Ideal Gases Real Gases

Ideal Gases obey all gas laws under all conditions of
temperature and pressure.
The volume occupied by the molecules is negligible as
compared to the total volume occupied by the gas.
The force of attraction among the molecules are negligible.
Obeys ideal gas equation
PV = nRT
Real Gases obey gas laws only at low pressures and high
temperature.
The volume occupied by the molecules is not negligible as
compared to the total volume of the gas.
The force of attraction are not negligible at all temperatures
and pressures.
Obey Van der Waals equation
(P + an2/V2) (V - nb) = nRT

Ideal and Real Gases

A gas which obeys the ideal gas equation, PV = nRT under all conditions of temperature and pressure is called
an ‘ideal gas’.However, there is no gas which obeys the ideal gas equation under all conditions of temperature
and pressure. Hence, the concept of ideal gas is only theoretical or hypothetical. The gases are found to obey
the gas laws fairly well if the pressure is low or the temperature is high. Such gases are, therefore, known as
‘Real gases.’ All gases are real gases. However, it is found that gases which are soluble in water or are easily
liquefiable, e. g. CO2, SO2, NH3 etc. show larger deviations than the gases like H2, O2, N2 etc.

Differences between Ideal Gas and Real Gas

Study of Deviations
To understand the deviations from ideal behaviour, let us first see how the real gases show deviations from
Boyle’s law. According to Boyle’s law, PV = constant, at constant temperature. Hence, at constant
temperature, plot of PV vs. P has to be a straight line which is parallel to x-axis. However, the real gases do not
show such a behaviour as shown in figure no. 1 below.
 Fig No. 1 PV vs P for Real and Ideal Gas
From the plots, we observe that for gases like H2 and He, PV increases continuously with increase of pressure
whereas for gases like CO, CH4 etc. PV first decreases with increase of pressure and reaches a minimum value
and then increases continuously with increase of pressure. Similarly, if we plot experimental values of pressure
versus volume at constant temperature (that is, for real gas) and theoretically calculated values from Boyle’s
law (that is,for ideal gas) the two curves do not coincide as shown in figure no. 2.

Fig. No. 2 Pressure vs Volume for Real and Ideal Gas

From above graphs, we observe that at higher pressure, volume which is observed is higher than that of
calculated volume. At lower pressures, the observed and the calculated volumes approach each other.
Alternatively, upto what extent a real gas deviates from ideal behaviour can be studied using the terms of a
quantity ‘Z’ which is known as the compressibility factor, and defined as:

(i) For an ideal gas, as PV = nRT, Z = 1

(ii) For a real gas, as PV ≠ nRT, Z ≠ 1.
Hence, two cases arise:
(a) When Z < 1, (For Example: for CH4, CO2 etc.) The gas is said to show negative deviation. Therefore gas
will show more compression than expected from ideal behaviour.
This is caused by predominance of attractive forces among the molecules of these gases.
(b) When Z > 1, the gas is said to show positive deviation. This implies that the gas will show less
compression than expected from ideal behaviour.
This is caused by the predominance of the strong repulsive forces among the molecules. Greater the departure
in the value of Z from unity, greater are the deviations from ideal behaviour.
At the same temperature and pressure, the extent of deviation depends upon the nature of the gas, as shown in
figure no. 3 Thus, at intermediate pressures, CO2 shows much larger negative deviation than H2 or N2.

Fig. No. 3 Z vs P for Different Gases

For the same gas, at a particular pressure, the extent of deviation depends upon temperature, as shown in figure
no. 4 for the case of N2 gas.

Fig. No. 4 Z vs P for N2 gas at different temperatures

Plots in fig. no. 4 show that as the temperature increases, the minimum in the curve shifts upwards. Ultimately,
a temperature is reached at which the value of Z remains close to 1 over an appreciable range of pressure. For
Example, in case of N2, at 323 K, the value of Z remains close to 1 upto nearly 100 atmospheres.
The temperature at which a real gas behaves like an ideal gas over an appreciable pressure range is
called Boyle temperature or Boyle point.
Further, from the plots shown in figure no. 3 and 4, it may be seen that at ordinary pressures (1-10 atm), Z is
very near to 1, that is, the deviations from ideal behaviour are so small that the ideal gas laws can be applied.

