REAL GAS (Physical Chemistry)

EXERCISE-1
DPP-1
VANDER WAALS' EQUATION

1. The correct expression for the Vander Waal’s equation of state is :

 a   an 2 
(A)  P + 2 2  (V – nb) = nRT (B)  P +  (V – nb) = nRT
 n V   V2 

 an 2   P + an 2 
(C)  P +  (V – nb) = nRT (D)   (V – nb) = nRT
 V2   V
2


2. Consider a real gas placed in a container. If the intermolecular attractions are supposed to
disappear suddenly which of the following would happen ?

(A) The pressure decreases

(B) The pressure increases
(C) The pressure remains unchanged

(D) The gas collapses

3. The pressure of real gases is less than the pressure of an ideal gas because of :
(A) higher number of collisions

(B) Finite size of molecule

(C) higher KE of molecules
(D) Intermolecular forces of attraction

4. If ‘V’ is volume of 1 molecule of a gas then, excluded volume (b) of 1 mole of gaseous molecule is -
(A) 4 NAV (B) NAV (C) 4V/NA (D) V
5. Equal moles three real gases A, B & C are placed in three separate containers at same temperature
& pressure. The value of vander Waal’s constant ‘a’ is 0.03 atm-lit2/mole, 0.1 atm-lit2/mole &
0.065 atm -lit2/mole respectively for A, B & C gases. If radius of molecules of all three gases are
same. Then find the correct relationship between volume of containers V A, VB & VC is which A, B
& C respectively are placed -
(A) VA > VB > VC (B) VA < VB < VC

(C) VB > VA > VC (D) VB < VC < VA

6. Under which of the following conditions a real gas resembles an ideal gas -
(A) ‘a’ and ‘b’ are very large

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(B) ‘a’ and ‘b’ are very small

(C) ‘a’ is large and ‘b’ is small
(D) ‘a’ is small and ‘b’ is large

7. Calculate the amount of He (in gm) present in the 10 litre container at 200 atm and 300K. Given
value of “b” for He is 0.08 dm3 mol–1 ; R = 0.08 atm lit mol–1 K–1.
8. A gas at 300 K and 11 atm has a molar volume 10% greater than that calculated from the perfect
gas law. Then calculate the molar volume (in ml) of gas under the above conditions.

9. Using the van der Waals equation, calculate the pressure in atm of 10.0 mol NH 3 gas in a 10.0 L
vessel at 27ºC.
Given : a = 4 L 2. atm/mol2 ; b = 0.04 L/mol ; R = 0.08 atm lit mol–1/K

10. Calculate from the van der Waals' equation, the temperature at which 128 gm of SO 2 would
occupy a volume of 10 dm3 at 15 atm pressure.[a = 6 atm lit2 mol2, b = 0.05 lit mol–1]

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DPP-2
Compressibility factor
1. Compressibility factor of ideal gas is :-

(A) z > 1 (B) z > 1 (C) z = 1 (D) z = 

2. At relatively high pressure, Vander Waal’s equation reduces to :

a
(A) PVm = RT (B) PVm = RT +
Vm

a
(C) PVm = RT + PB (D) PVm = RT –
Vma

3. Compressibility factor at room temperature for H 2 behaving as real gas is :

 a   Pb  RTV
(A) 1 (B)  1 −  (C)  1 +  (D)
 RTV   RT  (1 − a)

4. As per Vander Waal’s equation, Compressibility factor at low pressures (For 1 mole), is equal to
:

 a   RTV   a   RTV 
(A)  1 −  (B)  1 −  (C)  1 +  (D)  1 + 
 RTV   a   RTV   a 

5. What is the compressibility factor (Z) for 0.02 mole of a Vander Waal’s gas at pressure of 0.1 atm.
Assume the size of gas molecules is negligible.
Given : RT = 20 L atm mol–1 and a = 1000 atm L 2 mol–2
(A) 2 (B) 1 (C) 0.02 (D) 0.5

6. At 273 K temperature and 9 atm pressure, the compressibility factor for a gas is 0.9. The volume
of 1 milli-mole of gas at this temperature and pressure is :
(A) 2.24 litre (B) 0.020 mL (C) 2.24 mL (D) 22.4 mL

7. 'Z' v/s 'P' graph is plotted for 1 mole of hypothetical gas. Volume of gas at this point 'A' is [R =
0.08 atm L mole-K]

(A) 0.01 L (B) 0.09 L (C) 0.065 L (D) 0.65 L

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8. At 300K for CO2 gas, following Vander Waal’s equation, a graph is plotted between PV m v/s P,
where Vm is molar volume, then intercept of given graph will be
[Given : For CO2 ; a = 3 atm –L2/ mol2 ; b = 0.04 L/mole

R = 0.08 atm-L/mole – K]
9. If density of vapours of a substance of molar mass 18 gm at 1 atm pressure and 500 K is 0.36 kg
m–3, then calculate the value of Z for the vapours. (Take R = 0.08 L atm mole –1 K–1)
10. At 273.15 K and under a pressure of 10.1325 MPa, the compressibility factor of O 2 is 0.927.
Calculate the mass of O2 necessary to fill a gas cylinder of 100 dm 3 capacity under the given
conditions.

