TOPIC: REAL GASES

1.1 Introduction

A real gas obeys the gas laws at certain temperature and pressure, unlike ideal gas that obeys the

laws at all temperature and pressure. The concept of ideality is purely theoretical, no real gas is

ideal in practice. Nevertheless, a real gas may either approach or deviate from ideality under

certain conditions of temperature and pressure. At high pressure or low temperature, real gas

deviates from ideality. On the other hand, real gas approaches ideality at low pressure or high

temperature.

1.2 The Behaviour of a Real gas

Discussions around the behaviour of a real gas can be broadly understood by considering the

effects of the following factors.

(a) Existence of Intermolecular forces: One of the postulates of the kinetic theory suggests that

gas molecules do not exert force on each other and their collision is perfectly elastic. As result,

increase in pressure or decrease in temperature will results in reducing the volume, but no

condensation. However, in practice, molecules of real gas exert forces (attractive and repulsive)

on each other. That is, intermolecular forces exist between the molecules of real gases.

Repulsive forces aid expansion of gases. This becomes pronounced when molecules are close to

each other and almost touching. This implies that repulsive forces are short-range forces. On the

other hand, attractive forces bring about compression or liquefaction of gases. Attractive forces

are long-range forces, as they become operational when the molecules are fairly close.

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In summary, molecular interactions bring about expansion or liquefaction in gases. Gases

become liquefied when molecules are close together. Closeness of molecules is encouraged by

high pressure or low temperature. Hence the deviation from ideality at either of these conditions.

On the other hand, at low pressure or high temperature, real gases approach ideality.

(b) Existence of Volume: Another assumption of the kinetic theory is that gas molecules are

point masses, with negligible volume, compared to the total volume of the containing vessel. In

practice, each molecule occupies a certain volume that cannot be occupied by other molecules at

that instant. That means there will be a reduction in the volume available for each molecule by a

certain amount corresponding to the net volume of the total number of molecules.

1.3 Compressibility Factor

Compressibility factor or compression factor is the ratio of the measured volume of a real gas to

the measured volume if the gas were to behave ideally. It is a measure of the deviation of real

from ideal behaviour. Compressibility factor, Z, is as expressed as

g
Vm
Z= o 1.1
Vm

o V RT
V m= = (Molar volume of ideal gas)
n P

g g
V m RT P V m
Z= ÷ =
1 P RT

PV
Z= 1.2
RT

For ideal gas, Z equals 1, and this holds for all temperatures and pressures. A plot of Z against

pressure (Figure 1.1) gives a straight line for ideal gas (dotted lines). As shown in Figure 1.1, the

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nature of the plot of Z versus P for real gases is different from that of ideal gas. These major

differences are discussed.

Figure 1.1: Plots of Z versus Pressure

1. For some real gases, like H 2 in Figure 1.1, the curve rises immediately and continue to rise.

For such gases, Z is greater than 1. This suggests that such gases expand easily. Apart from H 2,

He is also a good example of such gases.

2. For others (N2, NH3 and CO2 in Figure 1.1), an initial depression is observed before the curves

begin to rise. For such gases, Z is less than 1, which suggests that they compress and liquefy

easily.

1.4 Explanation of the Trends on a Z versus P Plots

The trends observed in Figure 1.1, for N 2, NH3 and CO2 can be ascribed to the effects of

intermolecular forces. Intermolecular attractions hold the molecules slightly closer together,

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resulting in significant decrease in volume as pressure increases. This means molecules are

brought closer within the range of these attractive forces. This is why the curves dip downward

as pressure increases initially. This dip is more pronounce for heavier gas, like CO 2 in Figure 1.1.

As pressure continue to increase, the molecules begin to make incursions into each other

territory, which encourages the emergence of stronger repulsive forces. The gas begins to expand

and the curve eventually bends upward.

The extent of the initial dip is also affected by temperature, Figure 1.2. The plots in Figure 1.2

clearly demonstrate the effect of temperature on behaviour of a real gas. A decrease in

temperature encourages deviation of a real gas from ideal behaviour, while the gas approaches

ideal behaviour as temperature increases, Higher temperatures lead to increased thermal motion,

which tends to overcome the effect of intermolecular attraction, hence enhanced ideal behaviour.

Figure 1.2: Effect of Temperature on the Plots of Z and P

4.5 Corrections to the Ideal gas equation

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The use of the ideal gas equation for solving problems involving real gases is premised on the

assumption that the gases behave ideally. In practice, no real gas is ideal. Therefore, accurate

solutions to problems relating to real gases requires that corrections be made to the ideal gas

equation. These corrections can be made through the use of the Viral equation, Van der Waals’

equation of state or combination of both.

