LectureL/O/G/O

No.5

Advanced Engineering
Thermodynamics
Asst.Prof. Dr. Mahdi Hatf
Kadhum
(For Master Techniques )

29-11-2020
Liquefaction of gases
 Definition
Liquefaction of gases: It is a phenomena of converting a gas into liquid.

A gas is liquefied by controlling two factors:-

a) Lowering the temperature.(K.E of gas molecules decreases )

b) Increasing the pressure . (gas molecules comes closes due to force of

attraction and changed into liquid)

CO2 , NH3 , SO2, H2O etc. – Liquefied when temperature is lowered with
increase in pressure , these gases were named as Temporary Gases.

Why easily liquefied ? Because they have greater intermolecular forces of

attraction or high value of (a) in vander walls equation.
PV=nRT for ideal gas law

Subsequent experiments revealed deviations in the behavior of real gases

from the ideal gas law. These results were summarized by the Dutch
physicist Johannes Diderik van der Waals (1837−1923) who
in 1873 proposed a more accurate equation of state for a real gas. It is
called the Van der Waals equation. For one mole of a gas, it can be written
as:

Vander walls equation:  a 

 p  2 Vm  b   RT
 Vm 


where Vm is the molar volume

where a is a constant whose value depends on the gas.
where b is the volume per mole that is occupied by the molecules.
 van der Waals Coefficients
Gas a (Pa m6) b (m3/mol)
Helium 3.46 x 10-3 23.71 x 10-6
Neon 2.12 x 10-2 17.10 x 10-6
Hydrogen 2.45 x 10-2 26.61 x 10-6
Carbon dioxide 3.96 x 10-1 42.69 x 10-6
Water vapor 5.47 x 10-1 30.52 x 10-6
 Example: Predict the pressure of nitrogen gas at T = 175 K and v =
0.00375 m3/kg on the basis of (a) the ideal-gas equation of state, (b) the
van der Waals equation of state. Compare the values obtained to the
experimentally determined value of 10,000 kPa.

Sol. The gas constant of nitrogen gas is 0.2968 kPa m3/kg K

(a) Using the ideal-gas equation of state, the pressure is found to be

which is in error by 38.5 percent.

(b) The van der Waals constants for nitrogen are determined
 which is in error by 5.3 percent.

There are an equation which is in error by only less than 1% percent

SO2 > NH3 > H2O > CO2 etc. Decreasing value the (a)

There are some gases such as : H2 , N2 , O2 etc.

Are not liquefied under above condition , these gases were named
Permanent gases.

Why cannot be liquefied easily?

Because they have less intermolecular force of attraction (i.e.) (a).

Thus , the above two conditions is helpful in converting a gas into liquid. But
the effect of temperature is rather more important than that of pressure. The
essential conditions for liquefaction of gases were discovered by Andrews
in 1869.
 P-V-T relationship for CO2

He reported that above a certain temperature , it was

impossible to liquefy a gas whatever the pressure was
applied .

The maximum temperature at which the gas can be

liquefied by the application of pressure is called critical
temperature (Tc).

Pc= Pressure required to liquefy a gas at Tc.

Vc= volume occupied by 1 mole of substance at Tc.

Andrew studies on isotherm of CO2
 isotherms
These isotherms divided in to 3 categories:
A) Isotherms below 31.1oC
B) Isotherms above 31.1oC
C) Isotherms at 31.1oC

A) Isotherms below 31.1oC

2 isotherms
ABCD at 13.1 oC
EFGH at 21.5 oC

Isotherms ABCD at 13.1oC

i) Curve AB follows Boyles Law

ii) Horizontal curve BC: at point B Liquefactor start along BC. A slight increase in
pressure leads to sharp decrease in volume up to C. At point C it is completely
changed to liquid . Here it will have two- phase – liquid and vapor phase.
iii) Vertical curve CD: Along the CD the volume of gas changes by very small amount
, ever if there is large increase in pressure because liquid of CO2 is almost
incompressible
Isotherms EFGH at 21.5oC

i) It is analogues to curve ABCD . Horizontal part FG is smaller than BC i.e at

higher temperature difference between the volume of gas and the volume of
liquid obtained by liquefaction of gas decreases.

ii) At high temperature , higher pressure is needed for liquefaction of gas.

Isotherms Above 31.1oC ( i.e at 48.1 oC)

The horizontal part disappear and the gas shows purely ideal behaviors.
There is no possibility of liquefaction of CO2 how much P applied.