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DPP-3
Compressibility factor and Boyles temperature
1. Correct option regarding a container containing 1 mol of a gas in 22.4 litre container at 273 K is

(A) If compressibility factor (Z) > 1 then 'P' will be less than 1 atm.
(B) If compressibility factor (Z) > 1 then 'P' will be greater than 1 atm.
(C) If 'b' dominates, pressure will be less than 1 atm.

(D) If 'a' dominates, pressure will be greater than 1 atm.

2. Observe the following Z vs P graph.
Z
H2

Ne
1.0 NH3
?

The missing gas in the above graph can be :

(A) He (B) Ar (C) H2O (D) CH4

3. The density of a gaseous substance at 1 atm pressure and 750 K is 0.30 g/lt. If the molecular
weight of the substance is 27. Which forces dominates among gas molecules relative to ideal gas -
(A) Attractive

(B) Repulsive
(C) same as ideal gas
(D) can’t determine
PV
4. Consider the equation Z = , Which of the following statements is correct :
RT

(A) When Z > 1, real gases are easier to compress

(B) When Z = 1, real gases are easier to compress

(C) When Z > 1, real gases are difficult to compress
(D) When Z < 1, real gases are difficult to compress

5. The density of a gas 'A' at 1 atm and 750K is 0.3 gm/litre. If the molecular weight of 'A' is 27 then
choose the correct statement -
(A) 'A' behaves ideally

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(B) 'A' behaves non-ideally with +ve deviation

(C) 'A' behaves non-ideally with –ve deviation
(D) 'A' can be liquified by applying pressure at 750K.

6. A real gas most closely approaches the behaviour of an ideal gas at –

(A) 15 atm and 200 K (B) 1 atm and 273 K
(C) 0.5 atm and 500 K (D) 15 atm and 500 K

7. The Vander Waal’s constant for a gas are

a = 1.92 atm L 2 mol–2, b = 0.06L mol–1 . If R = 0.08 L atm K—1 mol–1, what is the Boyle's temperature
of this gas.

8. Consider the following statements:

The coefficient B as per Vander Waal’s equation
(i) is independent of temperature

(ii) is equal to zero at Boyle temperature

 B C 
PVm = RT  1 + + 2 + ........ 
 Vm Vm 

(iii) has the dimension of molar volume

Which of the above statements are correct.
(A) i and ii (B) i and iii (C) ii and iii (D) i, ii and iii

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DPP-4
critical constant
1. Select the incorrect relation for a Vander Waal's gas-

(A) TC = 8 a (B) PC = a
(C) VC = 4b (D) Tb = a
27 Rb 27b2 Rb

2. The critical temperature of water is higher than that of O 2 because the water molecule has

(A) Fewer electrons than O2 (B) two covalent bonds

(C) V-shape (D) dipole-dipole attraction
3. The van der Waals parameters for gases W, X, Y and Z are

Gas a(atm L 2 mol–2) b(L mol–1)

W 4.0 0.027
X 8.0 0.030

Y 6.0 0.032
Z 12.0 0.027
Which one of these gases has the highest critical temperature ?

(A) W (B) X (C) Y (D) Z

4. Consider the following statements: If the van der Waal’s parameters of two gases are given as
a (atm lit2 mol–2) b (lit mol–1)

Gas X: 6.5 0.056

Gas Y: 8.0 0.011
(i) VC (X) < VC(Y) (ii) PC (X) < PC (Y) (iii) TC (X) < TC(Y)

Select correct expression:

(A) (i) alone (B) (i) and (ii)
(C) (i), (ii) and (iii) (D) (ii) and (iii)

5. The critical density of the gas CO2 is 0.44 g cm–3 at a certain temperature. If r is the radius of the
molecule, r 3 in cm3 is approximately. (N is Avogadro number)
25 100 6 25
(A) (B) (C) (D)
N N N 4N

6. The values of van der Waals' constant 'a' for the gases O 2, N2, NH3 and CH4 are 1.360, 1.390, 4.170
and 2.253 L atm mol–2 respectively. The gas which can most easily be liquefied is :
(A) O2 (B) N2 (C) NH3 (D) CH4

