NOTE

C H E M I S T R Y

STATES OF MATTER
LET’S LIQUIFY GASES

What you already know What you will learn

• Separation of gases • Compressibility plot of a gas at different

• Real gas temperatures
• Effect of pressure on gas • Verification of van der Waals equation
• Units of a and b • Liquefaction of gases
• van der Waals equation • Andrews isotherm
• Critical isotherm

Recap

Real gas
Gases that do not obey the ideal gas law exactly under all the conditions of temperature and
pressure are real gases.
Compressibility factor (Z)
It is the ratio of the observed volume of the gas to the calculated volume at the same n, T and P.

Vm, real
Z=
Vm, ideal

van der Waals equation

 n 2a 
 P +  ( V − nb ) =
nRT
 V2 

Where, a = Attraction coefficient

    b = Molar excluded volume
    n = Number of moles of gas
• Unit of a = atm L2 mol-2
• Unit of b = L mol-1
Significance of a and b
• ‘a’ is the measure of the magnitude of the attractive forces.
• ‘b’ is the measure of the effective size of the gaseous molecules.

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Compressibility Plot of a Gas at Different Temperatures

Analogy to understand the compressibility plot

Consider a powerful cuboidal magnet with a hole in it (Fig. 1). A person is aiming to pass a steel
ball into this hole, but the ball ends up deviating from the hole. Then, he aims a sniper bullet
made of steel to pass through the hole, and this bullet could enter the hole in the magnet without
any deviation. Though the force of attraction was the same in both the cases, the influence this
attraction created on the object was different in both the cases. The high kinetic energy of the
bullet could overcome the attractive forces of the magnet and was therefore able to pass through
the hole.

Fig. 1: Powerful magnet with a hole

Relating the given analogy to the concept of

compressibility plot
From the postulate of the kinetic theory of gases, we
know that as the temperature of the gas particles
increases, there is a corresponding increase in the
kinetic energy of the gas particles. (Longer arrows represent
greater velocities)
Fig. 2: Increase in kinetic energy with
increase in temperature
Thus, on increasing the temperature, the interparticle
attraction remains the same but the effect of the T4
T3
interparticle attraction on the compressibility of T2
the gas changes. In the compressibility plot given
in Fig. 3, the red coloured curve corresponding to T1
PV
temperature T4 has the deepest depression and Z= Z=1
nRT
therefore, the effect of attractive forces is the
maximum. Thus, it can be inferred that the red
curve corresponds to the lowest temperature of
the gas, i.e., T4 is the lowest temperature. The pink
coloured (T3) and yellow coloured curves (T2) have P
less depression than the red one. As the depression Fig. 3: Compressibility plot of a gas at
of the pink curve is greater than that of the yellow different temperatures
curve, it can be concluded that T2 is greater than T3.

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 03

At temperature T1, the gas particles have got the least influence of the attractive forces and thus,
it is a straight line without any depression in the plot. Hence, it can be inferred that T1 is the highest
temperature among T1, T2, T3 and T4.
The overall order of temperatures is as follows:

T1 > T2 > T3 > T4

The compressibility plot for N2 gas at three different For N2 gas

200 K
temperatures is given in Fig. 4. When the temperature 500 K
is less, say 200 K, the red coloured curve is going
towards the Z < 1 region where the influence of 1000 K
PV
the attractive forces are dominant. Hence, it will Z=
nRT
show a greater depression. However, at a higher
temperature, say, 1000 K, it is a straight line (green
colour) that is not at all going to the region of Z < 1.
Therefore, the gas particles at this temperature have
negligible influence by the attractive forces and only 0 P
repulsion is dominating. Fig. 4: Compressibility plot of N2 at
different temperatures

BOARDS MAIN ADVANCED

Verification of the van der Waals Equation

The van der Waals equation is obtained at certain pressure and temperature conditions in order to
determine the compressibility factor, Z. Then, this is verified with the value of Z obtained from the
compressibility plots. Some important formulae discussed previously that are required for further
discussions are given below.
The ideal gas equation is given as follows:
PVideal = nRT
Videal
i.e., P = RT
n
⇒ PVm, ideal = RT
RT ...(1)
⇒ Vm, ideal =
P
Compressibility factor, Z, is given as follows:
V
Z = m, real ...(2)
Vm, ideal
By substituting (1) in (2) we get the following:
Vm, real
Z=
RT

