Fiziks: Chapter - 2

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Institute for NET/JRF, GATE, IIT‐JAM, M.Sc. Entrance, JEST, TIFR and GRE in Physics
Chapter - 2
Real Gases
2.1 Andrews’ Experiment on Carbon Dioxide
Andrews’ experiment investigated the behaviour of CO2 and analyse the Pressure
 P  versus volume V  at different temperature T .

The observations are following:
1. Above a temperature of about T  480 C  , the CO2 resembles that of Ideal gas.
2. As temperature is lowered, the isotherms exhibit distortion which gradually

increases, which is indication of deviation from the ideal gas character.
3. At 31.40 C a Kink is observed which suggests that gas can be liquified under
compression.
4. As temperature is lowered further, the kink spreads into a horizontal line, i.e.,
compression produces liquification.
From A to B , CO2 behaves as a gas. At point B , P D
K J
the liquification of the gas just starts. The gas
gas
P
liquid
condenses at constant pressure from B to C , so

that liquid and vapour phase co-exist. At C , the Condensation 480 C
C B 0
F A 31.40 C
gas is completely in the liquid phase. From C to 21.5 C
Q 13.10 C
D , the slope is very steep since a liquid is almost V
incompressible.
Conclusion: The temperature at which it becomes possible to liquefy a gas under
compression is known as critical temperature TC  [In Andrews’ experiment
TC   480 C ], corresponding pressure and volume is known as critical pressure  PC 
and critical volume VC  .
A gas can be liquified only if it is cooled upto or below its characteristic critical
temperature.
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Revised Edition 2019 48
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There exist a continuity of liquid and gaseous states, i.e. they are two distinct stages of a
continuous physical phenomenon.
2.2 Van der Waals equation of state.
The van der Waals equation for real gases are given by,
 a 
For 1 mole of gas,  P  2 V  b   RT
 V 
 n2 a 
And for n mole of gas,  P  2  V  nb   nRT .
 V 
Assumptions for real gas:

1. Gas molecules have finite size
2. There are weak interaction force, which depends only upon distance between them.
3. The molecular density is small and the number of collisions with the walls of the
container are exactly same for point and finite size molecules.
2.3 Correction in Ideal Gas equation to achieve van der Waals gas equation of state.
2.3.1 Correction for finite size
If V is volume available for one mole of gas (volume of container). If size of molecule
taken into account, then (V  b) is volume available for real gas which is less than V . b
is popularly known as co-volume, which is dependent on the nature of gas.
Example: If Vm is molecular volume of real gas, then prove
that b = 4NVm , if N is total number of molecule in container. d  2r

Vm
The volume available to first molecule = V
r r
The volume available to second molecule = V  Vs
Where, Vs is volume of exclusion i.e. around any molecule, a

Volume of exclusion
 4 d 3 
spherical volume is Vs    will be denied to every other
 3 
molecule.
4  2r 
3
Volume of exclusion, Vs   8Vm

3
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Similarly, volume available to the N th

molecule = V   N  1 Vs
Hence, the average volume available to each molecule is,

1 N N  N  1 Vs N N
V 
N
V   i  1V
i 1
s V 
2N
V 
2
Vs  V  8Vm  V  4 NVm
2
[As for large N , 1 can be neglected]
So, V  b   V  4 NVm  b  4 NVm
2.3.2 Correction for intermolecular attraction

A molecule in the interior of the gas is on average attracted equally in all direction, so
that there is no resultant force on it. But for outermost layer closes to the surface of
container, there will be net inward force. So whenever a molecule strikes the walls of
container, the momentum exchange will be less than that for an Ideal gas.
There forces are cohesive in nature and proportional to number of molecules. So, for real
a  a 
gas change in pressure is . So for real gas pressure will be P 2 
V2  V 
 a 
So, the gas equation reduces to  P  2  V  b   RT
 V 
RT a
Then, P   2
V b V
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2.3.3 Maxwell Equal Area