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7. Which set of conditions represents easiest way to liquefy a gas :

(A) Decreasing temperature and Increasing pressure
(B) Increasing temperature and decreasing pressure

(C) Decreasing temperature and decreasing pressure

(D) Increasing temperature and Increasing pressure
8. For two gases A and B, P v/s V isotherms are shown at same temperature, T K . T A & TB are critical
temperatures of A & B respectively, which of the following is true?
P A

(A) TA < T < TB (B) TA > T > TB (C) TA > TB > T (D) none of above

For a real gas (mol. mass = 30) if density at critical point is 0.40 g/cm 3 and its TC = 2  10 K, then
5
9.
821
Vander Waal's constant a (in atm L 2 mol–2) is

(A) 5.695 (B) 1.6875 (C) 0.1687 (D) None

10. Critical temperature and pressure of a real gas is 27°C & 75 atm respectively. The critical volume
of 1 mole of real gas is
(A) 12.47 litre (B) 0.12 litre

(C) 1.24 litre (D) Data insufficient

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EXERCISE-II
SCQ

1. For a particular gas at certain temperature following expression hold

d = 2.0 P + 0.02 P2 (gm/litre)
RT = 25 (atm - L/mole)

P is pressure in atmosphere
The molecular weight of gas is
(A)25 (B) 50 (C) 75 (D) 100

2. Density of a Vander Waal's gas at 500 K and 1 atm is found to be 0.8 kg/m 3. It is also found that
3
the gas diffuses √2 times slower than pure O2 gas under identical conditions. The value of Z for

the real gas is (R = 0.08 atm- /mol-K) :

(A) 2 (B) 3 (C) 1.8 (D) 0.8

3 2

3. The graph of compressibility factor (Z) vs P is plotted at constant temperature 273 K. If the slope
 dZ 
of graph at very high pressure   is 1 atm–1 , the volume of one molecule of real gas in cm3 is
 dp  10

[Given : R = 22.4 atm K–1 mol–1 and NA = 6 × 1023]

273

(A) 9.3 × 10–23 (B) 3.7 × 10–20 (C) 9.3 ×10–22 (D) 5.6 × 10–20
4. Berthelot proposed the following empirical relation to explain the real behavior of the real gases

 a 
P+  (Vm – b) = RT
 TVM2 

If the Berthelot equation of state be one of the forms of virial equation for 1 mole real gas is a
under:
𝐴 𝐵
PV = RT [1 + 𝑉 + 𝑉2 +. . . . . ]

where A, B are constant which are known as second & third coefficients respectively. Then what
will be the correct value of Boyle’s temperature (TB), the temperature at which real gas behave
as an ideal gas ?

a b aR a
(A) (B) (C) (D)
RB aR b Rb

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MCQ
5. Which of the following statement(s) is / are CORRECT -
(A) 'a' is measure of attractive forces among molecules

(B) Pressure exerted by real gas is lesser than that exerted by ideal gas under all conditions
(C) At high pressure repulsive forces dominates in real gases.
(D) Vander Waals constant ‘b’ is the measure of repulsive forces

6. Mark out the correct statement(s)

(A) Molar volume Vm > 22.4 L at 1 atm and 273 K when attractive force dominates.

(B) if compressibility factor of a gas at 1 atm & 273K is less than unity then its molar volume is
less than 22.4 L at 1 atm & 273K.

(C) Real gas shows negative deviation from ideal behaviour at low pressure condition.
(D) The gas having higher value of Vander Waal’s constant ''a'' will be more compressible than
one having lower value of ''a'', provided Vander Waal’s constant ''b'' is same for both the gases.
7. Which of the following statement(s) is / are CORRECT

(A) 'a' is measure of attractive forces among molecules

(B) Pressure exerted by real gas is lesser than that exerted by ideal gas under all conditions
(C) At high pressure repulsive forces dominates in real gases.

(D) Vander Waals constant ‘b’ is the measure of repulsive forces

8. Which of the following statement (s) are true about Z vs P graph for a real gas a particular
temperature.

Z behaviour of most
Real gases
p
X
d Z= 0
dP
(A) Z → 1 as P → 0 for most real gases

(B) dZ/dP is – ve as P → 0 for real gases

(C) dZ/dP→ 0 at a pressure where repulsive and attractive force are comparable.

(D) At point X, intermolecular attractive forces dominating over repulsive forces.

