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Solutions to Workbook-2 [Chemistry] | Thermodynamics

Daily Tutorial Sheet Level - 0

1. H  U  n g RT, n g  1  3   2

 22.3 kJ
2. U   78
0.532
H  U  n g RT
15
C6H6 ( )  O2 (g)  6 CO2 (g)  3H2O ( )
2
15
n g  6    1.5
2
3. (iii) CH4 (g)  2O2 (g)  CO2(g)  2H2O ( )
n g  (n p  n r )  1  3   2

H  U  n g RT

H   X  2RT
H  U , hence option (iii) is correct
4. Enthalpy change for the conversion of 1 mole liquid water at 10°C into 1 mole liquid water at 0°C,
H1  C p H2O(  )  T   75.3 J mol 1 K 1  10K   753 J mol 1
Enthalpy of fusion,
H2  H freezing   Hfusion   6.03 kJ mol 1
Enthalpy change for the conversion of 1 mole of ice at 0°C to 1 mole of ice at 10°C,
H3  C p H2O (s)  T   36.8 J mol 1 K 1  10 K   368 J mol 1

Htotal   (0.753  6.03  0.368) kJ mol 1   7.151kJ mol 1

5. Enthalpy change for the formation of 1 mole of H2O(  ) ,

1
H2 (g) O2 (g)  H2O( );  f H   286 kJ mol 1
2
Energy released in the above reaction, is absorbed by the surroundings.
It means q surr   286 kJ mol 1

q surr  286 kJ mol 1

S    0.9597 kJ K 1 mol 1  959.7 J K 1mol 1
T 298 K
6. The two condition under heat becomes independent of path are
(i) when volume remains constant
(ii) when pressure remains constant
13
7. (A) C4H10 (g)  O2 (g)  4CO2 (g)  5H2O( )
2

58 gm butane  2658 kJ energy

2658
11200 gm butane   11200 kJ energy
58
2658 11200
 Number of days    26 days
58 20000
(B) Number of days  26  0.67  17 days

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8. Given that, quantity of water = 18.0 g, pressure = 1 bar

As we know that, 18.0 g H2O = 1 mole H2O
Enthalpy change for vaporizing 1 mole of H2O = 40.79 kJ mol–1.
 Enthalpy change for vaporizing 2 moles of H2O  2  40.79 kJ  81.358kJ

Standard enthalpy of vaporization at 100°C and 1 bar pressure  vap H    40.79 kJ mol 1

9. Given that C v  heat capacity at constant volume.

Cp  heat capacity at constant pressure
Difference between C p and C v is equal to gas constant (R).
C p  C v  nR (where, n = no. of moles)
 10  4.184 J  41.84 J
10. In the first case, as the expansion is against constant external pressure
W   ext (V2  V1 )   2bar  (50  10)L
  80L bar (1L bar = 100 J)
  80  100 J   8kJ
If the given expansion was carried out reversibly, the internal pressure of the gas should be greater than
the external pressure at every stage. Hence, the work done will be more.
11. When compression is carried out in infinite

steps with change in pressure, it is a reversible

process. The work done can be calculated from p
– V plot as shown in the given figure. Shaded
area under the curve represents the work done
on the gas.

12. No, enthalpy is one of the contributing factors in deciding spontaneity but it is not the only factor.
Another contributory factor, entropy factor has also to be taken into consideration.
13. (a) The net enthalpy change, H for a cyclic process is zero as enthalpy change is a state
function, i.e., H (cycle) = 0
(b) Gibbs energy for a reaction in which all reactants and products are in standard state  r Go is
related to the equilibrium constant of the reaction as follows
 rG   r Go  RT ln Q
At equilibrium, 0   r G  RT ln K (  rG  0) & Q  k eq
or  rG   RT ln K
 rG  0 when K  1
For all other values of K,  rG will be non-zero.

14. Suppose total volume of the gas is Vi and pressure of the gas inside cylinder is p. After compression by
constant external pressure, (pext) in a single step, final volume of the gas becomes Vf.
Then volume change, v   Vf  Vi 

If W is the work done on the system by movement of

the piston, then
W = pext ( V )
W =  pext (Vf – Vi)

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This can be calculated from p – V graph as

shown in the figure. Work done is equal to
the shaded area ABVfVi
The negative sign in this expression is required to obtain conventional sign for W which will be positive.
Because incase of compression work is done on the system, so V will be negative.

15. Representation of potential energy/enthalpy change in the following processes

(a) Throwing a stone from the ground to roof.