The correction offered by the Viral equation underlines the deviation of real gas from ideal

behaviour by expanding the compressibility factor in powers of the inverse molar volume. On

the other hand, the corrections proposed by the Van der Waals’ equation of state address the

erroneous assumptions of absence of intermolecular forces and the existence of negligible

volume. The Van der Waals’ equation of state is discussed.

1.6 Van der Waals equation of state

Essentially, the Van der Waals equation of state introduced two terms to the ideal gas equation to

correct for two erroneous assumption of absence of intermolecular forces and negligible volume,

4.6.1 Correction for Volume

One of the assumptions of the kinetic theory is that molecules of gases do not have volume, but

are like point charges. However, in reality, they do have volume. If the volume of a molecule is

represented by ‘b’, the volume occupied by ‘n’ molecules will be nb. Hence the remaining

volume left for the pressure to act on will be V-nb. This is called the compressible volume. The

volume term, V, in the ideal gas equation can then be written correctly, as expressed in equation

1.3

P(V – nb) = nRT 1.3

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 nRT
( V – nb )= 1.4
P

nRT
V= +nb 1.5
P

V nRT nb
=V m= + 1.6
n nP n

RT
V m= +b 1.7
P

Equations 1.7 shows that the molar volume of a real gas is greater than that of ideal gas by ‘ b’.

The term ‘b’ is called the excluded volume per mole of the molecule (Figure 1.3). This is closely

related to the size of the molecule. It is not affected by temperature and pressure.

Figure 1.3: Pictorial representation of the Excluded volume

1.6.2 Calculation of the Excluded volume

In order to calculate ‘b’, we consider two molecules joined together (Figure 1.3). Therefore, the

collision diameter (represented by 2r in Figure 1.3), σ, can be taken to be the radius of the

excluded volume per pair of molecules. Therefore, excluded volume per pair of molecules is

given by

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 4 3
Excluded volume per pair of molecules ¿ πσ 1.8
3

Excluded volume per molecule ¿ (

σ
r= 1.10
2

Excluded volume per molecule can be related to the actual volume of the molecule. Actual

volume of the molecule is the volume a given gas will occupy in a container at a particular

pressure.

()
3
4 σ
Actual volume of molecule ¿ π 1.11
3 2

Actual volume of molecule ¿ (

Equation 4.12 shows that the excluded volume per pair of molecules is eight times the actual

volume of the molecule (equation 1.13), while the excluded volume per molecule is four times

the actual volume of the molecule (equation 1.14)

4
3
3
π σ =8 ×
1 4
8 3 (
πσ
3
) 1.13

¿1 4
2 3 ( )
π σ 3 =4 ×
1 4
8 3 (
π σ3 ) 1.14

2 3 2 3
Excluded volume per molecule ¿ π σ = π ( 2 r )
3 3

16 3
Excluded volume per molecule ¿ πr 1.15
3

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 16 3
Excluded volume per mole of molecule ¿ b=¿ πr NA 1.16
3

1.6.3 Correction for Molecular attraction

Collision between gaseous molecules and the wall of the container is the origin of pressure

exerted by gases. Pressure is affected by the force and frequency of such collision. The existence

of attractive forces between the molecules of gases reduces both the force and frequency of

collision, hence imparting on the magnitude of pressure. Consider a molecule which is on the

verge of striking the wall of the containing vessel, Figure 1.4. Attraction by other molecules

results in an inward pull thus reducing the force with which the molecule strikes the wall. The

frequency of collision is also reduced, because after collision. molecules stay together

momentarily, rather than bouncing off immediately. The gas is under the influence of not only

external pressure but also these attractive forces, which generate an additional pressure, called

internal pressure, P’.

Figure 1.4: Effect of attractive force on pressure

If there are ‘n’ molecules in a volume, V. The force of collision and the frequency of collision are

n
both directly proportional to .
V

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 n
F∝ 1.17
V

n
f∝ 1.18
V

2
n
P’ ∝ 2 1.19
V

2
n
P’=a 2 1.20
V

Therefore, equation 1.3 can be correctly written as

( P+P’ )( V −nb ) =nRT 1.21

( )
2
n
P+ a 2 ( V −nb )=nRT
V

( )
2
n nRT
P+ a =
V
2
( V −nb )

2
nRT n
P= −a 2 1.22
( V −nb ) V

Pressure exerted by 1 mol of the gas is

RT a
P= − 2 1.23
( V m −b ) V m

Equation 1.23 is known as the Van der Waals’ equation of state. The equation shows that the

a
pressure of a real gas is less by 2 when compared to that of an ideal gas. The constants ‘a’ and
Vm

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‘b’ are known as Van der Waals’ constants. The values of Van der Waals’ constants vary from

gas to gas. Table 1.1 shows values of Van der Waals’ constants of some gases.

The constant ‘a’ corrects for the erroneous assumption of the absence of intermolecular

attraction in gases. The value of ‘a’ is an indirect measure of the magnitude of attractive force

between the molecules. The higher the value of ‘a’, the more easily the gas can be liquified. The

units of ‘a’ are L2 mol-2 atm or m6 mol-2 atm.