9. If critical temperature for the real gas is 500K then the value of-

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(A) Boyle's temperature is 1687.5 K

(B) Vander Waal’s constant a for the gas is 21.6 atm-L2/mol2

(C) Gas will show ideal behaviour at high temperature & low pressure.
(D) At Boyle's temperature behaviour of gas is always ideal

10. For real gas the P–V curve was experimentally plotted and it had the following appearance. With
respect to liquification, choose the incorrect statement :

(A) At T = 500 K, P = 40 atm, the state will be liquid

(B) At T = 300 K, P = 50 atm, the state will be gas
(C) At T < 300 K, P = 20 atm, the state will be gas

(D) At 300 K < T < 500 K, P > 50 atm, the state will be liquid
11. A vander Waal's equation for real gas is cubic in V (Volume of gas). Which of the following
statement is true about Vander Waal's equation of state of real gas.
(A) Below critical temperature TC, three value of volume is predicted by equation.

(B) Above critical temperature only two real solution is possible.

(C) At critical temperature, three roots of Vander Waal's equation coincide.
(D) Vander Waal's constant a and b are obtained theoretically.

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Paragraph for Questions 12 to 14

For a non-ideal gas, the compressibility factor (Z) is defined as
pVm
Z= ; Vm = molar volume
RT

Compressibility of an unknown gas at 600K and 1.0 atm was found to be 1.2 Also this gas was
found to effuse 1.414 times slower than the Ne gas under identical conditions [Given:- at mass of
Ne = 20]

12. Density of the gas in the above mentioned experimental condition is -

(A) 0.98gL –1 (B) 0.68gL –1 (C) 1.02 gL –1 (D) 1.47gL –1
13. Molar volume of the gas in the given experimental condition is -

(A) 40.8 L (B) 39.2 L (C) 58.8 L (D) 27.2 L

14. The value of the virial coefficient “B” in the virial equation is (ignore the higher terms from the
equation during calculations).

Virial equation : Z = 1 + B + C2 + D3 + ....Vm is the molar volume -

Vm Vm Vm

(A) 8.16 L mol–1 (B) 7.84 L mol–1 (C) 11.76 L mol–1 (D) 5.44 L mol–1
Match the Column

15. CO 2 (g) is characterised by Vander Waal equation and its critical temperature is 31°C. Making

appropriate approximation. Match the column -

Column-I Column-II

(A) At low pressure and room temperature (P) Z < 1

(B) At very high pressure and room temperature (Q) Z > 1
(C) At 500K and low pressure (R) Attractive forces dominates

(D) At critical temperature and low pressure (S) Negative slope in Z vs P

curve
(T) Repulsive forces dominates.

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EXERCISE # III
(JEE-MAINS)
1. When does a gas deviate the most from it's ideal behaviour? [JEE MAIN 2015]

(A) At high pressure and low temperature

(B) At high pressure and high temperature
(C) At low pressure and low temperature

(D) At low pressure and high temperature

2 If Z is the compressibility factor, van der Waals' equation at low pressure can be written as :

[JEE MAIN 2014]

a
(A) Z = 1 – Pb (B) Z = 1 + Pb (C) Z = 1 + Pb (D) Z = 1 –
RT RT RT Vm RT
3. The compressibility factor for a real gas at high pressure is :- [JEE MAIN 2012]

(A) 1 – Pb (B) 1 + PT (C) 1 (D) 1 + Pb

RT Pb RT

4. 'a' and 'b' are van der Waals' constants for gases. Chlorine is more easily liquefied than ethane
because [JEE MAIN 2011]
(A) a for Cl2 < a for C2H6 but b for Cl2 > b for C2H6
(B) a for Cl2 > a for C2H6 but b for Cl2 < b for C2H6

(C) a and b for Cl2 > a and b for C2H6

(D) a and b for Cl2 < a and b for C2H6
5. In van der Waals' equation of state of the gas law, the constant 'b' is a measure of : [JEE-2004]

(A) intermolecular repulsions (B) intermolecular attractions

(C) volume occupied by the molecules (D) intermolecular collisions per unit volume
6. Consider the van der Waals constants, a and b, for the following gases. [JEE MAIN 2019]

Gas At Ne Kr Xe
a/(atm dm6 mol–2) 1.3 0.2 5.1 4.1
b/(10–2 dm3 mol–1 3.2 1.7 1.0 5.0

Which gas is expected to have the highest critical temperature ?

(A) Xe (B) Kr (C) Ne (D) Ar

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7. At a given temperature T, gases Ne, Ar, Xe and Kr are found to deviate from ideal gas behaviour.

