HINT & SOLUTIONS : REAL GAS

EXERCISE # S-I

 n 2  4.2 
1.  P   (V – nb) = n RT
 (10)2 
 (10)2  4.2 
 P   (10 – 10 × 0.037) = 10 × 0.082 × 300
 (10)2 

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. CaCO3 (s)   CaO (s) + CO2(g)
25
Moles of CaCO3 used =
100
25
Moles of CaO formed = = moles of CO2 formed
100
25
Mass of CaO formed = × 56 g = 14 g
100
14
Volume occupied by CaO = cc 4.2 mL
3.3
 Volume available for CO2 (g) = 504.2 – 4.2 mL = 0.5 L
Now applying the van der waals equation of state
 an 2 
 p   (v – nb) = nRT
 v2 
 4  (0.25)2 
  [0.5 – 0.25 × 0.04] = 0.25 × 0.082 × 1500
(0.5)2 
p

4  (0.25)2
 p = 62.83 – = 61.83 atm.
(0.5)2

8. 58.997 cm3/mole

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 18
9. Volume of one mole of given vapour = L = 50 L
0.36
RT 0.082  500
volume of one mole of an ideal gas = = = 41 L
P 1
V ,real 50
so value of. Z = m =
Vm ,ideal 41

PV
1 1 P2V2
10. Z1 = and Z2 =
RT1 RT2
Z1 P T V 1
= 1 2 1 V2 = litre
Z2 P2 T1 V2 3

11. 15.39 kg

12. Molar vol = 0.1351 L/mol; Z = 0.694

13. (a) 0.975; (b) 1.003

14.  very high pressure  neglect (a)

Pb
 Z=1+ Pb ...(1)
RT
Comparing above equation with y = mx + c
b
m=
RT
b
 = 0.01 (given m = 0.01)
RT
b = 0.01 RT .....(2)
(PV)real
Z=
(PV)ideal
(PV)real
Z= (given for n = 2, PV = 40)
nRT
40
Z=
2RT
20
Z= .....(3)
RT
Pb
as, Z = 1 
RT
from equation (3)

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 20 Pb
= 1 .....(4)
RT RT
10 = RT + Pb
Pb = 20 – RT .....(5)
 Pb 
(PV)real = 40 = ZnRT = 1 
2RT 
2RT

 40 =
40 = 2RT + 20 – RT
20 = RT .....(6)
From (2) & (4)
b = 0.01 × 20
b = 0.2
excluded volume for 20 moles
nb = 20 × 0.2
nb = 4

15. Negative, positive

a 1.36
16. Tb = 
Rb 0.0821 0.0318
= 521 K

8 a
17. (i) TC =
27 Rb
For Gas B TC is maximum
(ii) For Gas C, b is maximum

Molar mass 30
18. 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 L2 mol–2
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 EXERCISE # O-I
4
5. 4  r3  NA = 24
3

7. High T, low P

PV 0.9  0.0821 273

11. Z= ; V= = 2.24 litre/mol
nRT 9
 Volume of 1 mili-mole of gas = 2.24 mL

12. PV = Pb + RT
PV Pb
= 1
RT RT

 an 2 
13.  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
PV
Z= = 0.5
nRT

 a 
14.  P  V2  (V) = RT
 
a
PV + = RT
V
PV a
= 1
RT VRT

4 3
15. VC = 3 × N × r × 0.44
3

a
19. TC 
b

H.O. 92, Rajeev Gandhi Nagar, Kota (Raj.) Mob. 97831-97831, 70732-22177, Ph. 0744-2423333 31
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20.

(a) at T = 500 K, P = 40 atm corresponds to 'a' substance - gas

(b) at T = 300 K, P = 50 atm corresponds to 'b' substance - liquid
(c) at T < 300 K, P > 20 atm corresponds to 'c' substance - liquid
(d) at T < 500 K, P > 50 atm corresponds to 'd' substance - liquid
So, Answer (D)

24. If Z > 1 positive deviation

Z < 1 negative deviation

25. (A) – Slope of isotherm below critical point < 0.

Slope of isotherm above critical point < 0.
Slope of isotherm at critical point = 0.
So slope of isotherm at critical point is maximum.
8a
(B) – TC =
27Rb
TC  a
Larger value of TC It means less decreases in temperature is required to liquifly the gas.
Gas will liquify at higher temperature. So, easier'll be liquification.
(C) – When gas is below critical temperature. It is 'liquid' so vander waal equation of state is
not valid.
So, Answer (B).

29.

At 100 K and pressure below 20 atm it may have liquid or gaseous state depending on the
pressure.

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 EXERCISE # JEE-MAINS

a
4. Ease of liquification 
b
a
6. TC 
b

RT
7. P=
Vb
PV – Pb = RT
Pb
Z=
RT
 b 
Z=   P
 RT 
b is maximum for Xe

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.

H.O. 92, Rajeev Gandhi Nagar, Kota (Raj.) Mob. 97831-97831, 70732-22177, Ph. 0744-2423333 33
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 EXERCISE # 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 
PV = RT 1    = RT 1   b 
RT  
or
 V VRT   V
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 
  [v – nb] = nRT.
v2 
P a

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 litre2 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 / V2) (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 L2 mol–2

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  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

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.

H.O. 92, Rajeev Gandhi Nagar, Kota (Raj.) Mob. 97831-97831, 70732-22177, Ph. 0744-2423333 35
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