Chapter 5: Equation of State

Equation of State of an Ideal Gas ............................................................................................................. 1

Reasons for Modification of Gas Equation .............................................................................................. 2

Van der Waals Equation of State ............................................................................................................. 2

Estimation of Critical Constants .......................................................................................................... 4

Limitations of van der Waals equation .................................................................................................... 6

Critical Constants of Gases ...................................................................................................................... 6

Reduced Equation of State ....................................................................................................................... 6

Arpon Chakraborty, Lecturer, Department of Physics, BSMRSTU

 PHY103/Ch.5/2022-23

Equation of State of an Ideal Gas

Boyle's law states that at a constant temperature, the volume of a fixed amount of gas is inversely
proportional to its pressure. This means that as the pressure of a gas increases, its volume decreases, and
vice versa. This relationship can be expressed mathematically as:
1
𝑃∝
𝑉
⇒ 𝑃1 𝑉1 = 𝑃2 𝑉2 … … … … … (5.1)
where:
• P1 and P2 are the pressures of the gas at two different states
• V1 and V2 are the volumes of the gas at the two different states

Charles's law states that at a constant pressure, the volume of a fixed amount of gas is directly
proportional to its absolute temperature. This means that as the temperature of a gas increases, its volume
increases, and vice versa. This relationship can be expressed mathematically as:
𝑇∝𝑉
𝑉1 𝑉2
⇒ = … … … … … (5.2)
𝑇1 𝑇2

where:
• T1 and T2 are the temperatures of the gas at two different states (in kelvins)
Gay-Lussac's law states that at a constant volume, the pressure of a fixed amount of gas is directly
proportional to its absolute temperature. This means that as the temperature of a gas increases, its
pressure increases, and vice versa. This relationship can be expressed mathematically as:
𝑃1 𝑃2
= … … … … … (5.3)
𝑇1 𝑇2
Avogadro's law states that the volume occupied by an ideal gas at a constant temperature is directly
proportional to the number of molecules of the gas present in the container.
This statement gives rise to the molar volume of a gas, which at STP (273.15 K, 1 atm) is about 22.4 L.
The relation is given by:
𝑉∝𝑛
𝑉1 𝑉2
⇒ =
𝑛1 𝑛2
where n is equal to the number of molecules of gas (or the number of moles of gas).
The Combined gas law or General Gas Equation is obtained by combining Boyle's Law, Charles's law,
and Gay-Lussac's Law. It shows the relationship between the pressure, volume, and temperature for a
fixed mass of gas:
𝑃𝑉 = 𝑘𝑇
This can also be written as:
𝑃1 𝑉1 𝑃2 𝑉2
= … … … … … (5.4)
𝑇1 𝑇2
With the addition of Avogadro's law, the combined gas law develops into the ideal gas law:
𝑃𝑉 = 𝑛𝑅𝑇 … … … … … (5.5)
This is known as the equation of state of an ideal gas or simply gas law,

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Arpon Chakraborty, Lecturer, Department of Physics, BSMRSTU
 PHY103/Ch.5/2022-23

where:
• P is the pressure of the gas
• V is the volume of the gas
• n is the number of moles of gas
• R is the ideal gas constant (8.314 J/mol.K)
• T is the temperature of the gas (in kelvins)
The ideal gas law is a good approximation for the behavior of real gases at low pressures and high
temperatures. However, for real gases, the relationship between pressure, volume, and temperature is
not always linear. This is because real gases have molecules that have a finite size and can interact with
each other.
This law has the following important consequences:
i. If temperature and pressure are kept constant, then the volume of the gas is directly proportional
to the number of molecules of gas.
ii. If the temperature and volume remain constant, then the pressure of the gas changes is directly
proportional to the number of molecules of gas present.
iii. If the number of gas molecules and the temperature remain constant, then the pressure is
inversely proportional to the volume.
iv. If the temperature changes and the number of gas molecules are kept constant, then either
pressure or volume (or both) will change in direct proportion to the temperature.

Reasons for Modification of Gas Equation

The perfect gas equation PV = RT is not obeyed by real gases, particularly at high pressure and low
temperature. At ordinary temperatures and pressures, the deviation is small but at high pressures and
low temperatures the deviations are very large. In the derivation of the perfect gas equation, on the basis
of kinetic theory of gases, the following assumptions have been made, which do not hold true in case of
real gases. These are (i) the size of the molecule of the gas is negligible, and (ii) the forces of
intermolecular attraction are absent. But in actual practice, at high pressure the size of the molecule of
the gas becomes significant and cannot be neglected, in comparison with the volume of the gas. Also at
high pressure, the molecules come closer and the forces of molecular attraction are appreciable. Hence,
a perfect gas equation needs modification.