1 1
(b) H2 (g)  
Cl 2 (g)  o
 HCl (g) ;  r H   92.32 kJ mol
1
2 2

Energy increases in (a) and it decreases in (b) process. Hence, in process (b), enthalpy change is the
contributing factor to the spontaneity

16. The given diagram represent that the process is carried out in infinite steps, hence it is isothermal
reversible expansion of the ideal gas from pressure 2.0 atm to 1.0 atm to 1.0 atm 298 K.
1
W   2303 nRT log
2
 1 2
W   2.303  1mol  8.314 J K 1 mol 1  298 K log 2   
  1 
 2
W   2.303  1 8.314  298  0.3010J  W   1717.46 J

17. As (Cp  C v )  R  Cp  C v  R
 Cp  3 / 2 R  R  5 / 2 R
Heat given at constant pressure

( H)  nC p T  1  5 / 2 R  373  298 
 ( H)  1  5 / 2  1.987  75  372.56 cal
Work done in the process   PV
 nRT2 nRT1 
 
  P V2  V1   P 
 P

P 
 (As, PV = nRT)

   
  nR T2  T1   1  1.987  373  298  149.05 cal

From first law of thermodynamics E  q  W  372.56  149.05  223.51cal

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18.  Work is carried out at constant P and thus irreversible.

Work done   P  V  1   2.5  2.0    0.5 litre atm

0.5  1.987  4.184

 joule   50.63 J
0.0821
From I law of thermodynamics
 q  E  W
300  E  50.63
 E  249.37 joule
19. Volume of 1 mole liquid = 100 mL at pressure 1 bar
Volume of 1 mole liquid = 99 mL at pressure 100 bar
The process being irreversible as it is steeply changed from 1 bar to 100 bar
 w = P (V2  V1) = 100  (99  100) = 100 bar mL
Also E  q  w
E  w ( q = 0, adiabatic nature due to insulation)
 E  100 bar mL

Also 
H  E  PV  E  P2 V2  P1V1 
= 100 + (100  99  1  100) = 9900 bar mL
V2
20. w   2.303 nRT log
V1

(i) where w is work done by the system under isothermal reversible conditions (work done by the
system is negative)
P1
10  10 3   2.303  1  8.314  T log ......(i)
P2

Also, P1V1  P2 V2 (at constant temperature)

 1  107  V1  P2  10 V1

1  107
 P2   10 6 Pa
10
From Eq. (i)
107
10  103   2.303  1  8.314  T log
10 6
T  522.27 K
Using PV = nRT for one mol of gas
1  107  V1  1  8.314  522.27

 V1  4.34  10 4 m 3

522.27
(ii) If 2 moles of gas have been used, the temperature would have been  261.13 K
2
21. We know,
Path CA – Isothermal compression
Path AB – Isobaric expansion
Path BC – Isochoric change
Let V1 and Vf are initial volume and final volume at respective points.

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For temperature T1 (For C) :

PV = nRT1
2  10 = 1  0.0821  T1
T1 = 243.60 K
For temperature T2 (For C and B):
P1 V1 P2 V2

T1 T2

2  10 20  10

T1 T2

T2
  10  T2 = 243.60  10 = 2436.0 K
T1

Vi 10
Path CA : W   2.303 nRT1 log  2.303  1  2  243.6 log = +1122.02 cal
Vf 1
E  0 for isothermal compression; Also q = W
Path AB : W = P(Vf  Vi)
= 20  (10  1) = 180 litre atm
180  2
   4384.9 cal
0.0821
Path BC : W = P(Vf  Vi) = 0 ( Vf  Vi = 0) since volume is constant
For monoatomic gas heat change at constant volume  q v  E
Thus for path BC :
q v  C v  n  T  E

3 3
 qv 
2

R  1  2436  243.6   2
 2  1  2192.4  6577.2 cal

Since process involves cooling

 q v  E   6577.2 cal

Also in path AB, the internal energy in state A and state C is same. Thus during path AB, an increase in
internal energy equivalent of change in internal energy during path BC should take place. Thus E for
path AB = +6577.2 cal
Now q for path AB  E  WAB  6577.2  4384.9  10962.1 cal
Cycle: E  0;
q   W   [Wpath CA  Wpath AB  Wpath BC ]

   1122.02  (  4384.9)  0 

 q =  W = + 3262.88 cal

22. For adiabatic expansion,


1 

1 
 T1  P 
T P  const.     2 
T  P 
 2   1 
T1 P2
  log
T2

 1   log  P1

273 1
 1.4 log
T2

 1  1.4 log  10
 T2  141.4 K

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nR 14 
0.0821 141.4  273 
Work done in adiabatic expansion in L atm   T2  T1   32 
   1 1.4  1
w rev.   11.82 L atm

In calorie 
14


2  141.4  273 
3 1.4  1
w rev.   287.88 cal

23. Initially n = 3 mole,

T1  200 K, P1  2.0 atm, C v  27.5 JK 1 mol 1

After compression
T2  250 K, P2  ?