Their equation of state is given asP = RT at T. Here, b is the Vander Waals constant. Which gas
V−b
will exhibit steepest increase in the plot of Z (compression factor) v s p? [JEE MAIN 2019]

(A) Kr (B) Ar (C) Xe (D) Ne

8. Consider the following table : [JEE MAIN 2019]
Gas a/(k Pa dm6 mol–1) b/(dm3 mol–1)

A 642.32 0.05196
B 155.21 0.04136
C 431.91 0.05196

D 155.21 0.4382
a and b are van der Waals constants. The correct statement about the gases is :
(A) Gas C will occupy lesser volume than gas A; gas B will be more compressible than gas D

(B) Gas C will occupy more volume than gas A; gas B will be more compressible than gas D
(C) Gas C will occupy lesser volume than gas A; gas B will be lesser compressible than gas D
(D) Gas C will occupy more volume than gas A; gas B will be lesser compressible than gas D

9. The volume of gas A is twice than that of gas B. The compressibility factor of gas A is thrice than
that of gas B at same temperature. The pressures of the gases for equal number of moles are :
[JEE MAIN 2019]
(A) PA = 3PB (B) 3PA = 2PB

(C) 2PA = 3PB (D) PA = 2PB

an2
10. The unit of the van der Waals gas equation parameter 'a′ in (P + ) (V − nb) = nRT is :
V2

[JEE MAIN 2021]

(A) kgms −2 (B) dm3 mol −1

(C) kgmsm−1 (D) atmdm 6 mol −2

11. For a real gas at 25∘ C temperature and high pressure (99 bar) the value of compressibility
factor is 2, so the value of Vander Waal's constant ' 𝑏 ' should be
× 10−2 L mol−1

(Nearest integer) Given R = 0.083 L bar −1

mol−1 ) [JEE MAIN 2022]
12. The number of statement's, which are correct with respect to the compression of carbon dioxide
from point (a) in the Andrews isotherm from the following is _________. [JEE MAIN 2023]

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(A) Carbon dioxide remains as a gas upto point (b)

(B) Liquid carbon dioxide appears at point (c)

(C) Liquid and gaseous carbon dioxide coexist between points (b) and (c)
(D) As the volume decreases from (b) to (c), the amount of liquid decreases

13. Based on the given figure, the number of correct statement/s is/are _______ [JEE MAIN 2023]

(A) Surface tension is the outcome of equal attractive and repulsion forces acting on the liquid
molecule in bulk.
(B) Surface tension is due to uneven forces acting on the molecules present on the surface.
(C) The molecule in the bulk can never come to the liquid surface.
(D) The molecules on the surface are responsible for vapour pressure if the system is a closed
system.
14. For 1 mol of gas, the plot of pV vs p is shown below. p is the pressure and V is the volume of the
gas. [JEE MAIN 2023]

What is the value of compressibility factor at point A?

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(A) 1 − a (B) 1 + b (C) 1 − b (D) 1 + a

RTV V V RTV

15. Given below are two statements: One is labelled as Assertion A and the other is labelled as Reason
R.

Assertion A: Amongst He, Ne, A r and Kr; 1 g of activated charcoal adsorbs more of K r.
Reason R : The critical volume V c (cm3 mol–1) and critical pressure Pc (atm) is highest for Krypton
but the compressibility factor at critical point Z c is lowest for Krypton. [JEE MAIN 2023]

In the light of the above statements, choose the correct answer from the options given below.
(A) A is true but R is false
(B) A is false but R is true

(C) Both A and R are true but R is NOT the correct explanation of A
(D) Both A and R are true and R is the correct explanation A

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EXERCISE # IV
(JEE-ADVANCED)
 B 
1. One way of writing the equation for state for real gases is, PV = RT 1 + + ..... where B is a
 V 
constant. Derive an approximate expression for 'B' in terms of van der Waals' constants 'a' & 'b'.

[JEE 1997]

2. Using Vander Waals equation, calculate the constant "a" when 2 moles of a gas confined in a 4
litre flask exerts a pressure of 11.0 atm at a temperature of 300 K. The value of "b" is 0.05 litre
mol–1.
[JEE 1998]

3. A gas will approach ideal behaviour at : [JEE 1999]

(A) low temperature and low pressure
(B) low temperature and high pressure

(C) low pressure and high temperature

(D) high temperature and high pressure .