James Clerk Maxwell replaced the isotherm between a and c with a horizontal line
positioned so that the areas of the two hatched regions are 2
equal (means area of adb and bec are equal). The flat
P e
line portion of the isotherm now corresponds to liquid- 1 c
a
b
vapor equilibrium. As shown in figure. PV d
The portions a  d and c  e are interpreted as metastable
0
VL 1 2 VG 3 4
states of super-heated liquid and super-cooled vapor
respectively. The equal area rule can be expressed as:
VG
PV VG  VL    PdV
VL
where, PV is the vapour pressure (flat portion of the curve), VL is the volume of the pure
liquid phase at point a as shown in the diagram and VG is the volume of the pure gas
phase at point c as shown in the diagram. The sum of these two volumes will be equal to
the total volume V .
Example: One mole of a certain gas is contained in a vessel of volume V . At a
temperature T1 the gas pressure is p1 atm and at a temperature T2 the pressure is p2 atm.
Find the van der Waals parameters for this gas.
Solution: It is given that the number of mole n  1
 a 
 P1  2 V  b   RT1 (i)
 V 
 a 
 P2  2 V  b   RT2 (ii)
 V 
from (i) and (ii)
V 2 T1 P2  T2 P1 
a
T2  T1 
RT2  T1 
b V 
P2  P1 
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Example: Under what pressure will carbon dioxide of molar mass M have the density
 at the temperature T , if given gas is obeying van der Waals gas equation.
Solution: Assume M is molar mass of the carbon dioxide and V is the volume.
M
So,  
V
van der Wall equation (for one mole gas):
 a 
 P  2 V  b   RT
 V 
  2 a  M  RT  2a RT  2a
 P    b   RT  P    P  
 M 2    M  M2 M  b M 2
  b 
 
2.3.4 Critical Point
The van der Waals equation of state for a gas is given by
 
V  b   RT
a
P  2
 V 
where P, V and T represent the pressure, volume and temperature respectively, and a
and b are constant parameters. At the critical point, all the roots of the above cubic
equation are degenerate means all roots are equal.
Mathematically, the critical isotherm is the point of inflection.
On the basis of above definition, one can find the critical volume Vc , critical pressure Pc
and critical temperature Tc for van der waal gas.

For van der Waals equation,
 a 
 P  2  V  b   RT
 V 
RT a
P  2 (i)
V b V
 P 
   0 , for extremum point
 V T
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 P  RT 2a
    2  0 at V  Vc , T  Tc (ii)
 V T V  b  V
2
 2 P 
 2   0 , for inflection point
 V T
2 RT 6a
  0 , at V  Vc , T  Tc (iii)
V  b 
3
V3
8a
Solving (ii) and (iii), Vc  3b and Tc 
27 Rb
a
On putting the value of Vc and Tc , one can get Pc 
27b 2
RTc 8
  c c , which is popularly known as critical coefficient for van der Waals gas.
Pc vc 3
2.3.5 Van der Waals Equation of State and Virial Coefficient
According to virial theorem the equation of state is given by
 
pV      ..... (i)
V V2
Where  ,  and  are first, second and third virial coefficient.
For the Ideal gas,   RT and other coefficients are zero.
Virial coefficient for Van der Waals gas
To put van der Waals equation in virial form we first rewrite it as
1
 b a
pV  RT  1   
 V V
Using binomial theorem, we have
1
 b b b2
1    1   2  ....
 V V V
Hence
RTb  a RTb 2
pV  RT    ..... …. (ii)
V V2
As it will be noted, van der Waals equation has only three virial coefficients and on
comparison with equation (i) yields,
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  RT ,   RTb  a and   RTb 2

At the Boyle’s temperature, the second virial coefficient is zero.
Hence, RTB b  a  0
a
or TB 
Rb
From the preceding, section we recall that the critical temperature of a gas obeying van
der Waals equation of state is
8a
TC 
27 Rb
on comparing these expressions, we get
27
TB  TC  3.375 TC
8
i.e., the Boyle’s temperature, on the basis of van der Waals equation, is 3.375 times the
critical temperature.
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MCQ (Multiple Choice Questions)

