Liquefaction of Gases

Praveen G
What are the key changes we have to make in the
molecules of gas phase to convert it into liquid phase?

• We have to bring them closer so they are held together by

intermolecular attraction, in order to do it we have to reduce the
volume.
• If we apply pressure we can reduce the volume of gas. Furthermore,
we need to reduce temperature to slow down the speed of
molecules.
• That means we need to find that particular temperature, pressure and
volume in which we can liquefy real gas, and here Boyle’s law helps
us.
 CRITICAL TEMPRATURE AND PRESSURE

Two important properties of gases are important in developing

methods for their liquefaction: critical temperature and critical
pressure.

The highest temperature at which a substance can exist as a

liquid, is called its critical temperature (Tc).

There is corresponding pressure which is requires to bring

about liquefaction at this critical temperature called critical
pressure (Pc).
 For example, the critical temperature for carbon dioxide is 304 K
(87.8 F [31 C]).
 That means that no amount of pressure applied to a sample of
carbon dioxide gas at or above 304K (87.8 F [31 C]) will cause the
gas to liquefy.
 At or below that temperature, however, the gas can be liquefied
provided sufficient pressure is applied.
 The corresponding critical pressure for carbon dioxide at 304 K (87.8
F [31 C]) is 72.9 atmospheres.
 In other words, the application of a pressure of 72.9 atmospheres of
pressure on a sample of carbon dioxide gas at 304K (87.8 F [31 C])
will cause the gas to liquefy.
 On compressing, initially CO2 gas
remains gas till point ‘B’
 On applying still more pressure it
shows deviation from Boyle's law
and a little liquid CO2 appears
 On further compression the
pressure remains constant for a
period (point ‘B’ to ‘C’) and we
get a plateau for this phase. In
this region we get vapour CO2
that means a state in which liquid
and gas coexist.
 If we further compress it, a steep rise in pressure is observed (point ‘C’ to ‘D’). s the
plateau ends we start getting liquid CO2. All real gases show similar behaviour as
CO2. CO2 gas represents all real gases. But every gas has a particular set of critical
constants.
 Differences in critical temperatures among gases, that some
gases are easier to liquefy than are others.
 The critical temperature of carbon dioxide is high enough
so that it can be liquefied relatively easily at or near room
temperature.
 By comparison, the critical temperature of nitrogen gas is
126K (-232.6 F [147 C]) and that of helium is 5.3K (-449.9 F
[267.7 C]).
 Liquefying gases such as nitrogen and helium obviously
present much greater difficulties than does the liquefaction
of carbon dioxide.
The value of the critical temperature of a gas depends upon its size,
shape and intermolecular forces present in it.

When a gas measured at its critical temperature and critical pressure,

then at that stage volume of 1 lt of gas is called critical volume which is
represented by Vc.

The critical volume of O2 is 74.42 cm3 mol-1, of CO2 is 95.65cm3 mol-

1 and that of H2 is 64.51cm3 mol-1
 Methods of Liquefaction

Compressing the gas at temperature less than at its critical

temperature

Making the gas do some kind of work against an external

force causing the gas to lose energy

Making gas do work against own its internal forces, also

causing it to lose energy
Compressing the gas at temperature less than at its critical temperature

 In the first approach, the application of pressure alone is

sufficient to cause a gas to change to a liquid.
 For example, ammonia has a critical temperature of 406 K (271.4
F [133 C]).
 This temperature is well above room temperature, so it is
relatively simple to convert ammonia gas to the liquid state
simply by applying sufficient pressure.
 At its critical temperature, that pressure is 112.5 atmospheres,
although the cooler the gas is to begin with, the less pressure is
needed to make it condense.
 Making the gas do some kind of work against an
external force causing the gas to lose energy