Significance of compressibility factor

The significance of compressibility factor can be further understood from the following derivation:

If the gas shows ideal behaviour,

Substituting this value of nRT/P in eqn. (1), we get

Thus, compressibility factor is defined as the ratio of the actual molar volume of the gas (For
Example: experimentally observed value) to the calculated molar volume (considering it as an ideal gas) at the
same temperature and pressure.

Causes of Deviation from Ideal Behaviour

As stated above, the real gases obey ideal gas equation (PV = nRT) only if the pressure is low the temperature
is high. However, if the pressure is high or the temperature is low, the real gases show marked deviations from
ideal behaviour. The reasons for such a behaviour shown by the real gases have been found to be as follows:
The derivation of the gas laws (and hence of the ideal gas equation) is based upon the Kinetic Theory of Gases
which in turn is based upon certain assumptions. Thus, there must be something wrong with certain
assumptions. A careful study shows that at high pressure or low temperature, two assumptions of Kinetic
Theory of Gases are fails:

 When compared to the total volume of the gas, the volume occupied by the gas molecules is
negligible.
 The forces of attraction or repulsion between the gas molecules are negligible.

The above two assumptions are true only if the pressure is low or the temperature is high so that the distance
between the molecules is large. However, if the pressure is high or the temperature is low, the gas molecules
come close together. Hence, under these conditions:

 The forces of attraction or repulsion between the molecules.

 The volume occupied by the gas may be so small that the volume occupied by the molecules may not
be negligible.
Equation of State for the Real Gases (van der Waals
Equation)
To explain the behaviour of real gases, J .D. van der Waals, in 1873, modified the ideal gas equation applying
appropriate corrections so as to take into account

 The volume of the gas molecules

 The forces of attraction between the gas molecules

He put forward the modified equation, known after him as van der Waals equation. The equation is
For 1 mole of the gas,

For n moles of the gas,

Where ‘a’ and ‘b’ van der Waals constant.There values depend upon nature of gas.

Significance of Van der Waals Constants

 Van der Waals constant ‘a’: Its value is a measure of the magnitude of the attractive forces among
the molecules of the gas. There would be large intermolecular forces of attraction if the value ‘a’, is
large.
 Van der Waals constant ‘b’: Its value is a measure of the effective size of the gas molecules.
Its value is equal to four times the actual volume of the gas molecules. It is called Excluded
Volume or Co-volume.

Units of van der Waals Constants

 Units of ‘a’: As p = am2/V2, therefore a = (p × V2) / n2 = atm L2 mol-2 or bar dm6 mol-2
 Units of ‘b’: As volume correction v = n b, therefore b = v/n = Lmol-1 or dm3mol-1

Explanation of the Behaviour of Real Gases by van der

Waals Equation
 At Very Low Pressures, V is very large. Hence, the correction term a/V2 is so small that it can be
neglected, Similarly, the correction term ‘b’ can also be neglected in comparison to V. Thus, van der
 Waals equation reduces to the form PV = RT. This explains why at very low pressures, the real gases
behave like ideal gases.
 At Moderate Pressures, V decreases. Hence, a/V2 increases and cannot be neglected. However, is
still large enough in comparision to ‘b’ so that ‘b’ can be neglected. Thus, van der Waals equation
becomes

Thus, compressibility factor is less than 1. So at when at constant temperature, pressure is increased, V
decreases so that the factor a/RTV increases. This explains why initially a dip in the plot of Z versus P
is observed.

