THE PROPERTIES OF GASES

Critical constants
Consider a typical phase diagram for a pure substance shown:

On the above phase diagram, point B is the critical point of the

pure substance.
• The critical point provides the highest 𝑝 and the highest 𝑇 at
which a liquid can exist.
• At the critical point, both the first and second derivatives of
𝑝 with respect to (w.r.t.) 𝑉𝑚 are zero,
𝑑𝑝 𝑑2 𝑝
i.e. = 0 and 2 = 0.
𝑑𝑉𝑚 𝑑𝑉𝑚
• The temperature, pressure and molar volume at the critical
point are called the critical temperature, 𝑇𝑐 , the critical
pressure, 𝑝𝑐 , and the critical molar volume, 𝑉𝑐 , of the
substance, respectively.
• 𝑇𝑐 , 𝑝𝑐 and 𝑉𝑐 are known as the critical constants.
• The critical constants of a substance can be found by
determining the first and second derivatives of 𝑝 w.r.t. 𝑉𝑚 and
setting them equal to zero.
• After setting the 1st and 2nd derivatives to zero, then using the
equations obtained 𝑇, 𝑉 and 𝑝 can be solved to obtain the
expressions for the corresponding 𝑇𝑐 , 𝑉𝑐 and 𝑝𝑐 .
• For example, in order to obtain the van der Waals critical
constants, the following 3 equations are solved:
𝑅𝑇 𝑎
𝑝= − 2 𝑉𝑎𝑛 𝑑𝑒𝑟 𝑊𝑎𝑎𝑙𝑠 𝑒𝑞𝑛 _(1)
𝑉𝑚 − 𝑏 𝑉𝑚
• In the van der Waals equation, 𝑎, 𝑏 and 𝑅 are constants.
𝑑𝑝 𝑑 𝑅𝑇 𝑎 𝑑 𝑅𝑇 𝑑 𝑎
= − 2 = −
𝑑𝑉𝑚 𝑑𝑉𝑚 𝑉𝑚 − 𝑏 𝑉𝑚 𝑑𝑉𝑚 𝑉𝑚 − 𝑏 𝑑𝑉𝑚 𝑉𝑚2
𝑑𝑝 𝜕𝑝
• (Note: Strictly speaking in fact is meaning that 𝑇
𝑑𝑉𝑚 𝜕𝑉𝑚 𝑇
is kept constant, because the form of the van der Waals eqn in
eqn _(1) is a two-variable function; the variables are 𝑉𝑚 and 𝑇.)
 𝑑𝑝 𝑑 1 𝑑 1
= 𝑅𝑇 −𝑎
𝑑𝑉𝑚 𝑑𝑉𝑚 𝑉𝑚 − 𝑏 𝑑𝑉𝑚 𝑉𝑚2
𝑑 −1
𝑑
= 𝑅𝑇 𝑉𝑚 − 𝑏 −𝑎 𝑉𝑚−2
𝑑𝑉𝑚 𝑑𝑉𝑚
Note:
−1
• Apply the chain rule to differentiate 𝑉𝑚 − 𝑏 w.r.t. 𝑉𝑚 .
• Apply the power rule to differentiate 𝑉𝑚−2 w.r.t. 𝑉𝑚 .
Let 𝑦 = 𝑉𝑚 − 𝑏 −1
Let 𝑢 = 𝑉𝑚 − 𝑏 ⇒ 𝑦 = 𝑢−1
𝑑𝑦 𝑑 −1 −1−1 −2
−1 −1
= 𝑢 = −𝑢 = −𝑢 = 2 = 2
𝑑𝑢 𝑑𝑢 𝑢 𝑉𝑚 − 𝑏
𝑑𝑢 𝑑 𝑑𝑉𝑚 𝑑
= 𝑉𝑚 − 𝑏 = − 𝑏 =1
𝑑𝑉𝑚 𝑑𝑉𝑚 𝑑𝑉𝑚 𝑑𝑉𝑚
 𝑑
• Note: 𝑏 =0
𝑑𝑉𝑚
𝑑𝑦 𝑑𝑦 𝑑𝑢 −1 −1
= · = 2
·1= 2
𝑑𝑉𝑚 𝑑𝑢 𝑑𝑉𝑚 𝑉𝑚 − 𝑏 𝑉𝑚 − 𝑏
𝑑 −1
−1
⇒ 𝑉𝑚 − 𝑏 =
𝑑𝑉𝑚 𝑉𝑚 − 𝑏 2