 A simple example of the second method for liquefying gases is the

steam engine.
 The principle on which a steam engine operates is that water is boiled
and the steam produced is introduced into a cylinder.
 Inside the cylinder, the steam pushes on a piston, which drives some
kind of machinery. As the steam pushes against the piston, it loses
energy.
 That loss of energy is reflected in a lowering of the temperature of the
steam.
 The lowered temperature may be sufficient to cause the steam to
change back to water.
 Making gas do work against own its internal
forces, also causing it to lose energy

 In some ways, the simplest method for liquefying a gas is simply to

take advantage of the forces that operate between its own
molecules.
 This can be done by forcing the gas to pass through a small nozzle or
a porous plug.
 The change that takes place in the gas during this process depends
on its original temperature.
 If that temperature is less than some fixed value, known as the
inversion temperature, then the gas will always be cooled as it passes
through the nozzle or plug.
 In some cases, the cooling that occurs during this process
may not be sufficient to cause liquefaction of the gas.
However, the process can be repeated more than once.
 Each time, more energy is removed from the gas, its
temperature falls further, and, eventually, it changes to a
liquid.
 This kind of cascade effect can, in fact, be used with either
of the last two methods of gas liquefaction
BY THE ADIABATIC EXPANSION OF COMPRESSED GAS-LINDE’S PROCESS

JOULE-THOMSON’S EFFECT

“When a highly compressed gas is allowed

to escape out through a throttle (small hole),
the temperature falls to such an extent that it
changes into liquid form.”
 At high pressure, molecules of gas come close to each other. As a
result intermolecular attraction forces increase.
 When it is allowed to escape through a nozzle into a region of low
pressure, the molecules move apart.
 In doing so, energy is needed to overcome intermolecular attraction
forces. This energy is taken from the molecules themselves.
 Therefore the gas is cooled. This process is repeated many times
until the gas is completely changed into liquid state.
 LINDE’S METHOD
A. Air is compressed to 200 atm.
B. Most of the water in air is condensed and removed.
C. The heat generated as a result of compression is removed by
passing the gas through coils C.
D. The dry gas is then passed through a copper spiral coil E.
E. It is then expanded to almost 1 atm through a controlled valve J.
F. When the air comes out of the valve, expansion takes place from
200 atm to 1 atm. In this way fall of temperature occurs. This
cold air goes up and cools the incoming compressed air.
G. The cycle is repeated several times.
H. The temperature of the expanding gas finally drops and the
remaining air is liquefied.
I. The liquid air is collected in chamber F and can be drawn off.
 CONSTRUCTION OF APPLIANCES
 In a refrigerator, compressor compresses a gas such as
Freon.
 An increase in temperature takes place. The hot Freon
gas moves to a condenser on the outside of refrigerator.
 Air at room temperature cools the gas down and as a
result condenses into liquid.
 The liquid Freon, now at room temperature, is then
passed through small hole in a restriction valve into the
low pressure tubes which are inside the refrigerator.
 There, the Freon liquid vaporizes rapidly. The heat of
vaporization needed to do this is drawn from Kinetic
energy of the Freon molecules which then becomes very
cold.
 This cold gas absorbs heat from the refrigerator and its
content, thereby cooling. Cycle repeats
 SELF COOLING POP CAN

 A small container holding liquid CO2 is built

right into the can.
 When the can is opened, the liquid CO2
vaporizes and escapes out of the top of the
can.
 The heat absorbed by the vaporizing CO2 can
lower the temperature of the POP by about
16oC in a few seconds.
 Thus the temperature is lowered considerably.
BY THE ADIABATIC EXPANSION OF A COMPRESSED GAS
INVOLVING MECHANICAL WORK- CLAUDE’S PROCESS:-

This is based upon principle that when a gas

expands adiabatically against a piston in an
engine, it does some external work; hence
its internal energy falls and consequently the
temperature of the gas falls.

