G.G.PG .COLLEGE .QUETTA .CANTT..

ASSIGNMENT # 01

SUBJECT; Physical Chemistry

TOPIC; Critical Phenomenon

DEPARTMENT; Chemistry 3rd sem

DATE; 15th april,2024

SUBMITTED BY; Maryam Shafique

SUBMITTED TO; Miss Hala

 CRITICAL PHENOMENA:
LIQUEFACTION OF GASES

When the molecules of a gas are brought closer to each other due to increase in the attractive forces a
stage may be reached when the gas changes its phase to liquid. This phenomenon is called Liquefaction
of gases. Obviously, an ideal gas cannot be liquefied as there are no interactions in that case. For the
liquefaction of Real gases, we can do either of the following:

1. Increase the pressure on the gas

2. Decrease the Temperature of the gas

Both these processes will tend to bring the molecules closer and liquefaction may take place. But it is
observed practically that Temperature is the dominant factor for liquefaction and pressure assumes a
secondary role. For every real gas a temperature is observed above which it cannot be liquefied even on
the application of very high pressures. This characteristic temperature of a real gas above which it
cannot be liquefied is called “Critical Temperature” represented by TC. To understand this concept in
depth, observe the isotherms drawn in the following figure for a real gas at varying temperatures.

LIQUEFACTION OF GASES
We observe the following:

1. At high Temperatures like T4, the isotherms look just like those of ideal gas.

2. At low temperatures the curve is entirely different. For example, curve abcd at temperature T1. As
the pressure increases the volume of the gas decreases from point a to b. Then there is a sudden
reduction in volume without much increase in pressure of the gas from b to c. In this portion
liquefaction is taking place at constant pressure and due to the difference in the properties of gas and
liquid the volume is reducing so much. And after c even on increasing pressure there is no appreciable
decrease in volume as now only liquid is present. So, a b represents gaseous phase, b c represents
liquid-gas coexistence and cd represents liquid phase.

3. On carrying out the same process at a higher temperature we observe that the width of the
horizontal portion decreases and the pressure at which liquefaction takes place also becomes higher.
The horizontal portion decreases because at higher temperatures the properties of liquid approach that
of a gas and ΔV = VG – VL reduces.

4. At temperature TC the horizontal portion reduces to a mere point at which liquefaction takes place.
Point Y is called critical point ; at this point the boundary between liquid and gas phase (meniscus)
disappears indicating that both the phases have identical characteristics.

5. Above this temperature there is no liquefaction of gases and gas behaves almost ideally.

At critical point Y the tangent is horizontal , so that , dP/dV at critical point will be zero.Thus , the point Y
is also called the point of deflection.

CRITICAL CONSTANTS
In critical constant there are three terms;

Critical temperature, TC is the maximum temperature at which a gas can be liquefied that is a
temperature above which liquid cannot exist.

Critical Pressure, PC is the minimum pressure required for liquefaction to take place at the critical
condition.

Critical volume, VC is the volume occupied by one mole of the gas at critical temperature and critical
pressure.

These parameters are given by the following expressions:

TC = 8a/27Rb

PC = a/27b2

VC = 3b

Discovery of Critical phenomenon

Discovery of critical phenomenon by Andrew in 1869 showed that gases can not be liquefied by the
application of pressure alone; they must be cooled below their critical temperatures and then subjected
to adequate pressure to cause liquefaction.
Principles involved in Liquefaction are :
1. a gas must be at or below its critical temperature. Lower the temperature below the critical value ,
easier would be the liquefaction.

2. The gas is cooled either by doing external work or by expanding against the internal forces of
molecular attraction.

Lower temperature for liquefaction of gases can be achieved by the

following techniques :
(a) Cooling by rapid evaporation of a volatileliquid.

(b) Cooling by joule-thomson effect.

(c) Cooling by the adiabatic expansion involving mechanical work

Applications of Liquifaction of gases:

 Natural Gas Processing: The liquefaction of natural gas is essential for its storage and
transportation. Natural gas is compressed and cooled until it reaches its critical temperature,
causing it to become a liquid state, making it easier to transport by tanker ships or pipelines.
 Industrial Refrigeration: The liquefaction of gases such as ammonia, Freon, and carbon
dioxide is used as a refrigerant in various industrial processes and refrigeration systems.
 Cooling and Freezing Food: The liquefaction of gases like carbon dioxide and nitrogen is used
for quick cooling and freezing of food products in the food processing industry.
 Oxygen Production: The liquefaction of air is used to produce oxygen for medical, industrial
and scientific purposes.
 Cryogenics: The liquefaction of gases such as helium and nitrogen is used in cryogenic
applications, including superconductivity research, cryogenic fuel storage and rocket propulsion
systems.
 Fire Extinguishing: The liquefaction of gases like nitrogen and carbon dioxide is used as a fire
extinguishing agent in industries such as chemical plants and oil refineries.
 Welding and Metalworking: The liquefaction of gases like argon and helium is used as a
protective shielding gas in various welding and metalworking processes.
 Car Fuel: The liquefaction of gases such as propane and methane is used as a fuel for cars,
especially in rural areas where gasoline is not easily available.