Van der Waals Equation of State

In 1879 Van der Waals modified the perfect gas equation 𝑃𝑉 = 𝑅𝑇 by applying corrections for
a) Intermolecular force of attraction and
b) Finite size of molecules.
1. Correction for Pressure:
Consider a molecule A of the gas, well inside the vessel as shown in Fig. 5.1. It is attracted by other B
molecules in all directions with the same force and the net force acting on it is zero. But when it strikes
the wall of the vessel (position A'), it is pulled back by other molecules. Its velocity and hence
momentum with which it will strike the wall would be less than the momentum with which it will strike
in the absence of the force of attraction. This reduction in momentum results in decrease of pressure. In

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Arpon Chakraborty, Lecturer, Department of Physics, BSMRSTU
 PHY103/Ch.5/2022-23

other words, the observed pressure of the gas is less than the actual pressure. The correction for pressure
p depends upon
(i) No. of molecules striking a unit area per unit time of
the walls of the container, and
(ii) The resultant inward pull of cohesion on each of the
striking molecules.
Each of these factors is proportional to the density of the
gas.
1
∴ Correction for pressure 𝑝 ∝ 𝜌2 ∝ 𝑉 2
𝑎
𝑜𝑟, 𝑝 = 2
𝑉
Here a is a constant and V is the volume of the gas.
Therefore, the corrected or real pressure
=𝑃+𝑝
𝑎
= (𝑃 + 2 ) … … … (5.6)
𝑉
Fig. 5.1
where P is the observed pressure.
2. Correction for Volume:
Due to the finite size of gas molecules, the actual space
available for the movement of the molecules
is less than the volume of the vessel. The molecules have
the sphere of influence (Fig. 5.2) around
them of radius (2r), within which no other molecule can
penetrate.
Here r is the radius of each gas molecule.
4
Volume of the molecule = 𝑥 = 3 𝜋𝑟 3
The center of any two molecules can approach each other
only by a minimum distance of 2r. The volume of sphere of
influence of each molecule
4 4 Fig. 5.2
𝑠 = 𝜋(2𝑟)3 = 8 × 𝜋𝑟 3 = 8𝑥
3 3
Let us fill the whole space of the volume V with n molecules one by one.
The volume available for the first molecule = 𝑉
The volume available for the second molecule = 𝑉 − 8𝑥 = 𝑉 − 𝑠
The volume available for n-th molecule = [𝑉 − (𝑛 − 1) 𝑠].
∴ Average space available for each molecule
𝑉 + (𝑉 − 𝑠) + (𝑉 − 2𝑠) + ⋯ + [𝑉 − (𝑛 − 1) 𝑠]
=
𝑛
𝑛𝑉 𝑠
= − [1 + 2 + 3 + ⋯ + (𝑛 − 1)]
𝑛 𝑛
𝑛𝑉 𝑠 𝑛(𝑛 − 1)
= − .
𝑛 𝑛 2
𝑛𝑠 𝑠
=𝑉− +
2 2
𝑠
As the number of molecules is very large 2 can be neglected.

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Arpon Chakraborty, Lecturer, Department of Physics, BSMRSTU
 PHY103/Ch.5/2022-23

∴ Average space available of each molecule

𝑛𝑠
=𝑉−
2
𝑛(8𝑥)
=𝑉−
2
= 𝑉 − 4(𝑛𝑥)
= 𝑉 − 𝑏 … … … … (5.7)
where 𝑏 = 4(𝑛𝑥) = four times the actual volume of the molecules.
Thus, the Van der Waals equation of state for a gas is
𝑎
(𝑃 + 2 ) (𝑉 − 𝑏) = 𝑅𝑇 … … … … … (5.8)
𝑉
where a and b are Van der waals constants.

