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NURTURE

IIT CHEMISTRY
PHYSICAL CHEMISTRY
REAL GAS

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 EXERCISE # (S-I)

VAN DER WAALS' EQUATION OF STATE

1. Using the van der Waals equation, calculate the pressure of 10.0 mol NH 3 gas in a 10.0 L
vessel at 27ºC.
 2 a 
 P  n V2  (V – nb) = nRT a = 4.2 L . atm/mol b = 0.037 L/mol
2 2

 

2. Calculate the pressure (in kPa) exerted by 22 g of carbon dioxide in 0.5 dm3 at 298.15 K using:
(a) the ideal gas law and
(b) van der Waals' equation respectively.
Given : [a = 363.76 kPa dm6 mol–2 and b = 42.67 cm3 mol–1]

3. Calculate from the van der Waals' equation, the temperature at which 192 gm of SO2 would
occupy a volume of 10 dm3 at 15 atm pressure.[a = 6.7 atm lit 2 mol2, b = 0.0564 lit mol–1]

4. The molar volume of He at 10.1325 MPa and 273 K is 0.011075 of its molar volume at
101.325 KPa at 273 K.Calculate the radius of helium atom. The gas is assumed to show real
gas nature. Neglect the value of 'a' for He.

5. N2 molecule is spherical of radius 100 pm.

(a) What is the volume (in cm3) of one mole of molecules of a gas?
(b) What is the value of van der Waals' constant b (in cm3/mole)

6. To an evacuated 504.2 mL steel container is added 25 g CaCO3 and the temperature is raised to
1500 K causing a complete decomposition of the salt. If the density of CaO formed is 3.3 g/cc,
find the accurate pressure developed in the container using the Van der waals equation of state.
L2  atm L
The van der waals constants for CO2(g) are a = 4 2 , b = 0.04 .
mol mol
(Ca - 40, C - 12, O - 16). Report your answer as nearest whole number.

7. The gas having higher value of van der Waals' constant "a" will be __________ compressible
than the one having lower value of "a", provided van der Waals' constant "b" is same for both
the gases.

8. The density of mercury is 13.6 g/cm3. Estimate the b value (in cm3/ mole) (molar mass of
Hg = 200g/mole)

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 = 0.082 L atm mole –1 K–1)

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10. One litre gas at 400 K and 300 atm pressure is compressed to a pressure of 600 atm and 200 K.
The compressibility factor is changed from 1.2 to 1.6 respectively. Calculate the final volume
of the gas.

COMPRESSIBILITY FACTOR

11. 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 dm3 capacity under the given
conditions.

12. The density of water vapour at 327.6 atm and 776.4 K is 133.2 gm/dm3.
Determine the molar volume, Vm and the compression factor of water vapour .

13. 1 mole of CCl4 vapours at 27°C occupies a volume of 40 lit. If van der Waals' constants are
24.6 L2 atm mol–2 and 0.125 Lmol–1, then, calculate compressibility factor in
(a) Neglecting ‘b’ (b) Neglecting ‘a’

14. For a fixed amount of real gas when a graph of z v/s P was plotted then at very high pressure
slope was observed to be 0.01 atm–1. At the same temperature if a graph is plotted b/w pv v/s P
then for 2 moles of the gas ‘Y’ intercept is found to be 40 atm-liter. Calculate excluded volume
in litres for 20 moles of the real gas.

15. Sign of initial slope of compressibility factor (Z) versus P curve is ________ if a gas is below
its Boyle's temperature and ________ if it is above its Boyle's temperature.

BOYLE'S TEMPERATURE AND CRITICAL PHENOMENON

16. The van der Waals' constant for O2 are a = 1.36 atm L2 mol–2 and b = 0.0318 L mol–1.
Calculate the temperature at which O2 gas behaves ideally for longer range of pressure.

17. The van der Waals' constants for gases A, B and C are as follows
Gas a/dm6 kPa mol–2 b/dm3 mol–1
A 405.3 0.027
B 1215.9 0.030
C 607.95 0.032
Which gas has (i) the highest critical temperature, (ii) the largest molecular volume ?

3 2 105
18. For a real gas (mol. mass = 30) if density at critical point is 0.40 g/cm and its Tc = K,
821
then calculate van der Waals' constant a (in atm L2 mol–2).