 C P  27.5  8.314 JK 1 mol 1  35.814 JK 1 mol 1


Cp 35.814  T1 
   1.30    P11  T1  P21  T2  P21  P11  
Cv 27.5 T 
 2
1.30
0.3 0.3  200 
 P2   2    
 250 
 P2  5.2 atm
 
 nRT 3  0.0821  200 
Let the final pressure be P2 and volume be V2.  V    24.63 litre 
 P 2 

Now for volume V2 : P1 V1  P2 V2

 1.3
V  P  V2  2
  2  1      V2  11.8 litre
 V1  P2  24.63  5.2
For adiabatic process q  0
Since whole of the work done is made on the cost of internal energy of the system.
Thus E  W   4.157 kJ
Also H  m  Cp  T  3  35.814  50  5372.1  5.372 kJ

24. Let, S1 = Entropy change due to fusion of ice.

H f 6000 J
S1   = 21.96 Jmol 1K 1
Tf 273.1
S2 = Entropy change for heating 1 mole of water from 273.1 K to 373.1 K at constant pressure.

T2 Cp T2 T2
Then, S2 
 T1 T
dT = C p ln
T1
= C p  2.303 log
T1
373.1
= 75.2  2.303 log = 75.2  2.303  0.1354 = 23.45 J mol-1 K -1
273.1
S3 = Entropy change due to conversion of water into steam, or entropy change when

water is in equilibrium with vapour.

H v 40600
S3  = J mol-1K 1 = 108.8 J mol -1 K -1
Tv 373.1
 Total entropy change = S  S1  S2  S3

S  21.96  23.45  108.8 = 154.2 J mol-1 K -1

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25. We have to find out Hp = nCp dt

No. of moles of Ar
PV 1  1.25
n=  = 0.05
RT 0.082  300
For adiabatic expansion,

TV
 1 = Constant
Cp = C v + R = 12.48 + 8.314 = 20.8 Joules
Cp R
 1
Cv Cv
R R  R/C v  = Constant
  = 1+   -1 =  TV
Cv Cv
R/C v
R/C v  R/C v  T1 V 
 T1 V1  T2 V2   2 
T2  V1 

T1 R V2 8.314 2.50
 ln  ln  ln
T2 Cv V1 12.48 1.25
Antilog 0.199 = 1.58
300 8.314 300 300 300
 log  log2  log = 0.199  = 1.58  T2 =
T2 12.48 T2 T2 1.58
T2 = 189.87 K
 T = T2 – T1 = 189.87 – 300 = –110.13
H = 0.05  20.8  (-110.13) = – 114.53 Joules

Daily Tutorial Sheet 1 to 5 Level – 1 | JEE Main

1.(B) Work done ( W )   pext ( V2  V1 )


  3  6  4   6 L atm 
  6  101.32 J  1L atm  101.32 J 
  607.92   608 J
2.(D) In the adiabatic process no heat enters or leaves the system i.e., q = 0.

3.(B) For an isothermal process T  0 and E  0 and q  0 .

4.(A) V1 = 100 mL ; V2 = 250 mL

Pressure p  2 atm or 2 1.01 105 Nm 2

Work done by the gas W  pV or p  V2  V1 

Put the value in given formula

 
W  2  1.01  105 0.250  10 3  0.100  10 3  2  1.01  105  0.15  10 3  30.30 J

5.(A) From first law of thermodynamic.

E  q  W Given, q   300 cal ( Heat is absorbed)
W   500 cal ( Work done on surroundings)

 E  q  W  300   500   200 cal  

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6.(B) A  B, H   24 kJ / mol

 HB  H A   24 ........ (i)
B  C, H   18 kJ / mol
 HC  HB   18 ........ (ii)

 HB  HC   18
From Equations (i) and (ii), we have
HC  H A  6

HB  HC  H A

7.(C) This is based on Joule-Thomson effect.

8.(B) Molar heat capacity Heat required to raise the temperature of 1 mole of a substance by 1°C is called
molar heat capacity.
9.(A) Work done
(W)   Pext (V2  V1 )   1  105 Nm 2  (1  10 2  1  10 3 )m 3   105  9  10 3 J   900 J

10.(B) (A) Temperature constant (B) Pressure constant

(C) Heat exchange is zero (D) Volume constant

11.(C) Heat exchange is zero

12.(B) H  U  n g RT

3
U  3271   8.314  10 3  300
2
U  3267.25
Now for 1.5 mole
U  3267.25  1.5  4900.88 J

13.(B)  
W   Pext V2  V1   2  20   40 lt  atm

  40  101.3 J   4052 J
U  q  W  10000  4052  5948 J
nR
14.(A) V  T
P
nR
 log V  log T  log
p
 y  mx  C
Where m  1    45
nR 100  0.0821
C  log  log 0
p 8.21
P1 10
15.(B) W   nRT n   10  300  8.314 n   57441J
P2 1

W  mgh
57441
 m   58.6 kg
9.8  100
16.(A) For cyclic process, change in state function is zero. Since U and H are state variables, U  0
and H  0.

