Pressure of an Ideal Gas

The pressure of an ideal gas is due to collisions of gas molecules with the walls of the container.

Mathematical Derivation:

Consider n moles of an ideal gas be confined in a cubical box (container) of volume V as shown

in figure below.

The walls of the box are hold at temperature T. What is the connection between the pressure p

exerted by the gas on the walls and the speeds of molecules? Molecules motion is random and

collision is elastic. We ignore collision of molecules with one another.

Let a molecule of mass m collides with the shaded wall with velocity⃗⃗𝑣, only x component of

the velocity changes. Change in momentum along x-axis is

∆𝑝𝑥1 = (−𝑚𝑣𝑥1 ) − 𝑚𝑣𝑥1 = −2𝑚𝑣𝑥1

Force exerted on the molecule by the wall: If 𝐹𝑤 is the force exerted by the wall on the

molecule, then according to Newton’s 2nd Law in terms of momentum we can write

∆𝑝𝑥1
𝐹𝑤 = … (1)
∆𝑡

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Where ∆𝑡 be the time between successive collisions (i.e. time the molecule takes to travel to

the opposite wall and back again) and total distance covered during successive collisions is 2L.

Then

2𝐿
∆𝑡 =
𝑣𝑥1

Putting in equation (1) we get

2 2
∆𝑝𝑥1 −2𝑚𝑣𝑥1 −2𝑚𝑣𝑥1 −𝑚𝑣𝑥1
𝐹𝑤 = = = =
2𝐿 2𝐿 2𝐿 𝐿
𝑣𝑥1 𝑣𝑥1

Force exerted on the wall by the molecule: Let 𝐹𝑥1 be the force exerted by the molecule on

the wall then according to Newton’s 3rd law we can write

2
𝑚𝑣𝑥1
𝐹𝑥1 = −𝐹𝑤 =
𝐿

Net force: If we have N number of molecules exerted force on the shaded wall then force due

to each molecule can be written in similar way i.e.

2
𝑚𝑣𝑥2
𝐹𝑥2 =
𝐿

2
𝑚𝑣𝑥3
𝐹𝑥3 =
𝐿

And so on.

So the net force by N molecules is given as

2 2 2
𝑚𝑣𝑥1 𝑚𝑣𝑥2 𝑚𝑣𝑥𝑁
𝐹𝑥 = 𝐹𝑥1 + 𝐹𝑥2 + ⋯ +𝐹𝑥𝑁 = + + ⋯+
𝐿 𝐿 𝐿

Expression for Pressure: Now using the definition of pressure we can write

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 2 2 2
𝑚𝑣𝑥1 𝑚𝑣𝑥2 𝑚𝑣𝑥𝑁
( + + ⋯ +
𝐹𝑥 𝐿 𝐿 𝐿 ) 𝑚 2 2 2 )
𝑃= = = 3 (𝑣𝑥1 + 𝑣𝑥2 + ⋯ + 𝑣𝑥𝑁
𝐴 𝐿2 𝐿

2 2 2 )
𝑚𝑁 (𝑣𝑥1 + 𝑣𝑥2 + ⋯ + 𝑣𝑥𝑁
= ( )
𝐿3 𝑁

As 𝑉 = 𝐿3 , so

𝑚𝑁 2
𝑃= (𝑣𝑥 )𝑎𝑣𝑔 … (2)
𝑉

As 𝑁 = 𝑛𝑁𝐴 So equation (2) becomes

𝑚𝑛𝑁𝐴 2 𝑛𝑚𝑁𝐴 2
𝑃= (𝑣𝑥 )𝑎𝑣𝑔 = (𝑣𝑥 )𝑎𝑣𝑔
𝑉 𝑉

𝑛𝑀 2
𝑃= (𝑣 ) … (3)
𝑉 𝑥 𝑎𝑣𝑔

Where 𝑚𝑁𝐴 = 𝑀 (Molar mass of the gas).

Because molecules are moving randomly in all directions therefore the means square velocity

of the molecules will equally probable in all directions i.e.

(𝑣𝑥2 )𝑎𝑣𝑔 = (𝑣𝑦2 ) = (𝑣𝑧2 )𝑎𝑣𝑔

Hence total mean square velocity of the molecules is

(𝑣 2 )𝑎𝑣𝑔 = (𝑣𝑥2 )𝑎𝑣𝑔 + (𝑣𝑦2 ) + (𝑣𝑧2 )𝑎𝑣𝑔 = (𝑣𝑥2 )𝑎𝑣𝑔 + (𝑣𝑥2 )𝑎𝑣𝑔 + (𝑣𝑥2 )𝑎𝑣𝑔 = 3(𝑣𝑥2 )𝑎𝑣𝑔
𝑎𝑣𝑔

Hence

1 2
(𝑣𝑥2 )𝑎𝑣𝑔 = (𝑣 )𝑎𝑣𝑔 (𝑁𝑜𝑡𝑒: 𝑣𝑟𝑚𝑠 = √(𝑣 2 )𝑎𝑣𝑔 𝑖𝑠 𝑐𝑎𝑙𝑙𝑒𝑑 𝑟𝑜𝑜𝑡 𝑚𝑒𝑎𝑛 𝑠𝑞𝑢𝑎𝑟𝑒 𝑠𝑝𝑒𝑒𝑑)
3

Hence equation (3) becomes

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 𝑛𝑀(𝑣 2 )𝑎𝑣𝑔
𝑃= … (4)
3𝑉

We can also write equation (4) as

2
𝑛𝑀𝑣𝑟𝑚𝑠
𝑃= … (5)
3𝑉

RMS velocity by Kinetic Theory:

Using ideal gas law

𝑃𝑉 = 𝑛𝑅𝑇

Using equation (5)

2
𝑛𝑀𝑣𝑟𝑚𝑠
⇒( ) 𝑉 = 𝑛𝑅𝑇
3𝑉

2
𝑀𝑣𝑟𝑚𝑠
⇒ = 𝑅𝑇
3

2
3𝑅𝑇
⇒ 𝑣𝑟𝑚𝑠 =
𝑀

3𝑅𝑇
𝑜𝑟 𝑣𝑟𝑚𝑠 = √ … (6)
𝑀

1
Equation (6) shows that 𝑣𝑟𝑚𝑠 ∝ √𝑇 and 𝑣𝑟𝑚𝑠 ∝ √𝑀

Question: What will be the rms speed of Hydrogen Molecules at room temperature (300K)?

1920 m/s

Question: Which molecules would have the greater rms speed at room temperature; Hydrogen

or Oxygen?

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Average Translational Kinetic Energy:

1 1
𝐾𝑎𝑣𝑔 = ( 𝑚𝑣 2 ) = 𝑚𝑣𝑟𝑚𝑠
2
2 2

1 3𝑅𝑇 1 3𝑅𝑇
⇒ 𝐾𝑎𝑣𝑔 = 𝑚× = 𝑚×
2 𝑀 2 𝑚𝑁𝐴

3𝑅𝑇 3 𝑅
= = ( )𝑇
2𝑁𝐴 2 𝑁𝐴

3
⇒ 𝐾𝑎𝑣𝑔 = 𝑘𝑇
2

𝑅
Where 𝑘 = 𝑁 (Boltzmann’s constant). From the above equation we can say that when we are
𝐴

measuring the temperature of a gas, we are also measuring the average translational kinetic

energy.

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