𝑦𝑑𝑟𝑜𝑔𝑒𝑛
𝑚𝑎𝑠𝑠 𝑜𝑓 1 𝑣𝑜𝑙 𝑜𝑓 𝑎 𝑔𝑎𝑠
V.D = 𝑚𝑎𝑠𝑠 𝑜𝑓 2 𝑎𝑡𝑜𝑚𝑠 𝑜𝑓 ℎ𝑦𝑑𝑟𝑜𝑔𝑒𝑛
∴ V.D = relative molecular mass / 2
The density of hydrogen at S.T.P is 0.09𝑑𝑚3
Example
Calculate the vapour densities of the following gases from the given data.
1. 560𝑐𝑚3 of oxygen at S.T.P weighs 0.8g
2. 1,400𝑐𝑚3 of sulphur (iv) oxide weighs 4g
Solution
1. 1000𝑐𝑚3 of hydrogen at S.T.P weighs 0.09g 2. 1000𝑐𝑚3 of hydrogen at S.T.P weighs 0.09g.
560𝑐𝑚3 1400 ×0.09
∴ 560𝑐𝑚3 of hydrogen at 1000𝑐𝑚3 × 0.09 ∴ 1400 of hydrogen will weighs = 0.126g
1000
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑎 𝑔𝑖𝑣𝑒𝑛 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑔𝑎𝑠
= 0.05g Vapour density= 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑒𝑞𝑢𝑎𝑙 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 ℎ𝑦𝑑𝑟𝑜𝑔𝑒𝑛
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑎 𝑔𝑖𝑣𝑒𝑛 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑔𝑎𝑠
V.D = 𝑚𝑎𝑠𝑠 𝑜𝑓 1400𝑐𝑚3 𝑜𝑓 SO2
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑒𝑞𝑢𝑎𝑙 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 ℎ𝑦𝑑𝑟𝑜𝑔𝑒𝑛 ∴Vapour density of SO2 = 𝑚𝑎𝑠𝑠 𝑜𝑓 1400𝑐𝑚3 𝑜𝑓 𝐻2
∴Vapour density of oxygen 4𝑔
𝑚𝑎𝑠𝑠 𝑜𝑓 560𝑐𝑚3 𝑜𝑓 𝑜𝑥𝑦𝑔𝑒𝑛 0.8𝑔
= 0.126 = 31.74 = 32
= 𝑚𝑎𝑠𝑠 𝑜𝑓 560𝑐𝑚3 𝑜𝑓 ℎ𝑦𝑑𝑟𝑜𝑔𝑒𝑛 = 0.05𝑔 = 16
CLASS WORK
1. Arrange the following gases in decreasing order of diffusion rate: Chlorine, hydrogen chloride, hydrogen
sulphur and Carbon IV oxide [H=1, C= 12, O=16, S= 32, Cl=35.5]
2. 400 cm of a gas A diffuses through a porous partition in 5 seconds and 200cm of a gas B diffuses in 20 seconds
under the same condition of temperature and pressure: 1. Calculate the rates of diffusion of gases A and B 2.
Which gas is denser?
3. A gas X diffused through a porous partition at the rate of 2.5 cm/s. Under the same conditions, hydrogen
diffused at the rate of 10 cm/s. Calculate the RMM of the gas. [H = 1]

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GRAHAMS LAW OF DIFFUSION

Substituting, we have: 50 = √(x / 2.016)

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