The van der Waals equation is given as follows:

 n 2a 
 P +  (V − nb) =
nRT
 V2 

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In terms of molar volume, the van der Waals equation can be written as follows:
 a 
P +  (Vm − b) =
RT
 Vm 2 

At high pressure (moderate temperature)

As the pressure increases, the molar volume occupied by the gas (Vm) will decrease. Hence, b in
the (Vm - b) term of the van der Waals equation cannot be neglected because the excluded volume
cannot be neglected when the volume of the container decreases. Since, we are considering the
case of a higher pressure, a/Vm2 can be neglected from the term (P + a/Vm2).
Thus, the van der Waals equation becomes the following:
P(Vm − b) =
RT
⇒ PVm − Pb =
RT
By dividing L.H.S and R.H.S of the above equation by RT, we get the following:
PVm Pb
− =
1
RT RT
PVm Pb
⇒ =1+
RT RT
We know,
PVm
Z=
RT
Pb
i.e., Z= 1 +
RT PVm
Z=
RT
Pb
i.e., Z= 1 +
RT
Hence, Z > 1 at high pressure and moderate
temperature. In the deviation of real gases from the
ideal gas behaviour, it was discussed that at high
Z>1
pressure, the repulsive forces will dominate over
the attractive forces and it will become more difficult
to compress a real gas than an ideal gas.
A real gas is less compressible as
compared to an ideal gas.

At low pressure (Moderate temperature)

At low pressure, the molar volume (Vm) occupied by the gas particles will increase. Hence, b in
the (Vm - b) term of the van der Waals equation can be neglected as the volume occupied by the
gas particles is much higher than the excluded volume. Since, we are considering the case of low
pressure, a/Vm2 cannot be neglected from the term (P + a/Vm2).
Thus, the van der Waals equation becomes the following:

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 05

 a 
 P + 2  Vm =RT
 Vm 
a
⇒ PVm + =RT
Vm
By dividing L.H.S and R.H.S of the above equation by RT, we get the following:
PVm a
+ = 1
RT VmRT
PVm a
⇒ 1
=−
RT VmRT
a
i.e., Z= 1 −
VmRT

a
Z = 1−
Thus, at low pressure and moderate temperature, VmRT
Z < 1. Therefore, at low pressures, the attractive
forces dominate over the repulsive forces as
discussed in the deviation of real gases from the Z<1
ideal behaviour. Hence, the real gases are more
compressible when compared to an ideal gas at
low pressure. A real gas is more compressible
as compared to an ideal gas.

At low pressure and very high temperature

The van der Waals equation is given as follows:

 a 
P +  ( Vm − b ) =
RT
 Vm 2 
Consider the gas particles enclosed in a container having a movable piston. At a higher temperature,
the motion of the particles will become more random, increasing its kinetic energy. Hence, the
impact of the gas particles on the piston during the collision also increases. Thus, to balance
the internal pressure exerted on the piston by the gas particles and the external atmospheric
pressure, the piston will move in the upward direction, which will eventually cause an increase in
the volume occupied by the gas particles.
Thus, the molar volume occupied by the gas particles, Vm, is high and therefore, b in the (Vm - b)
term of the van der Waals equation can be neglected. Even though the pressure is low, a/Vm2 can
be neglected in the term (P + a/Vm2), as Vm is really high, which will eventually make 1/Vm2 negligible.
Hence, the van der Waals equation becomes the following:
PVm = RT
Compressibility factor, Z, is given as follows:
PVm
=Z = 1
RT
Thus, real gases will approach an ideal gas behaviour at a low pressure and a high temperature.

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BOARDS MAIN ADVANCED

Liquefaction of Gases

The liquefaction of gases is the phenomena of converting a gas into its liquid state.

Phenomenon of converting a gas Occurs when intermolecular

into liquid forces of attraction become high

Some important points related to the understanding of liquefaction of gases are as follows:
Population density: The number of particles or moles present per unit volume of the container is
known as the population density.

N n
Population density = or
V V

Where, N is the number of particles and n is the number of moles.