4. The compressibility of a gas is less than unity at STP. Therefore, [JEE 2000]
(A) Vm > 22.4 L (B) Vm < 22.4 L
(C) Vm = 22.4 L (D) Vm = 44.8 L

5. The compression factor (compressibility factor) for one mole of a van der Waals' gas at 0° C and
100 atmosphere pressure is found to be 0.5. Assuming that the volume of a gas molecule is
negligible, calculate the van der Waals' constant 'a'.
[JEE 2001]
6. The density of the vapour of a substance at 1 atm pressure and 500 K is 0.36 Kg m –3.
The vapour effuses through a small hole at a rate of 1.33 times faster than oxygen under the same
condition. Determine [JEE 2002]
(i) mol. wt.;

(ii) molar volume;

(iii) compression factor (z) of the vapour and

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(iv) which forces among the gas molecules are dominating, the attractive or the repulsive
7. Positive deviation from ideal behaviour takes place because of [JEE 2003]
𝑃𝑉
(A) molecular attraction between atoms and >1
𝑛𝑅𝑇

𝑃𝑉
(B) molecular attraction between atoms and <1
𝑛𝑅𝑇

(C) finite size of atoms and PV > 1

nRT

(D) finite size of atoms and PV < 1

nRT

8. For a real gas obeying van der Waals' equation a graph is plotted between PV m (y-axis) and P(x-
axis) where V m is molar volume. Find y-intercept of the graph. [JEE 2004]

9. The given graph represents the variation of Z (Compressibility factor = PV ) versus P, for three
nRT
real gases A, B and C. Identify the only INCORRECT statement. [JEE 2006]
Z
A

B
C
0
P(atm)

(A) for the gas A, a = 0 and its dependence on P is linear at all pressure
(B) for the gas B, b = 0 and its dependence on P is linear at all pressure
(C) for the gas C, which is typical real gas for which neither a nor b = 0. By knowing the minima
and the point of intersection, with Z = 1, a and b can be calculated.
(D) At high pressure, the slope is positive for all real gases A, B and C

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10. Match gases under specific conditions listed in Column I with their properties / laws in Column II.
Indicate your answer by darkening the appropriate bubbles of the 4 × 4 matrix given in the ORS.
[JEE 2007]
Column I Column II

(A) Hydrogen gas (P = 200 atm, T = 273 K) (P) Compressibility factor  1

(B) Hydrogen gas (P ~ 0, T = 273 K) (Q)Attractive forces are dominant

(C) CO2 (P = 1 atm, T = 273 K) (R) PV = nRT

(D) Real gas with very large molar volume (S) P (V– nb) = nRT

11. A gas described by van der Waals' equation [JEE 2008]

(A) behaves similar to an ideal gas in the limit of large molar volumes
(B) behaves similar to an ideal gas in the limit of large pressures

(C) is characterised by van der Waals' coefficients that are dependent on the identity of the gas but
are independent of the temperature
(D) has the pressure that is lower than the pressure exerted by the same gas behaving ideally

12. The term that corrects for the attractive forces present in a real gas in the Vander Waals' equation is
[JEE 2009]
𝑎𝑛2 𝑎 𝑛2
(A) nb (B) (C) – (D) – nb
𝑉2 𝑉2

13. For one mole of a van der Waals' gas when b = 0 and T = 300 K, the PV vs. 1/V plot is shown below.
The value of the van der Waals' constant a (atm. litre 2 mol–2) is [JEE 2012]
PV(litre-atm mol–1)

24.6
23.1 [Graph not to scale]
21.6
20.1


0 2.0 3.0

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1
(mol litre–1)
V

(A) 1.0 (B) 4.5 (C) 1.5 (D) 3.0

14. One mole of a monoatomic real gas satisfies the equation P(V– b) = RT where b is a constant. The
relationship of interatomic potential V(r) and interatomic distance r for the gas is given by -
[JEE ADVANCED 2015]

V(r) V(r)
V(r) V(r)
0 0
(A) r (B) r (C) (D)
0 0
r r

15. A gas has a compressibility factor of 0.5 and a molar volume of 0.4dm3 mol−1 at a temperature of
800 K and pressure 𝐱atm. If it shows ideal gas behaviour at the same temperature and pressure, the
molar volume will be y dm3 mol −1 . The value of 𝐱/𝐲 is
[Use: Gas constant, R = 8 × 10−2 L atm K −1 mol −1 ] [JEE ADVANCED 2023]

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ANSWER KEY
EXERCISE-I

DPP-1
1. (C) 2. (B) 3. (D) 4. (A) 5. (D) 6. (B) 7. (1000)
8. (2463) 9. 21 atm 10. (914.K)

DPP-2
1. (C) 2. (C) 3. (C) 4. (A) 5. (D) 6. (C) 7. (C)
8. (24) 9. (1.25) 10. (15.39kg)

DPP-3
1. (B) 2. (C) 3. (B) 4. (C) 5. (C) 6. (C) 7. (400)

8. (C)
DPP-4
1. (C) 2. (D) 3. (D) 4. (D) 5. (D) 6. (C) 7. (A)

8. (A) 9. (B) 10. (B)

EXERCISE-II
1. (B) 2. (B) 3. (C) 4. (D) 5. (ACD) 6. (CD) 7. (ACD)