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V2 20
17.(B) W   nRT n   1  8.314  298  2.303 log   298  8.314  107  2.303 log 2
V1 10

18.(C) ( CP )rxn  0,  H300  H310

19.(D) From given reaction n g  12  15  3

so Eo  Ho  n g RT  6542  3RT

1.5
for 1.5 mole, Eo  {–6542+3RT} = –4900.9 kJ
2
20.(C) n g  1  2  1

E  H  n g RT  H  RT  72.3  8.314  300  10 3  69.806 kJ/mol

So for 3 mole we will get E  69.806  3 kJ/mole  209.42 kJ/mole

21.(B) W  Pext ( V)  (1 atm)  500  50  10 3 L  25L atm  25  101.3  10 3 kJ  2.53 kJ

22.(A)
C 2H 4  H2  C2 H 6
50ml 50ml 0
X X 50ml
H  U  P( V)
0.31  U  1.5  1.01  105 ( 50  10 6 )  10 3
U  0.3024 kJ

23.(B) H2O(s)  H2O(l), H  1440 cal

H  U for solids and liquids

24.(A) Beaker is open and in open beaker external pressure remains constant.

Zn  H2SO4  ZnSO4  H2 (g)

130
 2 mole
65
PV = nRT
PV  n g RT

W  n g RT   2  2  300  1200 cal

25.(C) q  H  60 cal  nCP,m T

U  nC V T
m

60 60
   U   42.8 cal
U 1.4
3R 5R
n1C V  n 2C V 2  2
26.(B) (C V )mix  m m
 2 2  2R
m n1  n 2 4

V2 1
27.(B) W   nRT n   52  10 3  8.314  260  2.303 log  123 J
V1 3

28.(C)  
W   Pext V2  V1   3  2   6 lt - atm   6  101.3   607.8 J

 607.8  msT
 607.8  10  18  4.18  T  T  0.8  T2  290.8 K

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29.(B)

For adiabatic process, final volume and final temperature will be lower as compared to isothermal
process

30.(D) H  3 H1  H2  2H3  3 H 4 = – 747.4 kJ

H  U  n g RT, where n g  8

8  8.314  300
747.4  U o 
1000
U  727.44 kJ
31.(D) S  10.13  31.2  51.1  47.3  S H
2O

SH  45.13 cal/k mole.

2O

32.(A) G  29.3  103  (2  239.7  152.3  223)  298  1721.8 Joule

33.(D) U  0 [for isothermal process]

H  0
V2
 PV  constant S  nR ln
V1
S  0 for isothermal expansion

34.(B) Endothermic reaction  H  0

S  0 as gaseous moles are increasing

35.(C) In I part, entropy is decreasing as solid is formed

In II and III, entropy is increasing as gaseous moles are increasing

36.(ACD) Only heat exchange depends on path so it is a path function

All other options depends only on state so these are state function
 H vap 30000
37.(B) S   T   400 K
TB.pt 75

38.(ABD) P1V1  P2 V2 [for isothermal]

U  0 [for isothermal]
H  0 [for isothermal]
39.(A) U  q  W
40.(D) W   PV   nRT   1  R  1   R

41.(B) For adiabatic reversible process;


V 

PV  K  P2  P1  1  as V2  V1  
V 
 2
 So final pressure will be more for diatomic gas (less  )

42.(C) TV  1  K

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43.(D) Bond formation is exothermic.

44.(A) (A) At constant volume, w  0
q0 (Cooling)
U  0 (Temperature is decreasing)
(B) U  0 (isothermal)
w0 (expansion)
q0 ( U  q  w)
(C) q 0 (Adiabatic)
w 0 (Vacuum)
U  0
(D) w0 (expansion)
q 0 (endothermic)
H  U  0
45.(C) (A) q 0 (B) T  0 (C) H  0 (D) S  0

46.(ABCD)
For an isothermal process, E  0, H  0
T2 P1
S  nC p,m ln  nR ln 0
T1 P2

47.(D) PbO2  Pb  2PbO

4 0 2
Since,  r G  0 , hence +2 state of lead is favourable.