An analogy for understanding population density better is given in Fig. 5. During the day, the
highway is crowded with vehicles as shown in case A. However, at night, there are only a few
vehicles moving on the highway as shown in case B. Therefore, it can be said that the population
density during the day is higher than that at night. These moving vehicles can be assumed as
gas particles enclosed in a container (highway) and therefore, the analogy of the vehicles on a
highway can be related with the population density of the gas particles enclosed in the container.

Case A Case B
Fig. 5: Analogy for population density

Evaporation: It is a form of vaporization that Day 1 Day 10

happens on the surface of liquids, and it
involves the transition of liquid particles into
their gaseous phase. An illustration of an open
container filled with water is given in Fig. 6.
As days pass, the amount of water inside the
container will decrease, as the water molecules
are converted into vapour form, resulting in
evaporation. Fig. 6: Illustration for evaporation of water

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From Maxwell's distribution of molecular speed of gases, it can be observed that some gas
particles will have a greater speed of motion as compared to the others and they will be converted
into the vapour phase easily. Also, it can be observed that some of these gas particles in the
vapour state will come back to its original liquid state. This is described in the illustration in Fig. 7.
Three different stages of a beaker filled with water and enclosed in a container are analysed here.
In case 1, we can observe that the liquid particles evaporate into the vapour state. As time passes,
more and more liquid particles will enter into the vapour state. Also, some of the gas particles will
come back to the liquid phase as shown in case 2. In case 3, an equilibrium is established between
the liquid and vapour phase. Hence, the population density of the gas particles will remain constant
with further passage of time.

Case 1 Case 2 Case 3

Fig. 7: Attainment of equilibrium between liquid and vapour phase
Now an illustration to understand the concept of population density and evaporation is given.
Two different cases of identical water spillage across a surface in a room is given in Fig. 8.

Case 1:
Here, the water is spilled across a surface in a room and a bucket is used to cover it. After a few
days, when the bucket was removed, some amount of water droplets were still present. This is
because in this case, the volume available for the gas particles is simply the volume enclosed by
the bucket. Therefore, in order to attain a constant population density (i.e., to attain equilibrium),
less number of liquid particles will be converted into the vapour phase. Hence, some amount
of liquid will be left behind on the surface.
Case 2:
Here, the water spilled across the surface is
exposed to the atmosphere, and after a few days
not even a single drop of water was left behind, i.e.,
all of them evaporated. The reason behind this is
that the entire volume of the room is available for
the gas particles, which is much greater than what
was available in case 1. Therefore, in an attempt to
Case 1 Case 2
maintain a constant population density, a large
number of liquid particles got converted into the Fig. 8: Illustration of population density and
vapour state. evaporation

Note

Liquefaction of gases occurs when the intermolecular forces of attraction between the gas particles
become high.

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Methods of gas liquefaction

1. By increasing the pressure

When the pressure applied on the gas
molecules increases, the molecules will
Intermolecular forces of
come close to each other and therefore, P↑
the intermolecular forces of attraction attraction ↑
operating between them will increase. Thus,
liquefaction takes place.

Note

Applying the pressure alone will not cause the liquefaction

of gases. An illustration of a person applying pressure on
the syringe is shown in Fig. 9. On applying the pressure
on the syringe at room temperature, no liquid particles are
formed at the bottom of the syringe. Thus, we can conclude
that the normal room temperature is really high and it will
not favour liquefaction. Hence, it can be concluded that
along with high pressure, low temperature should also be
provided in order to liquify a gas.
Fig. 9: Liquefaction of air will not
happen at room temperature

2. By decreasing the temperature

From the postulates of the kinetic theory

of gases, it is known that temperature is
directly proportional to the kinetic energy. Kinetic energy of
On decreasing the temperature, the kinetic T↓
energy of the molecules will decrease, i.e., molecules ↓
the molecules will slow down and they can
be easily brought closer to each other, which
will eventually result in liquefaction.