Isotherms At 31.1oC
As the temperature is raised. The horizontal portion of isotherm becomes
smaller and smaller until at 31.1oC at which it reduces to a point P (called
Critical Point/ point of inflection).
At and Above this temperature the gas cannot liquefied by applying pressure
only is called Critical Temperature (Tc).
I J K L – Critical Isotherm

Here the gas and liquid has the same density and
indistinguishable.
The tangent at critical point at Point P is horizontal so that,
dp/dv at critical point will be zero.
Corresponding pressure at Tc = pc
Corresponding volume at Tc = vc of CO2

It may concluded from this explanation that is the area of the

left of the dotted line below the critical isotherm only liquid CO2
exists.
To the right of the dotted line gaseous CO2 exists . The
horizontal portion within the dotted line shows equilibrium
between the gas and liquid phase.
Critical Temperature Tc= it is the maximum temperature at which a
gas can be liquefied i.e temperature above which liquid cannot exist.

T>Tc no liquefaction
T<Tc liquefaction is possible

Critical pressure pc= it is the minimum pressure required to cause

liquefaction at critical temperature.
p<pc at Tc no liquefaction
p>pc at Tc liquefaction is possible

Critical volume vc= it is the volume occupied by one mole of a gas at

critical temperature and critical pressure.
 How to find Tc and Pc and Vc
From Vander walls equation:

 a 
 p  2 Vm  b   RT
 Vm 

 pVm 2  a 
 Vm  b   RT
 V 2 
 m 
 pV m
2

 a Vm  b   RTVm
2

3 2 2
pVm  bpVm  aVm  ab  RTVm ÷ p
2
3 2 a ab RTVm
Vm  bVm  Vm  
p p p
3 RT 2  a   ab 
Vm  (b  )Vm   Vm      0 This is a Cubic equation
p  p  p
Theoretically for any given T and P , there are three volume is possible

Curve for cubic equation

(Vander walls equation)
At critical temperature there is only one volume is possible.

Mathematically at Tc and pc cubic equation will have three same roots.(vc)

RTc  a   ab 
)Vm   Vm      0
3 2
Vm  (b  .......(1)
pc  pc   pc 
This equation will be same as the following:

Vm  Vc Vm  Vc Vm  Vc   0

Vm  Vc   0
3

Vm  Vc  3Vm Vc Vm  Vc   0
3 3

3 3 2 2
Vm  Vc  3Vm Vc  3Vc Vm  0
 RTc  a   ab 
)Vm   Vm      0
 
3 2
Vm  (b  .......(1)
pc  pc   pc 
2
  
Vm  Vm  - 3Vc   Vm 3Vc   Vc  0
3 2 3
 ...........(2)
Equation (1) & (2) are identical , we can compare the coefficients:
RTc
b  -3Vc
pc
RTc
b  3Vc ............(3)
pc We can calculate:
a 2
Pc & Tc & vc
 3Vc ............(4)
pc
ab 3 ab 3
  Vc  Vc ............(5)
pc pc
We can divided eq.(4) by (5):

Eq.(4) 1 3
Eq.(5)  Vc  3b
b Vc

Now we can use Eq. (5):

ab
  3b  ab
3

pc  27 b 3
pc

a a
 27 b 2
pc 
pc 27 b 2
 Now we can use Eq. (3):

RTc
b  3 3 b  27 b 2 RTc
a  8b
27 b 2 a
8ab 8a
Tc  Tc 
27 b 2 R 27 bR

If a & b are known , we can calculate Critical constants.

The constants a and b can be determined for any substance.
 H.W 1

Find the values of critical points (Tc, Pc, Vc )

for five gases depending on the constants a,b
from above equations?

You can choose five gases

 H.W 2

Find the critical points (Tc, Pc, Vc ) in another way?

 a 
 p  2 V  b   RT
 V 

 p   p
2
  0  2   0
 V  T Tc  V T Tc
 H.W 3

Show the qualification methods?

 Summary
1 A gas is liquefied by controlling two factors:-
a) Lowering the temperature.
b) Increasing the pressure .
2 Temporary Gases : CO2 , NH3 , SO2, H2O etc.
Permanent Gases : H2 , N2 , O2 etc.
3 T>Tc no liquefaction
T<Tc liquefaction is possible

p<pc at Tc no liquefaction
p>pc at Tc liquefaction is possible

a 8a
4 Vc  3b pc  Tc 
27 b 2 27 bR
L/O/G/O