SnO2  Sn  2SnO

4 0 2
Since,  r G  0 , it means forward reaction is not spontaneous.

2SnO  SnO2  Sn

2 4 0
For this  r G  0 , thus  4 state of tin is favourable.

48.(B) G   RT ln K
 H S
or, H  TS   RT ln K or, ln K  
RT R
S
Comparing with y = m.x + c  y intercept is
R
49.(D) The standard free energy change ( G ) is related to equilibrium constant K as
G    RT ln K ; G    2.303 RT log K

50.(B)  G   H  T  S   29.8  298   0.1   29.8  29.8  0

51.(A) The unit of entropy is J mol 1 K 1.

52.(A) For a system in equilibrium, G  0, when all the reactants and products are in the standard state
[at constant temperature and pressure].

53.(A) H2 (g)  Cl2 (g)  2HCl(g) S   Sp   SR  2 187  131  223  374  354  20 JK 1 mol 1
 
54.(A) Given, H  31400 cal , S  32 cal K 1 mol 1 , T  1000  273  1273K , G  ?
From Gibb’s-Helmholtz equation
G  H  T  S  31400 1273  32  31400  40736   9336 cal

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55.(C) For spontaneous adsorption process, standard Gibb’s free energy ( G) must be negative as well as the
degree of randomness of gas molecule on the surface of solid decreases. For exothermic process, H
must be negative. Hence, with the help of following equation.
H  G  T  S
T  S is negative. Thus, during adsorption S decreases.
 vapH 40.8 10 3
56.(B)  vapS  ;  vapS   109.4 JK 1 mol 1
T 373
57.(D) As we know that, G  H  TS
Hence, G may be greater, lesser or equal to H.
58.(D) For a reversible process Ssystem  Ssurroundings  0

59.(A) U  q  w  0 for cyclic process.

60.(A) | w | P2 ( V2  V1 )  P3 ( V3  V2 )

61.(BD) Reaction spontaneous at higher temperatures and non-spontaneous at lower temperatures,

 r H  0 and  r S  0.

62.(AD) G  RT ln K eq  H  TS

H 1 S
ln K eq   
R T R
H S
slope  , y intercept 
R R
Equilibrium can exist only if both H and S have similar signs.

63.(BCD) C (Graphite)  C(Diamond) H   ve

i.e. C (Graphite) is thermodynamically more stable.
64.(AB) Internal energy and molar enthalpy do not depend on path. So both are state function

65.(C)

H  heat of reaction (endothermic)

Ea  energy of activation

Thus, Ea  H

66. [A : 1, 2] ; [B : 1, 2] ; [C : 3] ; [D : 1, 2]

(A) CO2 (g)  C(s)  2CO(g)  r Ho  2  220   394 and  r So  0

   
  r Go  0 and  r Ho   r Uo  n g RT  2  1 RT  0
 
(B) SO2 Cl 2 (g)  SO2 (g)  Cl2 (g)  
 r S  0 and  r H   r U  n g RT  2  1 RT  0

(C) CO (g)  Cl 2 (g)  COCl2 (g)  

 r S  0 and  r H   r U  2  1 RT  0

(D) Cl (g)  2Cl (g)  

 r S  0 and  r H   r U  2  1 RT  0

Chemistry | Thermodynamics 41 Workbook-2| Solutions

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67. [A : 1, 3] ; [B : 2] ; [C : 1, 3] ; [D : 2, 4]
 In standard state heat of formation ( Hf ) and free energy change of formation ( G f ) will be zero.

68.(D) 
PCl5 (g)  PCl 3 (g)  Cl2 (g)  G  0
0  H  T S
Since gaseous moles are increasing S  0
Thus H  TS  H  0

69.(B) G  H  TS   95  1000  500   190    95000  95000  0

Upto T  500 K the synthesis of ammonia is spontaneous. After 500 K synthesis becomes non-
spontaneous, so ammonia will dissociate spontaneously.
70.(C) Internal energy of a gas depends upon its pressure and temperature. Thus, if a gas expands at
constant temperature and pressure, then its internal energy remains same.
71.(D) H   ve (combustion reaction)
S   ve (spontaneous at all temperature)
G   ve (because reaction is spontaneous)

72.(A) For spontaneous process, system and surrounding entropy should be positive
 Ssys.  Ssurr.  0

73.(A) 
A( )  A(g) at boiling point
H   100  ( 130)  30 kJ / mol ; S  200  100  100 kJ / mol
H
For equilibrium G  0  Tb   300 K
S
74.(A) For equilibrium G  0

75.(A) H2O (1 bar, 373 K )  H2O (g)(1 bar, 373 K)

 equilibrium  G  0
Since liquid  gaseous phase S  0

Daily Tutorial Sheet 6 to 10 Level – 2 | JEE Advanced Pattern

76.(BCD) (A) Expansion of an ideal gas against vaccum is an irreversible process.