Compression of a real gas

The liquefaction of a real gas on the application of pressure is discussed in Fig. 10. For better
understanding, an illustration is given in which a container that is initially filled with gas particles is
attached to a piston. A mass block is kept over the piston, whose size is changing throughout the
process, and the pressure exerted by this mass block on the piston is indicated by a barometer as
shown in Fig. 10. There are three stages involved in the process of liquefaction and they are given
as follows:

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Stage 1 Stage 2

Stage 3
Fig. 10: Different stages of the compression of real gas
Stage 1:
On increasing the mass over the piston, the piston moves down and will exert pressure on the gas
molecules enclosed inside the container. This will result in the formation of the first liquid droplet.
Stage 2:
On further increasing the mass on the piston, the pressure exerted by the piston on the gas
particles will increase. Thus, more and more gas molecules will enter into the liquid state. There
is an existence of the liquid-vapour equilibrium in this stage, as both the liquid and gas particles
are present in the container at this stage. This process will continue until all of the gas molecules
are converted into liquid.
Stage 3:
On reaching this stage, all the gas molecules inside the container will have been liquified. As the
liquid particles are almost incompressible, the increasing mass on the piston will cause only
negligible movement of the piston.
Here, the compression of the real gas molecules happened by the application of pressure. The
Andrews isotherms are used to understand how temperature can affect the liquefaction of gases.

Andrews Isotherm
D
Thomas Andrews investigated the complete relationship between
Pressure

volume, temperature, and pressure of a substance in its gaseous as

well as its liquid state by studying the behaviour of carbon dioxide.
The Andrews isotherm can be defined as a plot depicting the pressure-
volume-temperature study of CO2. The Andrews isotherm at 13.1°C is C B
shown in Fig. 11. For better understanding, the three different regions A
are marked in the plot as AB, BC, and CD. A detailed discussion of Volume
each of these regions are as follows. Fig. 11: Andrews isotherm
for CO2at 13.1 °C

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Region AB

Initially, the gas particles are enclosed in a container attached to a piston as shown in Fig. 12. On
compressing the piston, the gas molecules will come closer to each other and will therefore, result
in liquefaction. Point A represents CO2 in the gaseous state occupying a certain volume under a
certain pressure. As the pressure exerted by the piston on the gas molecules increases, there is a
consequent decrease in the volume occupied by the gas molecules as indicated by the curve AB.
The first liquid droplets are formed at point B.

13.1 °C 13.1 °C

Pressure
Pressure

B
A
A
Volume
Volume

Fig. 12: Formation of first liquid particles along AB

Note

The density of water in its liquid state at 0°C (i.e., 273 K) and 1 atm pressure is approximately 1 g/mL.
Therefore, we can say that 18 grams (i.e., 1 mole) of liquid H2O will occupy 18 mL volume. 1 mole of
water in its vapour state at 0°C and 1 atm pressure will occupy a volume of 22,400 mL.

Region BC (Liquid-vapour equilibrium exists in this region)

As the volume occupied by water in its vapour form is much more than that occupied in the
liquid form, it can be concluded that the gas molecules are very far from each other and the
liquid molecules are really close together.
On compressing the gas molecules, there is a sudden and drastic decrease in the volume occupied
by the gas as it gets converted into a liquid. Also, during compression, as the gas molecules are
converted into liquid state, there is a decrease in the number of particles remaining in the gas
phase (n represents number of gaseous particle)

n ↓, V ↓

Hence, the ratio of the number of moles to the volume occupied by them will remain constant.
Here, pressure is due to the pressure exerted by the gas molecules on the walls of the container,
which is known as the vapour pressure denoted as P0.

n
P0 ∝
V

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 11

13.1 °C

Pressure
Thus, we can say that vapour pressure P0 is constant.
Therefore, it can be concluded that at B, the B
liquefaction of the gas commences and thereafter, A
a rapid decrease in the volume takes place as more Volume
and more gas particles are converted into liquid state.
Thus, in the region ‘BC’, there is a sudden decrease
in volume, but the pressure remains constant since 13.1 °C
there are less number of gas particles that collide

Pressure
with the piston as in Fig. 13. CO2 exists partly as gas
and partly as liquid along BC. Hence, a liquid-vapour C B
equilibrium is established. A
Volume
Fig. 13: Liquid-vapour equilibrium exists
in region BC

Region CD
13.1 °C
Pressure

C B
A
At C, the gas has been completely liquified. Now, as the
liquid is only slightly compressible, further increase in Volume
pressure will result in a negligible decrease in volume.
This is shown by a steep line CD, i.e., almost vertical 13.1 °C
(Fig. 14). Thus, for the compression of the liquid at D
Pressure

constant temperature, high pressure is required to

cause even a small volume change.
C B
A
Volume
Fig. 14: Steep increase in pressure
along CD

Note

• As the entire process of compression of the gas molecules was done at a constant temperature
of 13.1 °C, this pressure-volume plot is known as an isotherm.
• Along the curve AB, CO2 will exist as a gas.
• Along the curve BC, CO2 will exist as a gas and a liquid.
• Along the curve CD, CO2 will exist as a liquid.