Estimation of Critical Constants

Consider the critical isothermal ACB as shown in Fig. 5.3. At the
critical point C, the curve is horizontal. Therefore, at point C,
𝑑𝑃
(𝑑𝑉 = 0). At this point, the tangent also crosses the curve. Therefore,
the tangent at such a point is said to be stationary and the point is
called 'the point of inflexion'. At the point of inflexion, we have
𝑑2 𝑃
=0
𝑑𝑉 2
Hence, at critical point C, we have
𝑑𝑃 𝑑2 𝑃
= 0 and 𝑑𝑉 2 = 0. Fig. 5.3
𝑑𝑉

The Van der Waals equation can be written as

𝑎
(𝑃 + 2 ) (𝑉 − 𝑏) = 𝑅𝑇
𝑉
RT 𝑎
⇒P= − 2
(𝑉 − 𝑏) 𝑉
𝑑𝑃 𝑅𝑇 2𝑎
⇒ =− 2
+ 3
𝑑𝑉 (𝑉 − 𝑏) 𝑉
2
𝑑 𝑃 2𝑅𝑇 6𝑎
𝑎𝑛𝑑 2
= 3
− 4
𝑑𝑉 (𝑉 − 𝑏) 𝑉
At the critical point C, we have
𝑑𝑃 𝑑2𝑃
𝑇 = 𝑇𝑐 , 𝑃 = 𝑃𝑐 , 𝑉 = 𝑉𝑐 , = 0 and =0
𝑑𝑉 𝑑𝑉 2
Substituting in the above equations,
RTc 𝑎
Pc = − 2 … … … … (5.9)
(𝑉𝑐 − 𝑏) 𝑉𝑐
𝑅𝑇𝑐 2𝑎 𝑅𝑇𝑐 2𝑎
0=− + ⇒ = … … … (5.10)
(𝑉𝑐 − 𝑏)2 𝑉𝑐3 (𝑉𝑐 − 𝑏)2 𝑉𝑐3
2𝑅𝑇𝑐 6𝑎 2𝑅𝑇𝑐 6𝑎
0= − ⇒ = … … … (5.11)
(𝑉𝑐 − 𝑏)3 𝑉𝑐4 (𝑉𝑐 − 𝑏)3 𝑉𝑐4
Dividing (5.10) by (5.11),

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Arpon Chakraborty, Lecturer, Department of Physics, BSMRSTU
 PHY103/Ch.5/2022-23

𝑉𝑐 − 𝑏 𝑉𝑐
=
2 3
⇒ 3𝑉𝑐 − 3𝑏 = 2𝑉𝑐
∴ 𝑉𝑐 = 3𝑏
Substituting the value of 𝑉𝑐 in equation (5.10), we get
𝑅𝑇𝑐 2𝑎
2
=
(3𝑏 − 𝑏) (3𝑏)3
𝑅𝑇𝑐 2𝑎
⇒ 2=
4𝑏 27𝑏 3
8𝑎
∴ 𝑇𝑐 =
27𝑏𝑅
Substituting the value of 𝑉𝑐 and 𝑇𝑐 in equation (5.9), we get
8𝑎𝑅 𝑎
Pc = −
27𝑏𝑅(3𝑏 − 𝑏) (3𝑏)2
8𝑎 𝑎
= −
27 × 2𝑏 2 9𝑏 2
𝑎 8 𝑎 1
= 2 [ − 1] = 2 ×
9𝑏 6 9𝑏 3
𝑎
𝑃𝑐 =
27𝑏 2
We have,
8𝑎
𝑇𝑐 =
27𝑏𝑅
𝑎 27𝑅𝑇𝑐
= … … … … (5.12)
𝑏 8
But,
𝑎
𝑃𝑐 =
27𝑏 2
𝑎
= 27𝑃𝑐 … … … … (5.13)
𝑏2
Dividing (5.12) by (5.13),
𝑎 𝑏2 8𝑎 1
× = ×
𝑏 𝑎 27𝑏𝑅 27𝑃𝑐
𝑅𝑇𝑐
∴𝑏=
8𝑃𝑐
Substituting the value of 𝑏 in equation (5.12), we get
𝑎 27𝑅𝑇𝑐
=
𝑅𝑇𝐶 8
8𝑃𝐶
𝑅𝑇𝐶 27𝑅𝑇𝑐
𝑎= ×
8𝑃𝐶 8
2 2
27𝑇𝐶 𝑅
∴𝑎=
64𝑃𝑐

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Arpon Chakraborty, Lecturer, Department of Physics, BSMRSTU
 PHY103/Ch.5/2022-23