(B) Spontaneous process is always irreversible.
(C) As per definition of reversible process.
(D) If expansion is carried out reversibly, system will do work and hence, it will absorb more heat
from the surroundings.
77. [A : 1, 2] ; [B : 3] ; [C : 1, 2, 3] ; [D : 4]
(A) For isothermal process : U  H  0
(B) For reversible adiabatic process : S  0
(C) For cyclic process : U  H  S  0
(D) For isochoric process : w  0
78.(C) Wirr  Pext (V2  V1 )
8.314 JK 1 mol 1
W   1(20  10)  10 dm 3 atm  10 dm 3    1013 J
0.0821 dm 3 K 1 mol 1
From, 1st w of thermodynamics U  q  W  800 J  ( 1013 J)   213 J

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79.(D) In neutralization reaction, when acid and base both are weak, a large amount of heat is utilized to
ionise them. Thus, for such reactions, enthalpy of the reaction is least.

Hence, enthalpy is least for HCN  NH4OH  NH4CN  H2O

80.(B) S  16 J mol 1 K 1, H v  6 kJ mol 1

H vapour 6  1000
Tbp    375 K
S vapour 16

81.(B) For Zn (s)  H2SO4 (aq)  ZnSO4 (aq)  H2 (g)

U  0, H  0, W  0 (expansion)

82.(D)

 1  8.314  373 
U  q  W  41000  1  105    0   (41000  3101.122) J  37.9 kJ
 1  10 5 
 
83.(B)  
W   Pext V2  V1   3  2   6 lt - atm   6  101.3   607.8 J

 607.8  msT
 607.8  10  18  4.18  T
T  0.8  T2  290.8 K

P dP
84.(BCD) , PQ, are intensive properties
Q dQ
85.(AB) For isothermal and cyclic process, E  0
T2 V2 V2 10
86.(B) ( S)sys  nC V,m n  nR n  nR n (T2  T1 )  2  8.314  n  38.29 J K 1mol 1
T1 V1 V1 1

87.(B) Expansion from state A to state B occurs at constant pressure (isobaric expansion) = 2P
88.(C) Expansion from state D state A occurs at constant volume (isochoric process) = V
89.(A) Work done in cyclic process = area of PV curve
| w | PV
Work = –PV (clockwise)
90.(D) In conversion from B to C, volume does not change or V  0, therefore w = 0.
91.(D) q  w  q  PV
PV
92.(A) T 
nR
93.(D) In cyclic process, H  0
94.(B) In expansion from state 1 to state 2.
P  1 atm
V1  22.44L

V2  44.88L

3
CV  R
2
T  T2  T1  546  273  273K
3
 U  nC v T  1   8.314  273  3.40  10 3 J
2
Chemistry | Thermodynamics 43 Workbook-2| Solutions
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95.(C) In conversion from state 2 to state 3

T  T2  T1  273  546  273K
3
CV  R
2
96.(B)  vap Ho  29.4 kJ mol 1 and Tboiling  334.7 K

 vap H  29.4 kJ mol 1 and Tboiling  334.7 K

 vapH
  vapS   87.84 J mol 1 K 1  10.6 R
Tboiling

97.(D) Sucrose (molecular weight)  342

From G  H  TS   6000  103  300  180   6054  103 kJ / mol

6054
For 34.2 gm energy available  kJ  34.2  605.4 kJ
342
98.(D) 
H2O(  )  H2O(s) ;  r H  0 and  r S  0

99.(C)   rG  RTn K eq  0 [ K eq  1]

  r G  0 and  r G   r H  T r S

Clearly,  r S  0   rG   r H

1
100.(CD) S  and  rG   r H  T r S
T

101.(A)  r H   f HCH 4
  74.9 kJ / mol
  
and  r S  SCH 4
 2SH 2
 SC  186.3  2  130.7  5.6   80.7 J / mol

 r G   r H  T r S   74.9  298    80.7   10 3   50.85 kJ / mol

 Reaction is spontaneous due to highly negative enthalpy change.

102.(B) 
CCl 4 ( )  CCl 4 (g)
 f H 135.4 103.0  r H   103   135.4   32.4 kJ / mol

Sm 215.4 308.7  r S  308.7  215.4  93.3 J / K / mol

 r H 32.4  103
Tboiling    347.3 K  74.3 C
 r S 93.3
nRT
103.(C) For an isothermal process : dG  VdP  G 
 VdP   P
 dP

P2 2
 G  nRT n  1  8.314  293 n   1.7 kJ / mol
P1 1

104.(A)  r STotal  56   r Ssystem

 
  r Ssurrounding


  r Hsystem 4.1  10 4
Ssurr    109.9 J / K
373 373
Ssys  56  110  54 J / K

q surrounding 64  10 3
105.(D) Ssurrounding    213.3 J / K
Tsurrounding 300

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106.(ACD) Absolute value of heat content, internal energy and Gibbs energy of the system can not be calculated.
Absolute value of entropy can be calculated.