8. (ABD) 9. (ABC) 10. (ABC) 11. (AC) 12. (B) 13. (C) 14. (C)
15. A-(P, R, S) ; B-(Q, T) ; C-(P, R, S) ; D-(P, R, S)
EXERCISE-III JEE MAIN

1. (A) 2. (D) 3. (D) 4. (B) 5. (C) 6. (B) 7. (C)

8. (B) 9. (C) 10. (D) 11. (25) 12. (B) 13. (B) 14. (A)
15. (A)

EXERCISE-IV JEE ADVANCED

 a 
1. B = b−  2. (6.52 atm L2 mol–2 ) 3. (C) 4. (B)
 RT 

5. (1.256 atm L2 mol–2 ) 6. ((i) 18 g/mol , (ii) 50 L mol–1 , (iii) 1.218 , (iv) repulsive)

7. (C) 8. (RT) 9. (D) 10. ((A)→P,S; (B)→R; (C)→P,Q; (D)→R)

11. (ACD) 12. (B) 13. (C) 14. (C) 15. (100)

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SOLUTION
EXERCISE-I
DPP-1

8. From ideal gas equation, molar volume is

nRT 1  .0821  300 24.63
V= = =
P 11 11
Actual molar volume = 10 % greater than molar volume calculated from ideal gas equation
24.63 24.63 10
= + 
11 11 100

24.63  1
= 1 +  = 2.463
11  10 

= 2.463  103 m = 2463m

DPP-2

3. PV = Pb + RT
PV Pb
= 1+
RT RT

 a 
4.  P + 2  (V) = RT
 V 

a
PV + = RT
V
PV a
= 1−
RT VRT

 an 2 
5.  P +  (V – nb) = n R T
 V2 

an 2
PV + =nRT
V

1000 (0.02) 2
0.1 × V + = 0.02 × 20
V
V = 2C

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PV
Z= = 0.5
nRT

PV 0.9  0.0821 273

6. Z= ;V = = 2.24 litre/mol
nRT 9

 Volume of 1 milli-mole of gas = 2.24 mL

18
9. Volume of one mole of given vapour = L = 50 L
0.36
DPP-3

Mol.wt.
5. Vm =
density

27
= = 90 lit
0.3
PVm 1 90
Z= = = 1.5
RT 0.08  750
6. High T, low P

DPP-4
a
4. TC 
b
4
5. VC = 3 × N × r3 × 4 = 44/0.44
3

Molar mass 30
9. VC = = = 75 cm3
Density 0.4

= 0.075 lit
VC = 3b
b = 0.025
8 a
TC =
27 Rb

2  105 8 a
=  × 0.025
821 27 0.0821

a = 1.6875 atm L 2 mol–2

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10. PC = 75 atm TC
VC = ? mole =1
PC .VC
ZC =
RTC

3 75  VC
=
8 0.0821 300
3 24.63
VC =  = 0.12
8 75

EXERCISE: II
1. PM = dRT

(
PM = 2P + .02P 2 RT )
M = ( 2 + 0.02) RT

90
If H2O( ) = = 90ml then M = 2RT
1
 M = 2  25 = 50gm / moles

rO2 3 Mgas
2. = =  Mgas = 48
rgas 2 32

1000
Vm, real = × 48 = 60
800
RT 0.08  500
Vm, ideal = = = 40
P 1
60 3
Z= =
40 2

3. At very high pressure

Pb
Z = 1+
RT
dZ b 1
= = atm–1
dP RT 10
22.4 273
b=  = 2.24 litre / mole
273 10

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b = 4 × V × NA

22.4  103
V=  9.3 × 10–22 cc Ans.
4  6  10 23
4. For 1 mole real gas

 a 
P +  (V – b) = RT
 TV 2 
−1
a RT a  b
PV + = Þ PV + = RT 1 − 
TV  b TV  V
1 + 
 V 
2
a b b
PV + = RT [1 + +   + ....]
TV V V

 a 
b+ 
 RT 2 
PV = RT [1 + + ....] ; at Boyle’s temperature, T → TB ; A = 0
V

a a
b– =0 ; TB =
RTB2 RB

6. (A) When attractive forces dominate, molar volume V1 = 127.4ml at 1 atm & 273 k

(D) Vander Waal's constant ‘a’ is a measure of attractive force, more the value of a ; more will be the
attractive forces  gas having more value of ‘a’ is more compressible than one having lower value of
a, provided value of ‘b’ is same.
rNe = 1.414rgas
12.

rNe = 2rgas

rNe M gas
=
rgas M Ne

M gas
2= ,
 20 squaring both side

 M gas = 20  2  2 = 40

Using PM = zdRT for non-ideal gas

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1  40  1.2  d  .0821  600

40 −1
d= = .68gm
1.2  .0821  600

molar mass 40
= = = 58.8
13. Molar volume density 0.68

B C C
Z +1+ + 2 + 3 ......., Vm
Vm Vm Vm
14. is the molar volume
Higher volume terms are neglected
B
 Z = 1+
Vm

B
1.2 = 1 +
Vm

 B = 58.8  0.2 = 11.76Lmol−1

15. (A) At low pressure & room temperature, Vander Waal’s const. ‘a’ dominates  Z  1 , attractive
forces dominates, there is negative slope in Z vs P curve.