Q1. A gas behaves as an ideal gas at
(a) very low pressure and high temperature
(b) high pressure and low temperature
(c) high temperature and high pressure
(d) low pressure and low temperature
 a 
Q2. In the van der Waals equation, the terms  2  and  b  are introduced to account for the
V 
(a) inter-molecular attraction and the total volume occupied by the gas
(b) molecular size and the size of the containing vessel
(c) inter-molecular attraction and the volume of the molecules
(d) inter-molecular attraction and the force exerted by the molecules on the walls of the
container
Q3. ‘Critical temperature’ is defined as the
(a) lowest temperature at which the gas can be liquified at constant pressure
(b) lowest temperature at which the gas can be liquified by increase of pressure alone
(c) highest temperature at which the gas can be liquified by increase of pressure alone
(d) highest temperature at which the gas can be liquified at constant pressure
Q4. The work performed by one mole of a van der Waals gas during its isothermal expansion
from the volume V1 to V2 at a temperature T is given by
V2  b 1 1 V2  b 1 1
(a) RT ln  a   (b) RT ln  a  
V1  b  V2 V1  V1  b  V1 V2 
V1  b 1 1 V1  b 1 1
(c) RT ln  a   (d) RT ln  a  
V2  b  V1 V2  V2  b  V2 V1 
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Q5.
D
P
A E
C
B
13.1o C
V
Consider the above graph in respect of van der Waals equation of state. Which portion of
the graph cannot be explained?
(a) AB (b) BC (c) DE (d) BCD
MSQ (Multiple Select Questions)

Q6. Which of the following are important in case of a van der Waals gas?
(a) Short range attraction (b) Long range repulsion
(c) Short range repulsion (d) Long range attraction
Q7. Which of the important results of Andrews’ experiment are correct?
(a) There exists a temperature called critical temperature, above which a gas cannot be
liquefied, however great the applied pressure is.
(b) There exists a temperature called critical temperature, below which a gas cannot be
liquefied, however great the applied pressure is.
a
(c) For van der Waal gases critical temperature is .
27 Rb
(d) Oxygen, nitrogen and hydrogen are permanent gases and they cannot be liquefied.
 a 
Q8. In the equation of state for real gases,  P  2 V  b   RT
 V 
(a) The critical points are point of inflection.
(b) Critical volume is given by Vc  3b
a
(c) Critical pressure is given by Pc 
27b 2
8a
(d) Critical temperature is given by Tc 
27 Rb
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NAT (Numerical Answer Type Questions)

Q9. If the value of van der Waals constant b for a real gas is 32 cm 3 / mol, then the
approximate volume of one molecule of the gas is ……… 10 23 cm3 (Avogadro constant
 6.02  10 23 ) (Answer must be upto one decimal)
 RT 
Q10. van der Waals equation predicts that the critical coefficient of a gas  c  has the
 PcVc 
value………..(Answer must upto one decimal point )
RT  a 
Q11. If equation of state is given by P  exp    then critical volume
V b  RTV 
Vc  ……….. b .
RT  a 
Q12. If equation of state is given by P  exp    , then critical temperature
V b  RTV 
a
Tc  ….. .
Rb
RT  a 
Q13. If equation of state is given by P  exp    then critical coefficient
V b  RTV 
RTc
 ........
PV
c c
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Solutions
MCQ (Multiple Choice Questions)
Ans. 1: (a)
Solution: The relation between PV and P is given as
PV  A  BP  CP 2  DP 2   (i)
A, B, C  are virial constant A  B  C  D  . If P is very high then PV  constant.
So, for ideal gas P should be small and T should be large.
Ans. 2: (a)
Solution: The ideal gas equation is PV  RT , whereas gas equation, for real gases is given by
 a 
van der Waals which is  P  2 V  b   RT where, the factor b is due to volume
 V 
 a 
occupied by the molecules itself and  2  is due to molecular attractive force.
V 
Ans. 3: (c)
Ans. 4: (a)
Solution: We know van der Waals gas equation:
 a 
 P  2 V  b   RT (i)
 V 
W   dW   pdV
RT a
from (i): P  2
V b V
V b  1 1
V2
 RT a 
then W    2 dV  RT ln 2  a  
V1 
V b V  V1  b  V2 V1 
Ans. 5: (d)
D
Solution: The van der Waals equation is given as
P
 a  A E
 P  2 V  b   RT C
 V 
B
13.1o C
where a, b are constants.
V
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The graph drawn is shown as the curve ABCDE . This does not agree with the
experimental isothermals for CO2 as obtained by Andrews. However, the portion DE
has been explained as due to super cooling of vapours and the portion AB due to super
heating of the liquid. But the portion BCD cannot be explained because it shows
decrease in volume with decrease in pressure.
MSQ (Multiple Select Questions)