𝑑 −2
𝑉𝑚−2 = −2𝑉𝑚−2−1 = −2𝑉𝑚−3 = 3
𝑑𝑉𝑚 𝑉𝑚
𝑑 −2
−2
⇒ 𝑉𝑚 = 3
𝑑𝑉𝑚 𝑉𝑚
𝑑𝑝 −1 −2
= 𝑅𝑇 · 2
−𝑎· 3
𝑑𝑉𝑚 𝑉𝑚 − 𝑏 𝑉𝑚
𝑑𝑝 −𝑅𝑇 2𝑎
= 2
+ 3
𝑑𝑉𝑚 𝑉𝑚 − 𝑏 𝑉𝑚
𝑑𝑝
=0
𝑑𝑉𝑚
−𝑅𝑇 2𝑎
⇒ 2
+ 3=0 _(2)
𝑉𝑚 − 𝑏 𝑉𝑚
𝑑2 𝑝 𝑑 𝑑𝑝 𝑑 −𝑅𝑇 2𝑎
2 = 𝑑𝑉 = 2
+ 3
𝑑𝑉𝑚 𝑚 𝑑𝑉𝑚 𝑑𝑉𝑚 𝑉𝑚 − 𝑏 𝑉𝑚
𝑑 −𝑅𝑇 𝑑 2𝑎
= +
𝑑𝑉𝑚 𝑉𝑚 − 𝑏 2 𝑑𝑉𝑚 𝑉𝑚3
𝑑 1 𝑑 1
= −𝑅𝑇 + 2𝑎
𝑑𝑉𝑚 𝑉𝑚 − 𝑏 2 𝑑𝑉𝑚 𝑉𝑚3
𝑑 −2
𝑑
= −𝑅𝑇 𝑉𝑚 − 𝑏 + 2𝑎 𝑉𝑚−3
𝑑𝑉𝑚 𝑑𝑉𝑚
Note:
• Apply the chain rule to differentiate 𝑉𝑚 − 𝑏 −2 w.r.t. 𝑉𝑚 .
• Apply the power rule to differentiate 𝑉𝑚−3 w.r.t. 𝑉𝑚 .
• Let 𝑦 = 𝑉𝑚 − 𝑏 −2
• Let 𝑢 = 𝑉𝑚 − 𝑏 ⇒ 𝑦 = 𝑢−2
𝑑𝑦 𝑑 −2 −2−1 −3
−2
= 𝑢 = −2𝑢 = −2𝑢 = 3
𝑑𝑢 𝑑𝑢 𝑢
𝑑𝑦 −2
=
𝑑𝑢 𝑉𝑚 − 𝑏 3
𝑑𝑢 𝑑 𝑑𝑉𝑚 𝑑
= 𝑉𝑚 − 𝑏 = − 𝑏 =1
𝑑𝑉𝑚 𝑑𝑉𝑚 𝑑𝑉𝑚 𝑑𝑉𝑚
𝑑
• Note: 𝑏 =0
𝑑𝑉𝑚
𝑑𝑦 𝑑𝑦 𝑑𝑢 −2 −2
= · = 3
·1= 3
𝑑𝑉𝑚 𝑑𝑢 𝑑𝑉𝑚 𝑉𝑚 − 𝑏 𝑉𝑚 − 𝑏
𝑑 −2
−2
⇒ 𝑉𝑚 − 𝑏 =
𝑑𝑉𝑚 𝑉𝑚 − 𝑏 3
 𝑑 −3 −3−1 −4
−3
𝑉𝑚 = −3𝑉𝑚 = −3𝑉𝑚 = 4
𝑑𝑉𝑚 𝑉𝑚
𝑑 −3
−3
⇒ 𝑉𝑚 = 4
𝑑𝑉𝑚 𝑉𝑚

𝑑2𝑝 −2 −3
2 = −𝑅𝑇 · 𝑉 − 𝑏 3 + 2𝑎 · 4
𝑑𝑉𝑚 𝑚 𝑉𝑚
𝑑2𝑝 2𝑅𝑇 6𝑎
2 = 𝑉 −𝑏 3− 4
𝑑𝑉𝑚 𝑚 𝑉𝑚
𝑑2𝑝
2 =0
𝑑𝑉𝑚
2𝑅𝑇 6𝑎
⇒ 3
− 4=0 _(3)
𝑉𝑚 − 𝑏 𝑉𝑚
• The solutions of the above equations are
8𝑎 𝑎
𝑉𝑐 = 3𝑏, 𝑇𝑐 = and 𝑝𝑐 =
27𝑅𝑏 27𝑏2
The critical compression factor, 𝑍𝑐 , for all gases
obeying the van der Waals equation is as given below:
𝑝𝑉𝑚
𝑍=
𝑅𝑇
𝑝𝑐 𝑉𝑐 3
⇒ 𝑍𝑐 = =
𝑅𝑇𝑐 8
Homework 1:
1. Consider eqns _(i), _(ii) and _(iii) below:
𝑅𝑇 𝑎
𝑝= − 2 _(i)
𝑉𝑚 − 𝑏 𝑉𝑚
−𝑅𝑇 2𝑎
2
+ 3=0 _(ii)
𝑉𝑚 − 𝑏 𝑉𝑚
2𝑅𝑇 6𝑎
3
− 4=0 _(iii)
𝑉𝑚 − 𝑏 𝑉𝑚

Using equations _(i), _(ii) and _(iii) above, by solving for 𝑇, 𝑉

and 𝑝 show that the critical constants, i.e. 𝑝𝑐 , 𝑉𝑐 and 𝑇𝑐 , for a
gas that obeys the van der Waals equation are as given below:
8𝑎 𝑎
𝑉𝑐 = 3𝑏, 𝑇𝑐 = and 𝑝𝑐 =
27𝑅𝑏 27𝑏2
2. Show that for all gases obeying the van der Waals
equation, the critical compression factor, 𝑍𝑐 , is as
follows:
3
𝑍𝑐 =
8