107.(ACD) H2O (s)  H2O ( ) [spontaneous process because G  O ; S  O]

1
108.(A) H2 (g)  O2(g)  H2O (g)  r H298 K   241kJ / mol 1
2
 1 

 r H373 
K   r H298 K  CP (T2  T1 )   241.8   C P  H2O   CP H2  2  CP O2   373  298 
 
1
  241.8  [33.6  28.8   29.4]  (373  298)  10 3   242.6 kJ / mol
2
109.(D) Larger the molecule, more is the entropy. Also, Entropy of a molecule is larger in gaseous state them in
solid state.
 SC  SC ; SCO  SCO ; SI  SI
2H2 2 H6 2 2 (s) 2 (g)

110.(A) 
Protein A (S)  Protein A (  )  r H A  2.73 kcal / mol


Protein B (S)  Protein B ( )  r HB  3.0 kcal / mol
 rHA 2.73  r HB 3.03
S A    10 3  10 Jmol 1 K 1 and S A    103  10 Jmol 1 K 1
TA 273 TB 303

111.(A) Using :   r G  RT n K eq    rG  8.314  298 ln10 14  7.99  10 4 J

112.(B)  G   H  T S At equilibrium, G  0
For a reaction to be spontaneous G should be negative, so T should be greater than Te.

113.(B) Standard Gibb’s energy of formation ( Gf ) of a substance is defined as the Gibb’s energy change when
mole of the substance is formed from its elements in their standard states. The following reaction
1 1
define Gf , H2 (g)  F2 (g)  HF (g)
2 2
114.(B) C  D
 
A B
Given, S( A C)  50 eu

S(CD)  30 eu ; S(BD)  20 eu

Where, eu is entropy unit

Therefore, S(A  B)  S(A  C)  S(C  D)  S(D  B)

 S(A C)  S(C  D)  S(B  D)  50  30  20  60 eu

H 1 S
115.(D) Variation of K eq with temperature t is given by van’t Hoff equation ln K eq    
R T R
A R
Slope of the given line is positive indicating that term A is positive thus H is negative. Thus, reaction
is exothermic.
116.(B) For a reaction to be spontaneous G must be negative. According to relationship of G,
G  H  T  S
If H and S both are positive, then term T. S will be greater than H at high temperature and
consequently G will be negative at high temperature. (Boiling point of water) and reaction becomes
feasible.

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117.(B) Entropy of vapour is higher than liquid higher than solid.

118.(C) G  H  T S
If G   ve  reaction is spontaneous H  0 and S  0
It implies that entropy term can make G negative which is possible at higher temperature.
 298  160.2 
119.(A) G  H  TS  179.1   kJ / mol  179.1  47.74  131.36 kJ   ve
 1000 
 
 non-spontaneous at 298K.
Let at T, reaction is spontaneous.
G  0  H  TS  0
H 179.1  1000
T  K
S 160.2
T  1118 K
1 3
120.(D) X2  
Y2  XY3
2 2
1 3 
S  50    60   40   50  90   40 kJ / mol
2 2 
 

G  0   30  10 3  T  ( 40)

40T  30  103  T  750 K

121.(C) G  G   RT nQ
At equilibrium G  0 and G  H  T S and Q  K
H  T S
nK  
RT
122.(D) S   ve
H   ve
G  H  TS
For a reaction to be spontaneous ; G   ve which can be below a certain temperature only

123.(B) G  H  TS  2808  310  182.4  10 3  2864.5 kJ

124.(A) Since, expansion occurred at constant temperature,

V2 1 3.0
S  nR ln   8.314 ln  0.36 JK 1
V1 32 0.75

Since, this is case of free expansion, Pext  0   W  Pext V  0, q  0

Also, since, T  0  H  E  0.
1
125.(B) Cu2O(s)  
O2 (g)  2CuO(s)
2
Greaction  [2  ( 30.4)]  ( 34.98)  25.82 kcal

and 25.82  103  2.303  2  298 log K

 K  1019, a very high value, hence reaction will be almost complete with a trace of Cu2O .

