REAL GAS

An ideal gas is a hypothetical gas whose pressure, volume and temperature behaviour is
completely described by the ideal gas equation. Actually no gas is ideal or perfect in nature.
All gases are real gases.
Real gases do not obey the ideal gas laws exactly under all conditions of temperature and
pressure. Real gases deviates from ideal behaviour because of mainly two assumptions of
"Kinetic theory of gases".
(i) The volume of gas particle is negligible compared to volume of container (while the
real gas particles have some significant volume).
(ii) There is no interaction between gaseous particles (while attraction forces exist between
real gas particles).

 Deviation from Ideal behaviours :
 Compressibility factor :
The extent to which a real gas departs from the ideal behaviour may be expressed in terms of
compressibility factor (Z), where Z is
Vm PVm
Z= = [Vm = molar volume]
Vm(ideal) nRT
When Z > 1, Vm > 22.7 L at STP ;
When Z < 1, Vm < 22.7 L at STP

 Plots of compressibility factor vs pressure :

(i) For an ideal gas Z = 1 and is independent of temperature and pressure.
(ii) Exceptional behaviour of H2 and He :
for these gases Z > 1. For such gases repulsive forces predominants.
(iii) Effect of pressure :
At very low P, PV  RT i.e. Z  1
At low P, PV < RT i.e. Z < 1
At moderate P, PV  RT i.e. Z  1
At high P, PV > RT i.e. Z > 1
(iv) For the gases which are easily liquefied (e.g. CO2) Z dips sharply below the ideal line in
the low pressure region.

1
 (v) Effect of temperature : An increase in temperature shows a decrease in deviation from
ideal behaviours i.e. PV approaches unity or Z approaches unity with increase in
temperature.

Conclusions :
Z = 1 for ideal gas ; Z > 1 at all pressures for He/H2
Z < 1 at low pressure (for all other gases) ; Z > 1 at high pressure (for all other gases)
2. Vander Waal Equation of real gases :
The ideal gas equation does not consider the effect of attractive forces and molecular volume.
Vander Waal's corrected the ideal gas equation by taking the effect of
(a) Molecular volume (b) Molecular attraction
2.1 Volume correction :
In the ideal gas equation, PiVi = nRT, Vi represents the ideal volume where the molecules can
move freely. In real gases, a part of the total volume is occupied by the gas molecules.
Hence the free volume Vi will be less than volume of container.
1 4 
Excluded volume per molecule =   (2r)3  = Co-volume per molecule.
2 3 
The volume that is not available for free movement is called excluded volume.
let us see, how this excluded volume is calculated.
For above example, the entire shaded region is excluded, as its
centre of mass cannot enter this region. r r
1 2
If both molecules were ideal, then they would not have
experienced any excluded volume but not in the case, of real gas
as the centre of mass of ‘2’ cannot go further.
Excluded volume
Hence for this pair of real gas molecules, excluded volume per (not available for free momement)
4 
molecule = 4   r 3 
3 
4 
Excluded volume per mole of gas (b) = NA × 4 ×   r 3  = 4 x NA x Volume of individual
3 
molecule.
For n moles, excluded volume = nb
Vi = V – nb volume correction
2
2.2 Pressure correction :
Due to these attraction, speed during collisions will be reduced
Momentum will be less
Force applied will be less
Pressure will be less.
Pideal = P + {correction term}
Correction term a no. of molecules attracting the colliding molecule  (n/v).
n
Correction term density of molecules   
v
n
no. of collision a density of molecules   
v
n n
So net correction term     
v v
an 2
So net correction term =
V2
‘a’ is constant of proportionality and this is dependent on force of attraction
Stronger the force of attraction greater will be ‘a’ (Constant)
an 2
Pi = P +
v2
'a' is a constant which depends upon the nature of the gas, V is the volume of 1 mole of gas.
Combining the two corrections, for 1 mole of gas
 a 
 P  2  (V – b) = RT
 V 
 n 2a 
For n mole of gas  P  2  (V – nb) = nRT
 V 