The constant ‘b’ corrects for the erroneous assumption of negligible volume. The magnitude of

‘b’ is an indirect measure of the size of the molecule. The higher the value of ‘b’, the larger the

size of the molecule and the smaller the compressible volume (V – nb). The unit of ‘b’ is L mol-1

or m3 mol-1.

1.6.4 Critical constants and Van der Waal constants

The critical temperature, Tc, of a gas is the temperature above which the gas cannot be liquefied.

If a gas is compressed at the critical temperature, the phase boundary between the liquid and the

gas phase disappears. The pressure required to liquefy a gas at the critical temperature is called

the critical pressure, Pc, of the substance. The molar volume at the critical point is called the

critical molar volume, Vc. The quantities Tc, Pc and Vc are called the Critical constants. These

quantities are unique to each substance.

Table 1.1: Van der Waals’ constants of some gases

a (L2 mol-2 atm) b (L mol-1)

Acetic acid 17.46 0.1065

Acid anhydride 19.88 0.1263

Acetone 15.80 0.1124

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 Acetonitrile 17.56 0.1168

Acetylene 4.45 0.0522

Ammonia 4.17 0.0371

Argon 1.34 0.03201

Benzene 17.98 0.1193

Bromobenzene 28.94 0.1539

Butane 14.45 0.1226

Carbon dioxide 3.59 0.04267

Carbon disulphide 11.61 0.07685

Carbon monoxide 1.48 0.03985

Chlorine 6.49 0.05622

Helium 0.034 0.0238

Hydrogen 0.244 0.02661

The critical constants of gases can be related to their Van der Waal constants by these relations

a
Pc = 2 1.24
27 b

8a
T c= 1.25
27 Rb

V c =3 b 1.26

The above equations are alternative ways of determining the Van der Waal constants.

1.6.5 Limitation of the Van der Waals’ equation of state

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The Van der Waals’ equation of state is consistent with the behaviors of real gases at moderately

high pressures, but there are appreciable deviations at too low temperature or too high pressures.

The values of Van der Waal constants do not remain constant over the entire range of

temperature and pressure. This makes the equation valid only over specific range of temperature

and pressure.

1.7 The Principle of Corresponding state

The validity of the principle of corresponding state is hinged on the use of a set of quantities,

called the reduced variables. These quantities are used to represent the macroscopic quantities

of pressure, volume and temperature of gases. Pressure is represented as reduced pressure, Pr,

temperature as reduced temperature, Tr, and volume as reduced volume, Vr, Reduced variables

are expressed in terms of the critical constants, as shown in the following equations

P
Pr = 1.27
Pc

P
T r= 1.28
Tc

V
V r= 1.29
Vc

The principle of corresponding state states that all fluids at the same reduced temperature and

pressure have the same compressibility factor and all of them deviate from ideality about the

same degree. In coming up with this proposition, Van der Waal was of the opinion that gases in

the same reduced volume at the same reduced temperature would exert the same pressure (that is,

the gas behave the same). Essentially, the principle suggests that any pure gas at the same

reduced temperature and reduced pressure should have the same compressibility factor.

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Figure 1.5: Generalized compressibility factor plot

For real gases, pressure-volume-temperature (PVT) data varies from one pure gas to another.

Nonetheless, when the compressibility factors of various single-component gases are plotted

against pressure, at the same temperature, many of the plots display similar isotherm shapes. A

generalized plot, Figure 1.5, that can be used for different gases, can be obtained if the

compressibility factor data is normalized using reduced temperature and pressure. This

underscores the relevance of the concept of reduced variables to the understanding of the

principle of corresponding state. The principle is not applicable to non-spherical or polar

molecules. This is because Van der Waal defines a molecule as a sphere.

Using the reduced variables, a reduced equation of state can be obtained the from Van der

Waals’ equation of state (equation 1.23).

RT a
P= − 2 1.23
( V m −b ) V m

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Insert Pc, Tc and Vc (as defined in equations 1.24, 1.25 and 1.26) into equation 1.30 to give

a Pr 8 aR T r a
= − 1.30
27 b
2
27 Rb ( 3 bV r −b ) 2 2
9b V r

Pr 8Tr 1
2
= 2
− 2 2 1.31
3b 3 b ( 3 V r −1 ) b Vr

Pr 8Tr 1
= − 1.32
3 3 ( 3V r−1 ) V 2r

8Tr 3
Pr = − 1.33
( 3V r−1 ) Vr
2

Equation .33 is the reduced equation of state. The equation has the same form as the original Van

der Waals’ equation of state, without the coefficients, ‘a’ and ‘b’. This suggests that the Van der

Waals’ equation of state is compatible with the principle of corresponding state.

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