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 12

Andrews performed this experiment of compressing CO2 at various other temperatures and he
plotted the observations as given in Fig. 15.

50 °C
50 °C
Pressure (atm)

Pressure (atm)
31.1 °C 31.1 °C

21.5 °C 30.98 °C (Tc ) 30.98 °C

21.5 °C
13.1 °C
13.1 °C

Volume (L) Volume (L)

Fig. A Fig. B
Fig. 15: Andrews isotherms of CO2 at different temperatures
A dome-like region (Fig. B) can be observed in the Andrews isotherm plotted at various temperatures.
This belongs to the region where the liquid-vapour equilibrium is established. Thus, at all the
points that fall under the dome, there exists a liquid-vapour equilibrium.

Effect of temperature on Andrews isotherm

The Andrews isotherm (EFGH) for carbon dioxide at 21.5 °C is given in purple (Fig. 16). On increasing
the temperature, there is an increased randomness in the motion of the gas molecules due to
higher kinetic energy. Hence, a higher pressure has to be applied when compared to what was
applied when the temperature was 13.1 °C at the same volume as shown in the region EF. The
vapour pressure remains constant along the region ‘FG’, as the liquid-vapour equilibrium is existing
in this region. Towards point G, almost all the gas molecules are converted to liquid. Hence, a
very high pressure is required to compress the liquid, as the liquid molecules are only slightly
compressible. Thus, there is a steep increase in pressure along GH.

21.5 °C 21.5 °C 21.5 °C

Pressure

Pressure

Pressure

F G F
E E E
Volume Volume Volume

21.5 °C 21.5 °C H 21.5 °C

Pressure
Pressure
Pressure

G F
F GF
E
E E
Volume Volume Volume
Fig. 16: Effect of temperature on the Andrews isotherm

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Critical isotherm

In the Andrews isotherm discussed in Fig. 17, it is observed that the horizontal region of the
isotherm representing the decrease in volume, becomes shorter and shorter with an increase
in temperature. However, at 30.98 °C, it reduces into a point (represented by J). Thus, above
this temperature, Andrews concluded that the isotherm is continuous. There is no evidence of
liquefaction above this temperature. Andrews concluded that if the temperature of CO2 is above
30.98 °C, it cannot be liquified, no matter how high the pressure is applied. Hence, he named this
point ‘J’ as the critical point, and the isotherm IJK is known as the critical isotherm (Fig. 18).

30.98 °C 30.98 °C
Pressure

Volume Pressure Volume

30.98 °C
Pressure

Volume
Fig. 17: Various stages of critical isotherm

K
Critical point
Pressure (atm)

J
Pc

Vc
Volume (L)
Fig. 18: Critical isotherm for CO2

In the illustration given in Fig. 19, the liquid particles that are present deep inside and away from the
surface have a uniform attraction from all the sides. Hence, the net influence on these molecules
are zero. However, the particles present on the surface experience a non-uniform influence from
the liquid particles present at the bottom of the surface. This is the reason behind the surface
tension experienced by liquids. On increasing the temperature, the liquid particles will break their
attractive forces and will enter into the vapour phase

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 14

Fig. 19: Illustration of the interactions of

liquid particles
At initial temperature T1 (<TC), more particles are present in the liquid state than in the vapour state.
Hence, at this temperature, the density of liquid is greater than the density of vapour. When the
temperature is further increased, more and more particles from the liquid state get converted into
the vapour state, which eventually decreases the density of the liquid and increases the density
of the vapour. However, at a particular temperature, the density of the liquid will be equal to the
density of the vapour due to the establishment of the liquid-vapour equilibrium as discussed in
Andrews isotherm, and this temperature is known as the critical temperature (Tc).