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 EXERCISE # (O-I)
PART - I ONLY ONE OPTION CORRECT TYPE

VAN DER WAALS' EQUATION OF STATE

1. The correct expression for the van der Waals' equation of state is :
 a   an 2 
(A)  P  2 2 
(V – nb) = nRT (B)  P  2  (V – nb) = nRT
 nV   V 
 an 2   P  an 2 
(C)  P  2  (V – b) = nRT (D)  2  (V – nb) = nRT
 V   V 

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 becuase of :
(A) Increase in number of collisions (B) Finite size of molecule
(C) Increases in KE of molecules (D) Intermolecular forces of attraction

4. 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

5. Calculate the radius of He atoms if its Vander Waal's constant ‘b’ is 24 ml mol–1.
(Note 1 ml = 1 cubic centimeter)
(A) 1.355 Å (B) 1.314 Å (C) 1.255 Å (D) 0.355 Å

6. On heating vapours of S8(g) decomposes to S2(g). Due to this, the van-der Waal’s constant ‘b’
for the resulting gas
(A) increases (B) decreases (C) remains same (D) changes unpredictably

7. 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

8. At relatively high pressure, van der Waals' equation reduces to :

a a
(A) PVm = RT (B) PVm = RT + (C) PVm = RT + PB (D) PVm = RT – a
Vm Vm

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

Ne
1.0 NH3
?

P
The missing gas in the above graph can be :
(A) He (B) Ar (C) H2O (D) CH4

COMPRESSIBILITY FACTOR
10. 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.

11. At 273 K temp. and 9 atm pressure, the compressibility factor for a gas is 0.9. The volume of
1 mili-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

12. Compressibility factor at room temperture for H2 behaving as real gas is :

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

13 What is the compressibility factor (Z) for 0.02 mole of a van der Waals’ 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 L2 mol–2
(A) 2 (B) 1 (C) 0.02 (D) 0.5

14. At low pressures (For 1 mole), the Vander Waal’s equation is written as
 a 
p  V2  V = RT
The compressibility factor is then equal to :
 a   RTV   a   RTV 
(A) 1  (B) 1  (C) 1  (D) 1 
 RTV   a   RTV   a 

15. 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, r3 in cm3 is approximately. (N is Avogadro number)
25 100 6 25
(A) (B) (C) (D)
N N N 4N

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 BOYLE'S TEMPERATURE AND CRITICAL PHENOMENON
16. Select incorrect statement :
(A) we can condense vapour simply by applying pressure
(B) to liquefy a gas one must lower the temperature below T C and also apply pressure
(C) at TC, there is no distinction between liquid and vapour state hence density of the liquid is
nearly equal to density of the vapour
(D) However great the pressure applied, a gas cannot be liquified below it’s critical
temperature.

17. 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 moment

18. The van der Waals parameters for gases W, X, Y and Z are
Gas a(atm L2 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

19. 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
then (i) : VC (X) < VC (Y) (ii) : PC (X) < PC (Y) (iii) : TC (X) < TC(Y)
Select correct alternate:
(A) (i) alone (B) (i) and (ii) (C) (i), (ii) and (iii) (D) (ii) and (iii)

20. For a real gas the P-V curve was experimentally plotted and it had the following appearance.
With respect to liquifaction. Choose the correct 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.

H.O. 92, Rajeev Gandhi Nagar, Kota (Raj.) Mob. 97831-97831, 70732-22177, Ph. 0744-2423333 18
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21. 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

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

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

23. Consider the following statements:

The coefficient B in the virial equation of state
(i) is independent of temperature
 B C 
(ii) is equal to zero at boyle temperature 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

PART - II ONE OR MORE THANONE OPTION CORRECT TYPE

24. The curve of pressure volume (PV) against pressure (P) of the gas at a particular temperature is
as shown, according to the graph which of the following is correct (in the low pressure region):
CO CH4
O2 H2
He
Ideal gas
pV

0 p

H.O. 92, Rajeev Gandhi Nagar, Kota (Raj.) Mob. 97831-97831, 70732-22177, Ph. 0744-2423333 19
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 (A) H2 and He shows +ve deviation from ideal gas equation.
(B) CO, CH4 and O2 show negative deviation from ideal gas equation.
(C) H2 and He show negative deviation while CO, CH4 and O2 show positive deviation.
(D) H2 and He are less compressible than that of an ideal gas while CO, CH 4 and O2 more
compressible than that of ideal gas.