2.3 Significance of 'a' and 'b' :

Van der Waals constant for attraction 'a' and volume 'b' are characteristic constants for a given
gas.
(i) The 'a' values for a given gas are measure of intermolecular forces of attraction.
More are the intermolecular forces of attraction, more will be the value of a.
(ii) For a given gas van der Waals constant of attraction 'a' is always greater than van der
Waals constant of volume 'b'.
(iii) The gas having higher value of 'a' can be liquefied easily and therefore H 2 and He are
not liquefied easily.
(iv) Unit of 'a' is lit 2 mole–2 atm or cm4 mole–2 dyne.
(v) Unit of 'b' is lit mole–1 or cm3 mole–1.

3
 Gas a (dm6 atm mol–2) b (dm3 mol–1)
Ammonia 4.17 0.0371
Argon 1.35 0.0322
Carbon dioxide 3.59 0.0427
Carbon monoxide 1.49 0.0399
Chlorine 6.49 0.0562
Ethane 5.49 0.0638
Ethanol 2.56 0.087
Ethylene 4.47 0.0571
Helium 0.034 0.0237
Hydrogen 0.024 0.0266
Hydrogen chloride 3.67 0.0408
Hydrogen bromide 4.45 0.0433
Methane 2.25 0.0428
Neon 0.21 0.0171
Nitric oxide 1.34 0.0279
Nitrogen 1.39 0.0319
Oxygen 1.36 0.0318
Sulphur dioxide 3.71 0.0564
Water 5.44 0.0305

Ex.1 Arrange following in decreasing ’a’ factor (H2O, CO2, Ar)

Sol. H2O > CO2 > Ar
polar

Ex.2 Arrange following gases according to ‘a’ (He , Ar, Ne, Kr).
Sol. aKrKr > aAr > aNe > aHe

Ex.3 Arrange the following according to liquification pressure (n-pentane ; iso-pentane , neo
pentane).
Sol. an-pentene > aiso-pentane > aneo-pentane

Ex.4 Two Vander Waals gases have same value of b but different a values. Which of these would
occupy greater volume under identical conditions ?
Sol. If two gases have same value of 'b' but different values of 'a', then the gas having a larger value
of 'a' will occupy lesser volume. This is because the gas with a larger value of 'a' will have
larger force of attraction and hence lesser distance between its molecules.

4
2.4 VERIFICATION OF VANDER WAAL’S EQUATIONS :
Variation of Z with P for vander waals' equation at any temperature.
Vander waal equation for 1 mole
 a 
 P  2  (Vm – b) = RT
 Vm 
Vm = volume of 1 mole of gas

2.4.1 AT LOW PRESSURE :

At low pressure Vm will be high.
a
Hence b can be neglected in comparision to Vm. but can't be neglected as pressure is low
Vm2
Thus equation would be
 a 
 P  2  Vm = RT
 Vm 
a
PVm + = RT
Vm
PVm a
+ =1
RT Vm RT
a
Z=1– Z<1
Vm RT
Real gas is easily compressible as compared to an ideal gas.

2.4.2 At high pressure (moderate temp.)

Vm will be low
so b can't be neglected in comparison to Vm
a
but 2 can be neglected as compared to much higher values of P.
Vm
Then vander Waals' equation will be
P(Vm – b) = RT
PVm – Pb = RT
PVm Pb
= +1
RT RT
Pb
Z= + 1 (Z > 1)
RT
If Z > 1, then gas is more difficult to compress as compared to an ideal gas.