Limitations of van der Waals equation

In spite of the fact that Van der Waals' equation has been very helpful in understanding many of the
properties of real gases, the evaluation of critical constants, the derivation of the equation of
corresponding states, the continuity of the gaseous to the liquid state, when it is subjected to
experimental verification, we find considerable discrepancies.
i. The isothermals which are obtained theoretically from van der Waals' equation do not tally with
those obtained experimentally by Andrews.
ii. The values of 'a' and 'b' are not constant but varies with temperature.
iii. From van der Waals' equation 𝑉𝑐 = 3𝑏, but experiments show that 𝑉𝑐 = 2𝑏 approximately, ranging
from 1.41b for argon gas to 2.8b for hydrogen gas.
𝑅𝑇𝑐
iv. The value of critical coefficient, according to the equation should be 2.67 for all gases, but
𝑃𝑐 𝑉𝑐
experimentally it is different for different gases, and its average value is 3.75.

Critical Constants of Gases

1. Critical temperature (𝑻𝒄 ): It is defined as the maximum temperature at which a gas can be
liquefied by the increase of pressure alone. Above this temperature, the gas cannot be liquefied
howsoever large the applied pressure may be.
2. Critical pressure (𝑷𝒄 ): The pressure necessary to liquefy a gas at critical temperature is called the
critical pressure.
3. Critical volume (𝑽𝒄 ): It is the volume which unit mass of a gas occupies at the critical temperature
and critical pressure.
These three quantities, T, P and V are called critical constants of a gas.
4. Critical point: It is that point on the isothermal for the critical temperature at which the change of
state from the gaseous state to the liquid state takes place under constant values of 𝑃𝑐 and 𝑉𝑐 .

Reduced Equation of State

When the actual pressure, volume and temperature of a fixed mass of a gas are divided by the critical
values of these quantities, the resulting ratios are called the reduced pressure (𝑃𝑟 ), reduced volume (𝑉𝑟 )
and reduced temperature (𝑇𝑟 ), respectively.
Thus, we have
𝑃 𝑉 𝑇
𝑃𝑟 = , 𝑉𝑟 = 𝑎𝑛𝑑 𝑇𝑟 =
𝑃𝑐 𝑉𝑐 𝑇𝑐
𝑎
𝑃 = 𝑃𝑐 𝑃𝑟 = 𝑃
27𝑏 2 𝑟
𝑉 = 𝑉𝑐 𝑉𝑟 = 3𝑏𝑉𝑟
8𝑎
𝑇 = 𝑇𝑐 𝑇𝑟 = 𝑇
27𝑅𝑏 𝑟
Substituting these values of P, V and T in equation
𝑎
(𝑃 + 2 ) (𝑉 − 𝑏)
𝑉

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Arpon Chakraborty, Lecturer, Department of Physics, BSMRSTU
 PHY103/Ch.5/2022-23

we get
𝑎 𝑎 8𝑎
( 𝑃𝑟 + 2 2 ) (3𝑏𝑉𝑟 − 𝑏) = 𝑅 𝑇
27𝑏 2 9𝑏 𝑉𝑟 27𝑅𝑏 𝑟
𝑎 3 1 8𝑎
⇒ (𝑃𝑟 + ) 3𝑏 (𝑉𝑟 − ) = 𝑇
27𝑏 2 𝑉𝑟2 3 27𝑏 𝑟
3 1 8
⇒ (𝑃𝑟 + 2 ) (𝑉𝑟 − ) = 𝑇𝑟
𝑉𝑟 3 3
This equation does not contain the constants a and b; which are characteristic of a particular gas.
The equation is called Van der Waals reduced equation of State.

Problems
1. Calculate the van der Waals constants for dry air, given that 𝑇𝑟 = 132𝐾, 𝑃𝑐 = 37.2 atm and R per
mole = 82.07 cm3 atms K-1.
2. The van der Waals constants a and b for 1 gram molecule of hydrogen are a = 0.245 atms-litre2-
mole2 and b = 2.67×10-2 litre-mole-1. Calculate the critical temperature.
3. For hydrogen gas the critical pressure is 12.8 atms and the critical volume is 69.68 cc per gm-mol.
Calculate the values of the constants of van der Wall's for one gm-molecule of the gas and calculate
the critical temperature.

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Arpon Chakraborty, Lecturer, Department of Physics, BSMRSTU