 At High Pressures, V is so small that ‘b’ cannot be neglected in comparison to V. The factor a/V2 is
no doubt large but as P is very high, a/V2 can be neglected in comparison to P. Thus, van der Waals
equation reduces to the form:

Thus, compressibility factor is greater than 1. As P is increased (at constant T), the factor Pb/RT
increases. This explains why after minima in the curves, the compressibility factor increases
continuously with pressure.

 At High Temperatures: V is very large (at a given pressure) so that both the correction factors
(a/V2 and b) become negligible as in case (i). Hence, at high temperature, real gases behave like ideal
gas.

Explanation of the exceptional behaviour of hydrogen

and helium
From figure no. 3, it may be seen that for H2 and He, the compressibility factor Z is always greater than 1 and
increases with increase of pressure. This is because H2 and He being very small molecules, the intermolecular
forces of attraction in them are negligible, that is, ‘a’ is very small so that a/v2 is negligible. The van der Waals
equation, therefore, becomes
 Thus, PV/RT that is, Z > 1 and increases with increase in the value of P at constant T.
Watch this Video for more reference

A gas which obeys the gas laws and the gas equation PV = nRT strictly at
all temperatures and pressures is said to be an ideal gas.The molecules of
ideal gases are assumed to be volume less points with no attractive forces
between one another. But no real gas strictly obeys the gas equation at all
temperatures and pressures. Deviations from ideal behaviour are observed
particularly at high pressures or low temperatures.

The deviation from ideal behaviour is expressed by introducing a factor Z known as compressibility factor in
the ideal gas equation. Z may be expressed as Z = PV / nRT
 In case of ideal gas, PV = nRT ∴ Z = 1
 In case of real gas, PV ≠ nRt ∴ Z ≠ 1
Thus in case of real gases Z can be < 1 or > 1
 When Z < 1, it is a negative deviation. It shows that the gas is more compressible than expected from ideal
behaviour.

 When Z > 1, it is a positive deviation. It shows that the gas is less compressible than expected from ideal
behaviour.
Causes of Deviation from Ideal Behaviour
The causes of deviations from ideal behaviour may be due to the following two assumptions of kinetic theory of
gases.

 The volume occupied by gas molecules is negligibly small as compared to the volume occupied by the gas.

 The forces of attraction between gas molecules are negligible.

The first assumption is valid only at low pressures and high temperature, when the volume occupied by the gas
molecules is negligible as compared to the total volume of the gas. But at low temperature or at high pressure,
the molecules being in compressible the volumes of molecules are no more negligible as compared to the total
volume of the gas.
The second assumption is not valid when the pressure is high and temperature is low. But at high pressure or
low temperature when the total volume of gas is small, the forces of attraction become appreciable and cannot
be ignored.

Example 1:

Question
1 mole of SO2 occupies a volume of 350 ml at 300K and 50 atm pressure. Calculate the compressibility factor of the gas.
Solution:
P = 50 atm
V = 350 ml = 0.350 litre
n = 1 mole
T = 300L Z = PV / nRT
∴ Z = 50 × 0.350 / 1 × 0.082 × 300 = 0.711
Thus SO2 is more compressible than expected from ideal behaviour.

Van der Waals’ Equation of State for a Real Gas

This equation can be derived by considering a real gas and 'converting ' it to an ideal gas.
 Volume Correction

We know that for an ideal gas P´V = nRT. Now in a real gas the molecular
volume cannot be ignored and therefore let us assume that 'b' is the volume
excluded (out of the volume of container) for the moving gas molecules per
mole of a gas. Therefore due to n moles of a gas the volume excluded would
be nb. \ a real gas in a container of volume V has only available volume of
(V - nb) and this can be thought of as an ideal gas in container of volume
(V - nb).
Hence, Ideal volume

Vi = V – nb …..........(i)
n = Number of moles of real gas
V = Volume of the gas

b = A constant whose value depends upon the nature of the gas

The Van der Waals constant b (the excluded volume) is actually 4 times the volume of a single molecule.

b = 4 × volume of a single molecule = 4 × 6.023 × 1023 ×(4/3) r3, where r

is the radius of a molecule.
Pressure Correction
Let us assume that the real gas exerts a pressure P. The molecules that exert the force on the container will get
attracted by molecules of the immediate layer which are assumed not to be exerting pressure.