(B) At very high pressure & room temperature, vander wool constant ‘b’ dominates, i.e. repulsive
force dominates
Z 1

(D) At critical temp. & low pressure

EXERCISE # III (JEE-MAIN)

a
6. TC 
b
RT
7. P=
V−b
PV – Pb = RT
Pb
Z=
RT

 b 
Z=   P
 RT 

b is maximum for Xe

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8.  Gas A and C have same value of 'b' but different value of 'a' so gas having higher value of 'a' have
more force of attraction so molecules will be more closer hence occupy less volume.

 Gas B and D have same value of 'a' but different value of 'b' so gas having lesser value of 'b' will be
more compressible.
9. ZA = 3ZB
PA VA 3PB VB
=
nRT nRT
⇒ PA × 2VB = 3PB VB
⇒ 2PA = 3PB
a2
10. P+ (v − nb) = nRT
v2

Pressure correction value is equals

an2
v2
lit 2
a = atm ×
mol2
1 lit = 1dm3
dm6
a = atm ×
mol2
11. For real gas under high pressure
Pb RT
Z=1+ ⇒b=
RT P
0.083 × 298
=
99
= 25 × 10−2 Lmol −1

P Critical
Isotherm
d
12.
c b a

At
(a) → CO2 exist as gas
(b) → liquefaction of CO2 starts

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(c) → liquefaction ends

(d) → CO2 exist as liquid.
Between (b) & (c) → liquid and gaseous CO2 co-exist.
As volume changes from (b) to (c) gas decreases and liquid increases.

14. For 1 mole of real gas

PV = ZRT
from graph PV for real gas is less than PV for ideal gas at point A
Z<1
a
Z =1−
Vm RT
3
15. Adsorption ∝ vanderwaal attraction forces Zc = 8 for all real gases

EXERCISE # IV (JEE-ADVANCED)
1. According to the van der Waals equation,
P + (a)
(V – b) = RT
v2
RT a
or P = − 2
V−b V
RTV a
or Pv = −
V−b V
−1
 b a  b a
or Pv = RT 1 −  − = RT 1 +  −
 V V  V V

Neglecting higher powers of b / V

 b a   1 a 
or PV = RT 1 + −  = RT 1 + V  b − RT  
 V VRT    

Comparing with the given form of the equation. We get

a
B=b–
RT

2. Vander Waal’s equation for n moles of gas is,

 n2 
 P + a [v – nb] = nRT.
 v 2 

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Given, v = 4L, P = 11 atm, T = 300 K, b = 0.05 litre/mol

n=2

 22 
Thus, 11 + a 2  [4 – 2(0.05)] = 2 × 0.082 × 300
 4 

a = 6.46 atm litre 2 mol–2

5. We know that, compressibility factor, Z = PV / RT

0.5 = 100 *V/0.082 *273

 V = 0.1117 L

Note :- Further when volume of a gas molecule is negligible, van der Waal’s equation becomes
(P + a / V 2) (V – 0) = RT
Or PV = RT – a/V or a = RTV – PV2

Substituting the values

A = (0.082 * 0.1119 * 173) – (100 * 0.1119 * 0.1119)
= 1.253 atm L 2 mol–2

 a 
8.  P − 2  (Vm – b) = RT
 Vm 

a ab
PVm – Pb – + 2 = RT
Vm Vm

at y intercept, x = 0
i.e. P = 0

 Vm ⎯→ 
So the equation becomes
PVm – Pb = RT

PVm = Pb + RT
y=mx+c
c is the y intercept

 c = RT

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14. Since a = 0
Hence, only repulsive forces are present which are contributive only at very close distance.
Thus, the potential energy will increase abruptly.
V
15. Compressibility factor (Z) = V real = 0.5
ideal

Vreal = 0.4dm3 mol −1 = 0.4 L/mol

0.4
∴ Videal = 0.5 = 0.8 L/mol

∴ y = 0.8 L/mol

Using ideal gas equation: PV = nRT

1 × 8 × 10−2 × 800
P=
0.8
x 80
X = 80 atm ∴ = = 100
y 0.8

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