5
2.4.3 At low pressure and very high temperature.
Vm will be very large
a
hence ‘b’ can't be neglected and 2 can also be neglected as Vm is very large
Vm
PVm = RT (ideal gas condition)

2.4.3 For H2 or He a ~ 0 because molecules are smaller in size or vander Wall's forces will be very
weak, these are non polar so no dipole-dipole interactions are present in the actions.
Pb
P(Vm – b) = RT so Z=1+
RT

Ex.5 Calculate the pressure exerted by 5 mole of CO2 in one litre vessel at 47ºC using van der waal's
equation. Also report the pressure of gas if it behaves ideal in nature.
Given that a = 3.592 atm L2 mol–2, b = 0.0427 L/mol. Also, if the volume occupied by CO2
molecules is negligible, then calculate the pressure exerted by one mole of CO 2 gas at 273 K.
Ans. P = 77.218 atm, PIdeal = 131.36 atm, P = 0.9922 atm
Sol. Vander waal's equation
 n 2a 
 p  [V – nb] = nRT
 V 2 
n CO2 = 5, V = 1 litre, T = 320 K, a = 3.592, b = 0.0427
 3.592 
  P  25  1  [1 – 5 × 0.0427] = 5 × 0.0821 × 320
  P = 77.218 atm
For ideal behaviour of gas, PV = nRT
 P × 1 = 5 × 0.0821 × 320
  P = 131.36 atm
6
  a 
For one mole  P  2  [V – b] = RT
 V 
RT a
 P= 
V V2
0.0821 273 3.592
 P= 
22.4 (22.4) 2
 P = 0.9922 atm

Ex.6 Two moles of ammonia gas are enclosed in a vessel of 5 litre capacity at 27ºC. Calculate the
pressure exerted by the gas, assuming that
(i) the gas behaves like an ideal gas (using ideal gas equation).
(ii) the gas behaves like a real gas (using van der Waal’s equation)
Given that for ammonia, a = 4.17 atm litre2 mol–2 and b = 0.037 litre mol–1.
Ans. 9.85 atm, 9.33 atm
Sol. Given,
n = 2 moles
V = 5 litres
T = 27ºC = (27 + 273) K = 300 K
a = 4.17 atm litre2 mol–2
b = 0.037 litre mol–1
Also, we know that
R = 0.0821 litre atm K–1 mol–1
(i) If the gas behaves like an ideal gas, we have
PV = nRT
nRT 2  0.0821 300
 P= = = 9.85 atm
V 5
(ii) If the gas behaves like a real gas, we apply van der Waal's equation i.e.
 an 2 
 P   (V – nb) = nRT
 V2 
nRT an 2 2  0.0821 300 4.17  (2) 2
or P=  2 =  = 9.33 atm
V  nb V 5  2  0.037 (5) 2

Ex.7 1 mole of CCl4 vapours at 77ºC occupies a volume of 35.0 L. If vander waal's constants are
a = 20.39 L2 atm mol–2 and b = 0.1383 L mol–1, calculate compressibility factor Z under,
(a) low pressure region. (b) high pressure region.
Ans. (a) 0.98 (b) 1.004
Sol. (a) Under low pressure region, V is high
  (V – b)  V

7
  a 
 P  2  V = RT
 V 
a
PV + = RT
V
PV a
 =1
RT RTV
PV  a  20.39
Z= = 1   =1– = 0.98
RT  RTV  0.0821 350  35

(b) Under high pressure region, P is high,

 a 
P  2   P
 V 
 P (V – b) = RT  PV – Pb = RT
PV Pb
 =1
RT RT
PV Pb  PV P 1 
 Z= =1+   1 or  
RT RT  RT RT V 
b 0.1383
Z=1+ =1+ = 1 + 0.004 = 1.004
V 35

2. VIRIAL EQUATION OF STATE :

It is a generalised equation of gaseous state. All other equations can be written in the form of
virial equation of state.
 1 
Z is expressed in power series expansion of P or  
 Vm 
B C D
Z=1+ + 2 + 3 + .....................
Vm Vm Vm
B – second virial coefficient, C – third virial coefficient, D – fourth virial coefficient.
The coefficients B, C...depend on the temperature but not the density and are known as virial
coefficients. Both B and C are negatige at low temperature and positive at high temperature.
The virial coefficients are determined by the intermolecular potential.
B represents the effects of interactions between pairs of molecules, C interactions among
triplets of molecules, and so forth.
Vander waals' equation in virial form :
 a 
 P  2  (Vm – b) = RT
 Vm 
RT a
P= – 2
(Vm  b) Vm