This principle combined with the Joule-Thomson effect, has been applied in the
Claude’s process for liquefaction of air.
CLAUDE’S PROCESS
COMPRESSOR

AIR

D Y

LIQUID AIR
Thermo & Stat Mech - Spring 2006 Class
19
G 14
FIGURE:-14
 The purified air i.e. air free from CO2 and water vapours is first compressed to
about 200 atmospheres by compressor.
 The compressed air then passes through the tube which bifurcates the incoming
gas part of the air goes into the cylinder fitted with an air tight piston and rest of
the air passes through the spiral coil which ends in a jet.
 The air that goes into the cylinder pushes the piston and thus does some
external work.
 As a result, the internal energy of air falls and hence temperature falls.
 The cooled air then enters the chamber at lower end.
 The air that passes through the spiral coil is cooled by Joule-Thomson effect as
it comes out through the jet in low pressure region (50 atm) of chamber.
 The cooled air is circulated again and again with the incoming air till the air gets
liquefied.
 The liquefied air collects in the chamber and is withdrawn.
Magnetic Cooling: Adiabatic Demagnetization
This process was given independently by Debye and Giauque. This
process is based upon the principle that when a magnetised body is
demagnetised adiabatically the temperature of the body must fall.

 First, the sample to be cooled (typically a gas) is allowed to touch a cold reservoir (which
has a constant temperature of around 3-4 K, and is often liquid Helium), and a magnetic
field is induced in the region of the sample.
 Once the sample is in thermal equilibrium with the cold reservoir, the magnetic field
strength is increased. This causes the entropy of the sample to decrease, because the
system becomes more ordered as the particles align with the magnetic field. The
temperature of the sample is still the same as that of the cold reservoir at this point.
 Then the sample is isolated from the cold reservoir, and the magnetic field strength is
reduced. The entropy of the sample remains the same, but its temperature drops in
reaction to the reduction in the magnetic field strength. If the sample was already at a
fairly low temperature, this temperature decrease can be ten-fold or greater.
 This process can be repeated, permitting the sample to be cooled to very low temperatures.
 Linde – Hampson system
The salient features of this system are as follows.
• Linde – Hampson cycle consists of compressor, heat
exchanger and a J – T expansion device.
• Only a part of the gas that is compressed, gets
liquefied.
• Being an open cycle, the mass deficit occurring is
replenished by a Makeup Gas connection.
• All the processes are assumed to be ideal in nature
and there are no irreversible pressure drops in the
system.
• Compression process is isothermal while the J – T
expansion is isenthalpic.
 Linde – Hampson system
• The system incorporates a Two-
Fluid heat exchanger which is
assumed to be 100% effective.
• The heat exchange process is an
isobaric process and it is used to
conserve cold in the system.
• That is, the stream of gas (2-3) is
cooled by the stream of gas (g-1).
• The J – T expansion device is used
for phase change of gas stream to
liquid stream by lowering the
temperature.
 Linde – Hampson system
• Consider a control volume for this system as shown in
the figure.
• It encloses the heat exchanger, J – T device and the
liquid container.
• The 1st Law of Thermodynamics is applied to analyse
the system.
• The changes in the velocities and datum levels are
assumed to be negligible.
• The quantities entering and leaving this control
volume are as given below.
 Linde – Hampson system

Using 1st Law , we get

Rearranging the terms, we have

Linde – Hampson system

The fraction of gas liquefied or liquid yield is defined as

y depends on the initial conditions

and the compression pressure.
• The values of h1 and hf are governed by the initial
conditions, which are often ambient.
• In order to maximize y, the value of h2 should be as
small as possible.
• To have a minimum h2, the change in enthalpy for a
given change in pressure should be zero at temperature
T1.
Mathematically,

Using calculus, for variables enthalpy (h),

pressure (p) and temperature (T), we have

Substituting the J – T coefficient and the

Cp for the second and third terms
respectively, we have
Cp is a positive quantity and hence cannot
be zero.

Therefore,

It implies that, in order to maximize y, the

state 2 should lie on the inversion curve for
a particular gas at the temperature of
compression process.
For a Linde – Hampson system following hold true.

• As the compression pressure increases, the liquid

yield y increases for a given compression
temperature.

• As the compression temperature decreases, the

liquid yield y increases for a given compression
pressure.