25. Which of following statement (s) is true

(A) – Slope of isotherm at critical point is maximum.
(B) – Larger is the value of TC easier is the liquification of gas.
(C) – Vander waals equation of state is applicable below critical temperature at all pressure.
(D) – Above critical condition, a real gas behaves like an ideal gas.

26. Which of the following are correct statements ?

(A) vander Waals constant ‘a’ is a measure of attractive force
(B) van der Waals constant ‘b’ is also called co-volume or excluded volume
(C) ‘b’ is expressed in L mol–1
(D) ‘a’ is expressed in atm L2 mol–2

27. Which of the following is correct for critical temperature ?

(A) It is the highest temperature at which liquid and vapour can coexist
(B) Below this temperature, the gas and the liquid phases have different at a particular pressure.
(C) At this temperature, the gas and the liquid phases have different critical densities
(D) At this temperature real gas behaves like ideal gas.

28. Select the INCORRECT statement(s):

(A) At Boyle's temperature a real gas behaves like an ideal gas irrespective of pressure.
(B) For hydrogen gas ‘b’ dominates over ‘a’ at all temperature.
(C) On increasing the temperature four times,collision frequency (Z1) becomes double at
constant volume.
(D) At high pressure van der Waals' constant 'b' dominates over 'a'.

29. Identify the true statement related to the above graph :

(A) between 50 K and 150 K temperature and pressure ranging from 10 atm to 20 atm matter
may have liquid state.

H.O. 92, Rajeev Gandhi Nagar, Kota (Raj.) Mob. 97831-97831, 70732-22177, Ph. 0744-2423333 20
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 (B) zero is the maximum value of the slope of P-V Curve
(C) If vander waal equation of state is applicable at critical point then cubic equation of V m will
have one root.
(D) At 100 K and pressure below 20 atm it has liquid state only

PART- III MATCH THE COLUMN

30. Column – I Column – II

pb
(A) At low pressure (p) Z=1+
RT
a
(B) At higher pressure (q) Z=1–
VmRT
(C) At low density of gas (r) gas is more compressible
(D) For H2 and He at 0°C (s) gas is less compressible

H.O. 92, Rajeev Gandhi Nagar, Kota (Raj.) Mob. 97831-97831, 70732-22177, Ph. 0744-2423333 21
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 EXERCISE # (JEE-MAINS)

Q.1 When does a gas deviate the most from it's ideal behaviour ? [JEE-MAINS(ONLINE)-2015]
(1) At high pressure and low temperature
(2) At high pressure and high temperature
(3) At low pressure and low temperature
(4) At low pressure and high temperature

Q.2 If Z is the compressibility factor, van der Waals' equation at low pressure can be written as :
[JEE-MAINS-2014]
Pb Pb Pb a
(1) Z = 1 – (2) Z = 1 + (3) Z = 1 + (4) Z = 1 –
RT RT RT VmRT

Q.3 The compressibility factor for a real gas at high pressure is :- [AIEEE-2012]
Pb PT Pb
(1) 1 – (2) 1 + (3) 1 (4) 1 +
RT Pb RT

Q.4 'a' and 'b' are van der Waals' constants for gases. Chlorine is more easily liquefied than ethane
because [AIEEE-2011]
(1) a for Cl2 < a for C2H6 but b for Cl2 > b for C2H6
(2) a for Cl2 > a for C2H6 but b for Cl2 < b for C2H6
(3) a and b for Cl2 > a and b for C2H6
(4) a and b for Cl2 < a and b for C2H6

Q.5 In van der Waals' equation of state of the gas law, the constant 'b' is a measure of : [AIEEE-04]
(1) intermolecular repulsions
(2) intermolecular attractions
(3) volume occupied by the molecules
(4) intermolecular collisions per unit volume

Q.6 Consider the van der Waals constants, a and b, for the following gases. [JEE-MAINS-2019]
Gas At Ne Kr Xe
6 –2
a/(atm dm mol ) 1.3 0.2 5.1 4.1
–2 3 –1
b/(10 dm mol 3.2 1.7 1.0 5.0
Which gas is expected to have the highest critical temperature ?
(1) Xe (2) Kr (3) Ne (4) Ar