It can be seen that the pressure the real gas exerts would be less than the pressure an ideal gas would have exerted.
The real gas experiences attractions by its molecules in the reverse direction. Therefore if a real gas exerts a
pressure P, then an ideal gas would exert a pressure equal to P + p (p is the pressure lost by the gas molecules
due to attractions).
 This small pressure p would be directly proportional to the extent of attraction between the molecules which are
hitting the container wall and the molecules which are attracting these.

Therefore p ∝ n/v (concentration of molecules which are hitting the container's wall)
P ∝ n/v (concentration of molecules which are attracting these molecules) p ∝ n2/v2
P = an2/v2 where a is the constant of proportionality which depends on the nature of gas.
A higher value of 'a' reflects the increased attraction between gas molecules.
Hence ideal pressure

Pi = (P + an2 / V2) …...........(ii)

Here,

n = Number of moles of real gas

V = Volume of the gas

a = A constant whose value depends upon the nature of the gas

Substituting the values of ideal volume and ideal pressure in ideal gas
equation i.e. pV=nRT, the modified equation is obtained as

The constants a & b

Vander Waals constant for attraction (a) and volume (b) are characteristic for a given gas. Some salient feature of a & b are:
 For a given gas Vander Waal’s constant of attraction ‘a’ is always greater than Vander Waals constant of volume (b).
 The gas having higher value of ‘a’ can be liquefied easily and therefore H2 & He are not liquefied easily.
 The units of a = litre2 atm mole–2 & that of b = litre mole –1
 The numerical values of a & b are in the order of 10–1 to 10–2 & 10–2 to 10–4 respectively.
 Higher is the value of ‘a’ for a given gas, easier is the liquefaction.

Different forms of Van der Waal’s equation

 At Low Pressures
 ‘V’ is large and ‘b’ is negligible
in comparison with V.
The Vander Waals equation reduces to:
(P + a / V2) V = RT;
PV + a/ V = RT
PV = RT – a/V or PV < RT
This accounts for the dip in PV vs P isotherm at low pressures.

 At Fairly High Pressures

a/V2 may be neglected in comparison with P.

The Vander Waals equation becomes
P (V – b) = RT
PV – Pb = RT
PV = RT + Pb or PV > RT
This accounts for the rising parts of the PV vs P isotherm at high pressures.
 At Very Low Pressures
V becomes so large that both b and a/V2 become negligible and the Vander Waals equation reduces to PV = RT.
This shows why gases approach ideal behaviour at very low pressures.

 Hydrogen and Helium

These are two lightest gases known. Their molecules have very small masses. The attractive forces between such
molecules will be extensively small. So a/V2 is negligible even at ordinary temperatures.
Thus PV > RT. Thus Vander Waals equation explains quantitatively the observed behaviour of real gases and
so is an improvement over the ideal gas equation. Vander Waals equation accounts for the behaviour of real
gases.
At low pressures, the gas equation can be written as,

(P + a/v2m) (Vm) = RT
or
Z = Vm / RT = 1 – a/VmRT
Where Z is known as compressibility factor. Its value at low pressure is less than 1 and it decreases with increase
of P. For a given value of Vm, Z has more value at higher temperature.
At high pressures, the gas equation can be written as

P (Vm – b) = RT
Z = PVm / RT = 1 + Pb / RT
Here, the compressibility factor increases with increase of pressure at constant temperature and it decreases with
increase of temperature at constant pressure. For the gases H2 and He, the above behaviour is observed even at
low pressures, since for these gases, the value of ‘a’ is extremely small.
 Example 2:

Question
One litre of a gas at 300 atm and 473 K is compressed to a pressure of 600 atm and 273 K. The compressibility factors found ar
respectively at initial and final states. Calculate the final volume.
Solution:
P1V1 = Z1nRT1 and P2V2 = Z2nRT2
P2V2 / T2 × T1 / P1V1 = Z2 / Z1
or V2 = Z2 / Z1 × T1 / T1 × P1V1 / P2 = 1.375 / 1.072 × 273 / 473 × 300 × 1 / 600 = 370.1 ml

Some Other Important Definitions

 Relative Humidity (RH)

At a given temperature it is given by equation

RH = (partial pressure of water in air) / (vapour pressure of water )

 Boyle’s Temperature (Tb)

Temperature at which real gas obeys the gas laws over a wide range of pressure is called Boyle’s Temperature.
Gases which are easily liquefied have a high Boyle’s temperature [Tb(O2)] = 46 K] whereas the gases which are
difficult to liquefy have a low Boyle’s temperature [Tb(He) = 26K].
Boyle’s temperature(Tb) = a / Rb = 1/2 T1
where Ti is called Inversion Temperature and a, b are called van der Waals constant.

 Critical Temperature (Tc)

It (Tc) is the maximum temperature at which a gas can be liquefied i.e. the temperature above which a gas can’t
exist as liquid.
T = 8a / 27Rb
 Critical Pressure (Pc)
It is the minimum pressure required to cause liquefaction at Tc
Pc = a/27b2
 Critical Volume
It is the volume occupied by one mol of a gas at Tc and Pc
Vc = 3b

Molar Heat Capacity of Ideal Gases

Specific heat c, of a substance is defined as the amount of heat required to raise the temperature of is defined as
the amount of heat required to raise the temperature of 1 g of substance through 10C, the unit of specific heat is
calorie g-1 K-1. (1 cal is defined as the amount of heat required to raise the temperature of 1 g of water through
10C)
Molar heat capacity C, is defined as the amount of heat required to raise the temperature of 1 mole of a gas
through 10C. Thus,
Molar heat capacity = Sp. Heat molecular wt. Of the gas

For gases there are two values of molar heats, i.e., molar heat at constant pressure and molar heat at constant
molar heat at constant volume respectively denoted by Cp and Cv. Cp is greater than Cv and Cp-R = 2 cal mol-1 K-
1

From the ratio of Cp and Cv, we get the idea of atomicity of gas.
For monatomic gas Cp = 5 cal and Cv =3 cal
∴ (γ = 5/3 = 1.67 (γ is poisson's ratio = Cp / Cv)
For diatomic gas Cp = 7 cal and Cv = 5 cal
γ = 7/5 = 1.40

For polyatomic gas Cp = 8 cal and Cv= cal

γ = 8/6 = 1.33

also Cp = Cpm,
where, Cp and Cv are specific heat and m, is molecular weight.
Example 3:

Question
Calculate Vander Waals constants for ethylene

TC = 282.8 k; PC = 50 atm
Solution:
b = 1/8 RTc / Pc = 1/8 × 0.082 × 282.8 / 50 = 0.057 litres/mole
a = 27 / 64 R2 × T2C / Pc = 27/64 × (0.082)2 × (282.8)2 × 1/50 = 4.47 lit2 atm mole–2
Question 1: When Z < 1 , it showns
a. a negative deviation
b. a positive deviation.
c. that the gas is showing ideal behaviour
d. that the gas is less compressible than expected from ideal behaviour
Question 2: A real gas behaves ideally at
a. high temperature and low pressure

b. high temperature and high pressure

c. low temperature and high pressure
d. low temperature and low pressure
Question 3: Which of the following equations represents the correct form of
Vandear waal’s equation at very low pressure?
a. PV = RT – a/V
b. pV = nRT

c. P (Vm – b) = RT
d. P (V – b) = RT
Question 4: The maximum temperature at which a gas can be liquefied is
called
a.boiling point.
b. melting point

c. Boyle’s temperature
d. critical temperature

Q.1 Q.2 Q.3 Q.4

a a b d