At T1 Density of liquid > Density of vapour

As T ↓ Density of liquid ↓ Density of vapour ↑

At Tc Density of liquid = Density of vapour

Two phases can

At a temperature below the critical temperature Below Tc
be distinguised
(Tc), both the liquid and vapour phases will
coexist, and it is possible to distinguish between
these phases. At Tc, the liquid particles will pass
into the gaseous phase continuously and the
boundary between the two phases will disappear. Liquid passes into
Hence, it is not possible to distinguish between the gaseous phase
the liquid and vapour phases. At Tc continuosly and the
boundary between the
two phases disappears

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Continuity of states

The process of transition from the gaseous phase to the liquid phase (or vice versa) is regarded
as continuous, as there is no distinction between the vapour and liquid phases at the critical
point. The existence of a single fluid is another important characteristic of the continuity of states.
At critical point J (point of inflection), the slope of P-V curve and the rate of change of slope with
respect to the volume is zero (Fig. 20).
dP d 2P
i.e.,
= 0=
and 0
dV dV 2

H Critical point (Point of inflection)

K

D
dP d2P
= = 0
Pressure (atm)

dV dV 2

J
Critical isothem
F
G
I
C B
E
A
Volume (L)
Fig. 20: Slope at the inflection point is zero
Gases cannot be liquified above a certain temperature. In Fig. 21, the given green coloured (case A)
and the red coloured (case B) curves represent isotherms for CO2 at 31.98 °C and 50 °C, respectively,
and they resemble the P-V plot obtained from Boyles’s law. The maximum temperature at which a
gas can be liquified by the application of pressure is known as the critical temperature.

31.98 °C 50 °C
Pressure

Pressure

Volume
Volume

31.98 °C 50 °C
Pressure

Pressure

Volume Volume
Case A Case B
Fig. 21: Critical isotherm for CO2 at 31.98 °C and 50 °C

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Critical constants

• Critical temperature (Tc): The maximum temperature at which a gas can be liquified by the
application of pressure is known as the critical temperature.
• Critical pressure (Pc): The minimum pressure required to liquify a gas at the critical temperature
is known as the critical pressure.
• Critical volume (Vc): The volume occupied by one mole of the gas at the critical temperature
and critical pressure is known as the critical volume.
Critical temperature (Tc), critical pressure (Pc), and critical volume (Vc) are collectively known as the
critical constants.
Significance of critical temperature (Tc)
Critical temperature is the temperature required to raise the kinetic energy of gases to such a
level beyond which the liquefaction of a gas is not possible. A higher temperature will have to
be provided for gases with higher intermolecular attractions to obtain enough kinetic energy
to prevent liquefaction. For more clarification, an example of two gases A and B with critical
temperatures 50 K and 250 K are taken. On attaining a temperature of 51 K, gas A cannot be
liquified further, but the liquefaction of gas B is still feasible.

Concept of critical temperature and intermolecular attractions

Predict the correct order of values of the critical temperature for the gases NH3, CO2, O2, N2, and
He
(a) NH3 > CO2 > N2 > He > O2 (b) NH3 > N2 > CO2 > He > O2
(c) NH3 > CO2 > O2 > N2 > He (d) CO2 > NH3 > O2 > N2 > He

Solution

NH3 is a polar molecule and others are nonpolar. Polar molecules have more attractions than
nonpolar molecules. As the intermolecular force of attraction increases, the critical temperature
(Tc) will increase and therefore, the gas can be easily liquified. Hence, NH3 will have the highest
critical temperature among the given molecules. Among the nonpolar molecules given, the one
with the higher molar mass has a higher strength of intermolecular forces and therefore a
higher critical temperature (Tc). The order of molar mass among the given nonpolar molecules
follows CO2 > O2 > N2 > He.
Hence, the correct order of critical temperatures is given by option (c)
NH3 > CO2 > O2 > N2 > He

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Comparison of the van der Waals Isotherm and the Andrews Isotherm

The van der Waals isotherm and the Andrews isotherm are given in Fig. 22. The theoretical plot
obtained by van der Waals and the experimental plot obtained by Andrews do not resemble
each other except at the critical point.

