What is Ideal Gas Equation?

In thermodynamics, Ideal gas law is a well-defined approximation of the behaviour of many

gases under diverse conditions. Ideal Gas Equation is the combination of empirical laws like
Charle’s law, Boyle’s law, Gay-Lussac’s law and Avogadro’s law.
Ideal Gas Equation is the equation defining the states of the hypothetical gases expressed
mathematically by the combinations of empirical and physical constants. It is also called
the general gas equation. It can be defined as:
The ideal gas law is the equation of state of a hypothetical ideal gas. It is a good approximation
of the behaviour of many gases under many conditions, although it has several limitations.

Equation of Ideal Gas Law

Thus, the ideal gas equation is often written as:
PV = nRT
Where,

 P is the pressure of the ideal gas.

 V is the volume of the ideal gas.
 n is the amount of ideal gas measured in terms of moles.
 R is the gas constant.
 T is the temperature.
The ideal gas concept is useful because it obeys the ideal gas law, a simplified equation of state,
and is amenable to analysis under statistical mechanics.

Ideal Gas Equation Units

The Ideal gas equation units, terms and corresponding definitions can be expressed as follows:

Terms Symbol Definition Units

Pressure P Force per units area Pa or N/m2

Three-dimensional space enclosed by the

Volume V m3
closed surface

Amount of
The ratio of the mass of the gas(m) to its
substances/number of n mole
molar mass(M).
moles

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 Physical constant relating the average
kinetic energy of an ideal gas with
8.3144598(48)
Ideal gas constant R temperature. It is expressed in units of
J.K-1.mol-1
energy per temperature increment per
mole

Temperature T Measure of heat K or 0C

What is Ideal gas?

Ideal gas does not exist in reality. It is a hypothetical gas proposed to simplify the calculations.
An ideal gas is a theoretical gas composed of a set of randomly-moving point particles that
interact only through elastic collisions.

 In Ideal gas, the gas molecules move freely in all direction and collision between them
are considered to be perfectly elastic, which implies no loss in the kinetic energy due to
the collision.
 Although there is no ideal gas, all real gas tend to approach that property when the
density gets low enough. This is possible because the molecules of the gas are so far apart
from one another that they do not interact with each other. Thus, the ideal gas concept
helps us in studying real gases.

Ideal Gas Equation – Explained

The researchers have found that no matter what gas you study if you take a one-mole sample of
that gas, put it in the same container, and maintain a constant temperature, the pressure is almost
the same, and at lower densities, even those tiny differences in the measurements disappear.
Thus, at really low densities, all the real gases tend to obey one universal law called ideal gas
law.
This law is described by an equation known as the Ideal gas equation:

PV = nRT

Limitations:
Although the ideal gas equation has many limitations.

 This equation holds well as long as the density is kept low.

 This equation is applicable for single gas or even a mixture of multiple gasses where ‘n’
will stand for the total moles of gas particles in the given mixture.

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

Study of Deviations

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.

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 Example 1:

Question
1 mole of SO2 occupies a volume of 350 ml at 300K and 50 atm pressure. Calculate the compressibility factor o
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

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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

Where ‘a’ and ‘b’ van der Waals constant.There values depend upon nature of gas.
For 1 mole of the gas,

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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

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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.

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 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

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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.

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

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 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.
3. What is the compressibility factor?
Compressibility factor is a measure of the deviation of the real gas from ideal gas behaviour.
It is given by Z=PVmRT; where, P is the pressure and Vm is the molar volume of the gas.
R is the gas constant and T is the temperature.
4. How the real gases classified in terms of compressibility?

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Z=PVmRT
Real gases can be classified into three types on the magnitude of the compressibility factor.
i) For an ideal gas, PVm = RT, so that Z=1 at all temperatures and pressure. But, there is no ideal
gas.
ii) Z > 1. PVm > RT. The gases having compressibility greater than 1, have a positive deviation
from the ideal gases at all temperatures and pressures. Hydrogen and noble gasses except
krypton are examples.
They have low ‘a’ values.
iii) Z < 1. PVm < RT. The gases having compressibility lesser than 1, show negative deviation
from the ideal gases at all temperatures and pressures. Hydrogen and Helium are examples.
They have larger ‘a’ values.
Most of the gases, show compressibility factor less than one at low pressures, and greater than
one at high pressures.

5. What is the Boyle temperature? Give an example.

Compressibility factor depends on the temperature also.

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 Compressibility factor is inversely proportional to temperature. So, an increase in temperature
decreases the deviation from ideal behaviour.
Every real gas has a certain temperature, where the compressibility factor shows little changes
and comes close one. Some gases obey ideal gas laws at high pressures at a certain temperature.
The temperature at which a real gas behaves like an ideal gas over a long range of pressure is
Boyle’s temperature for the gas. For example, nitrogen has a Boyle temperature of 323K.

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.

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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 are 1.072 & 1.375 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

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

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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

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