Ans. 6: (c) and (d)
 a 
Solution: van der Waals equation  P  2 V  b   RT , where a, b are constant. In this case
 V 
short range of repulsion and long range of attraction is important.
Ans. 7: (a) and (d)
Solution: From the result of Andrews’ experiment, we can define critical temperature as a
temperature above which a gas cannot be liquefied however great the applied pressure is
All gases are real gas so they can be liquified.
8a
For van der Waals gases, critical temperature is given by Tc 
27 Rb
Ans. 8: (a), (b), (c) and (d)
Solution: The van der Waals equation is given as
 a 
 P  2 V  b   RT
 V 
 P   d2P 
   0 and  2   0 (point of inflection ) thus, we get Vc  3b
 V T  dV T
8a a
and Tc   Pc  and Vc  3b
27 Rb 27b 2
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NAT (Numerical Answer Type Questions)

Ans. 9: 1.3
Solution: The van der Waals constant b is given as b  four times the actual volume of the
molecules.
b
volume of one molecule 
4N
32
volume of one molecule   1.3  10  23 cm 3
4  6  10 23
Ans. 10: 2.6
8a a
Solution: For van der Waal Gases Tc  , Vc  3b , Pc 
27 Rb 27b 2
RTc 8

PcVc 3
Ans. 11: 2
RT  a 
Solution: P  exp    critical point are point of inflection so, at critical points
V b  RTV 
 P   d2P 
   0 and  2   0 (point of inflection)
 V T  dV T
So, Vc  2b
Ans. 12: 0.25

RT  a 
Solution: P  exp    critical point are point of inflection so at critical points
V b  RTV 
 P   d2P 
   0 and  2   0 (point of inflection )
 V T  dV T
a
Vc  2b, Tc 
4bR
Ans. 13: 3.7
RT  a 
Solution: P  exp    , critical point are point of inflection so at critical points
V b  RTV 
 P   d2P 
   0 and  2   0 (point of inflection)
 V T  dV T
a a RTc e2
Vc  2b, Tc  and Pc  2 2  
4bR 4e b PV
c c 2
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 P  versus volume V  at different temperature T .

2. As temperature is lowered, the isotherms exhibit distortion which gradually

condenses at constant pressure from B to C , so

TC   480 C ], corresponding pressure and volume is known as critical pressure  PC 

and critical volume VC  .

Assumptions for real gas:

that b = 4NVm , if N is total number of molecule in container. d  2r

Where, Vs is volume of exclusion i.e. around any molecule, a

Volume of exclusion, Vs   8Vm

Similarly, volume available to the N th

Hence, the average volume available to each molecule is,

2.3.2 Correction for intermolecular attraction

2.3.3 Maxwell Equal Area

and critical temperature Tc for van der waal gas.

  RT ,   RTb  a and   RTb 2

MCQ (Multiple Choice Questions)

MSQ (Multiple Select Questions)

NAT (Numerical Answer Type Questions)

MSQ (Multiple Select Questions)

NAT (Numerical Answer Type Questions)

Ans. 12: 0.25

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