H.O. 92, Rajeev Gandhi Nagar, Kota (Raj.) Mob. 97831-97831, 70732-22177, Ph. 0744-2423333 22
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Q.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 as
RT
P= at T.
Vb
Here, b is the Vander Waals constant. Which gas will exhibit steepest increase in the plot of Z
(compression factor) vs p? [JEE-MAINS-2019]
(1) Kr (2) Ar (3) Xe (4) Ne

Q.8 Consider the following table :

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 [JEE-MAINS-2019]
a and b are van der Waals constants. The correct statement about the gases is :
(1) Gas C will occupy lesser volume than gas A; gas B will be more compressible than gas D
(2) Gas C will occupy more volume than gas A; gas B will be more compressible than gas D
(3) Gas C will occupy lesser volume than gas A; gas B will be lesser compressible than gas D
(4) Gas C will occupy more volume than gas A; gas B will be lesser compressible than gas D

Q.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-Mains-2019]
(1) PA = 3PB (2) 3PA = 2PB (3) 2PA = 3PB (4) PA = 2PB

H.O. 92, Rajeev Gandhi Nagar, Kota (Raj.) Mob. 97831-97831, 70732-22177, Ph. 0744-2423333 23
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 EXERCISE # (JEE-ADVANCE)

Q.1 One way of writing the equation for state for real gases is, [JEE 1997]
 B 
PV = RT 1   ..... where B is a constant.
 V 
Derive an approximate expression for 'B' in terms of van der Waals' constants 'a' & 'b'.

Q.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]

Q.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 .

Q.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

Q.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]

Q.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
(iv) which forces among the gas molecules are dominating, the attractive or the repulsive

Q.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
PV
(C) finite size of atoms and >1
nRT
PV
(D) finite size of atoms and <1
nRT
H.O. 92, Rajeev Gandhi Nagar, Kota (Raj.) Mob. 97831-97831, 70732-22177, Ph. 0744-2423333 24
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Q.8 For a real gas obeying van der Waals' equation a graph is plotted between PV m (y-axis) and
P(x-axis) where Vm is molar volume. Find y-intercept of the graph. [JEE 2004]

Q.9 The given graph represents the variation of Z

PV
(compressibility factor = ) versus P, for three real
nRT
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.

Q.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

Q.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

Q.12 The term that corrects for the attractive forces present in a real gas in the Vander Waals'
equation is [JEE 2009]
an 2 an 2
(A) nb (B) 2 (C) – 2 (D) – nb
V V

H.O. 92, Rajeev Gandhi Nagar, Kota (Raj.) Mob. 97831-97831, 70732-22177, Ph. 0744-2423333 25
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Q.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

)
1

0 2.0 3.0
1
(mol litre–1)
V
(A) 1.0 (B) 4.5 (C) 1.5 (D) 3.0

Q.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 2015]

V(r) V(r)

0 0
(A) r (B) r

V(r) V(r)

(C) 0 (D) 0
r r

H.O. 92, Rajeev Gandhi Nagar, Kota (Raj.) Mob. 97831-97831, 70732-22177, Ph. 0744-2423333 26
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 ANSWER KEY
EXERCISE # (S-I)
1. 21.37 atm. 2. (a) 2479 kPa, (b) 2225.55 kPa 3. 622.78K
4. 0.561Å 5. (a) 2.523 cm3, (b) 10.09 cm3 mol–1 6. 62 atm.
50
7. more 8. 58.997 cm3/mole 9.
41
1
10. litre 11. 15.39 kg 12. Molar vol = 0.1351 L/mol; Z = 0.694
3
3. (a) 0.975; (b) 1.003 14. 4 15. –ive, +ive
16. 521 K 17. (i) B, (ii) C 18. 1.6875

EXERCISE # (O-I)
1. D 2. B 3. D 4. C 5. A
6. B 7. C 8. C 9. C 10. B
11. C 12. C 13 D 14. A 15. D
16. D 17. D 18. D 19. D 20. D
21. A 22. A 23. C 24. ABD 25. AB
26. ABCD 27. AB 28. AB 29. ABC
30. (A) - q,r (B) – p,s ; (C) – q,r ; (D) – p,s

EXERCISE # (JEE-MAINS)
1. 1 2. 4 3. 4 4. 2 5. 3
6. 2 7. 3 8. 2 9. 3

EXERCISE # (JEE-ADVANCE)
 a 
B = b 6.52 atm L2 mol–2
RT 
1. 2. 3. C 4. B

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. A,C,D 12. B
13. C 14. C

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