T > Tc
T > Tc

T < Tc T < Tc
P P

Tc
Tc

V V
van der Waals Isotherms Andrews Isotherms
Fig. 22: van der Waals isotherm and Andrews isotherm
From the van der Waals plot, at the critical temperature, the values of the critical constants were
derived in terms of the van der Waals constant. Since van der Waals constants (a and b) are the
unique property of a particular gas, the critical constants are also unique for a particular gas.
Critical constants
The critical constants in terms of the van der Waals constants (a and b) are given as follows:

a 8a
Vc = 3b Pc = Tc =
27b2 27Rb

Compressibility factor at critical conditions

Compressibility factor, Z, is given as follows
PV
Z=
nRT
At critical conditions, Z is given as follows:
Pc Vc
Zc = ...(1)
RTc
Where, Pc is the critical pressure, Tc is the critical temperature, and Vc is the critical volume.
By substituting the values of the critical constants in the equation (1) we get the following:

a
Thus, it can be concluded that for any gas at × 3b
27b2 3
critical conditions, the value of compressibility = = 0.375
8a 8
factor, Zc, is equal to 0.375. R×
27Rb

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 18

Summary

1. Verification of the van der Waals equation

• At high pressure (Moderate temperature)
Pb
i.e., Z= 1 +
RT
Hence, Z > 1 at high pressure and moderate temperature. At high pressure, the repulsive
forces will dominate over the attractive forces and it will become difficult to compress a real
gas when compared to an ideal gas.
• At low pressure (Moderate temperature)
a
i.e., Z= 1 −
VmRT
Thus, at low pressure and moderate temperature, Z < 1. Thus, at low pressures, the attractive
forces dominate over the repulsive forces. Hence, a real gas is more compressible when
compared to an ideal gas under these conditions.
• At low pressure and very high temperature
Compressibility factor, Z, is given as follows:
PVm
= Z = 1
RT
Thus, real gases will approach an ideal gas behaviour at low pressure and high temperature.
The liquefaction of gases is the phenomena of converting a gas into its liquid state.
2. Methods of gas liquefaction
• By increasing the pressure
When the pressure applied on the gas molecules increases, the molecules will come close
to each other. Hence, the intermolecular forces of attraction operating between them will
increase. Thus, the liquefaction takes place
• By decreasing the temperature
On decreasing the temperature, the kinetic energy of the molecules will decrease, i.e.,
the molecules will slow down and they can be easily brought closer to each other, which will
eventually result in liquefaction.
3. Andrews Isotherm
Thomas Andrews investigated the complete relationship between volume, temperature,
and pressure of a substance in gaseous as well as liquid state by studying the behaviour
of carbon dioxide. The Andrews isotherm can be defined as a plot depicting the pressure-
volume-temperature study of CO2.
• As the entire process of compression of the gas molecules was conducted at a constant
temperature, this pressure-volume plot is known as an isotherm.
• Along the curve AB, CO2 will exist as a gas.
• Along the curve BC, CO2 will exist as a gas and a liquid.
• Along the curve CD, CO2 will exist as a liquid.
Critical isotherm
Andrews concluded that if the temperature of CO2 is above 31.98 oC, it cannot be liquefied
no matter how high the pressure applied is. Hence, he named this point ‘J’ as the critical point
and the isotherm IJK is known as the critical isotherm.

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 19

H Critical point (Point of inflection)

K

D
dP d2P
= = 0
Pressure (atm)

dV dV 2

J
Critical isothem
F
G 21.5°C
I
C 13.1°C B
E
A
Volume (L)
Fig. 23: Andrews isotherm for CO2
Continuity of states
The process of transition from gaseous phase to liquid phase (or vice versa) is regarded as
continuous, as there is no distinction between the vapour and the liquid phases at the critical
point. The existence of a single fluid is another important characteristic of the continuity of
states
Critical constants
• Critical temperature (Tc): The maximum temperature at which a gas can be liquified by
the application of pressure is known as the critical temperature.
8a
Tc =
27Rb
• Critical pressure (Pc): The minimum pressure required to liquify a gas at the critical
temperature is known as the critical pressure.
a
Pc =
27b2
• Critical volume (Vc): The volume occupied by one mole of the gas at critical temperature
and critical pressure is known as the critical volume.
Vc = 3b
Compressibility factor at critical conditions
• For any gas at critical conditions, the value of compressibility factor, Zc, is equal to
0.375.

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