Chemistry | Thermodynamics 46 Workbook-2| Solutions

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Daily Tutorial Sheet 11 Numerical Value Type for JEE Main

126.(225) For an ideal gas

3 
U  nC V [T]  1  R  [100  25]
2 
 U  225 cal

127.(32) w   8J; q  40J

From I law U  q  w  40  8  32 joule
128.(290.81)
Work is done against external pressure and thus process is irreversible
w  PV
V  5  3   2dm 3  2  10 3 m 3

P  3 atm  3  1.013  105 N m 2

w   3  1.013  105  2  10 3   607.8J

Since, the work is used in heating water and thus
 w  q  n  C  T
Or 607.8  10  4.184  18  T
T  0.81
Final temperature  290  0.81  290.81K

129.(190.70)
dU   Pext.  dV
 nRT2 nRT1 
nC v (T2  T1 )  Pext.[V2  V1]  P2   
 P2 P1 
 T2 T1 
C v (T2  T1 )   P2  R   
 P2 P1 
 T2 298 
1.5  (T2  298)   1.013  105  R  5
 6
 1.013  10 1.013  10 
T2  190.7K
130.(21.98)
Entropy change of fusion, Sf  Hf / T

Hf  6  103 J; T  273K

(6  103 )
S f   21.98 JK 1 mol 1
273
131.(172.28)
103
w  P(Vg  Vi )  PVg  nRT   8.314  373  172284.56 J  172.28 kJ
18
70
132.(50) Q p  Cp  T  Cp   14 cal C1
5
Cp  C v  nR

C v  14  2  2  10 cal K 1
Q v  C v T  10  5  50 cal

Chemistry | Thermodynamics 47 Workbook-2| Solutions

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133.(0) For isothermal process U  0

V2 20
134.(9.20) S  2.303nR log  2.303  2  2 log  9.2 cal K 1 mol 1
V1 2
135.(2.40) q  n  C P T
100
1000   75  T
18
T  2.4K
136.(1.01)
q surr q sys Wsys
Ssurr   
T T T
 Pext (Vf  Vi )  3(2  1)
Ssurr   L atm K 1
T 300
  0.01L atm K 1   0.01  101.3 JK 1   1.013 JK 1

u rmsT1 T1
137.(32) 
u rmsT2 T2
2u T1

u T2
T1
4
T2
T1
T2 
4
From TV 1  constant for adiabatic expansion
T1V11  T2 V21
1
 V1  T2 1
   
 V2  T1 4
1.4 1
 V1  1 V2
     32
 V2  4 V1

138.(2.70) H  U  nRT  2100  2  2  300  3300 cal / mol

G  H  TS  3300  300  20  2700 cal
H  U 50  113
139.(6.30) H  U  PV  P   6.3 k Nm 2
V 10
140.(114.51)
H  n  Cp  T and Cp  C v  R  12.48  8.314  20.794 JK 1 mol 1
For a given sample of argon gas, mole (n)
PV 1  1.25
n   0.05 mole
RT 0.0821  300
Also, for reversible adiabatic change TV  1  constant
T2 V21  T1V11
1 1.66 1 0.66
 V1   1.25  1
or T2  T1    300    300   
 V  
 2  2.50  2
T2  189.86 K
T  T2  T1  189.86  300   110.14 K
H  0.05  20.794  ( 110.14)  114.51 J

Chemistry | Thermodynamics 48 Workbook-2| Solutions

 Vidyamandir Classes

Daily Tutorial Sheet 1 to 3 JEE Main (Archive)

1.(C)

2.(BD) Refractive index depend only on nature of substance

3.(BCD) In B, C, D, energy is required

4.(C) A reversible process is that in which system and surroundings are always in equilibrium.

5.(A) Work and heat are path function 6.(C) H  nCp T

7.(A) Work and heat are path function. 8.(AB) Molar conductivity and emf. are intensive properties
vf
9.(A) w   2.303nRT log 10.(D) Gor  RT ln K p
vi
11.(D) For adiabatic process : q = 0
So from Ist law  U  q  w
We can write U  w

12.(A) Isothermal T = constant

PVm  constant PVm will remain constant with increase of pressure
1
P  k Pressure will increase linearly with increase in 1/Vm
Vm

13.(D) For reversible isothermal expansion of an ideal gas :

V2  V2  Final volume 
w   nRT ln  
V1  V1  Initial volume 
V2
 | w |  nRT ln  | w |  nRT ln V2  nRT ln V1
V1

So in a graph of | w | versus ln V2 , the intercept cannot be positive.

14.(A) Overall process
a b c d
 H2O(  ) 
H2O (ice)   H2O ( )  H2O (g) 
 H2O(g)
273 K 273 K 373 K 373 K 383 K

Hfusion 334
Sa    1.22
273 273
 373 
S b  4.2 ln    1.31
 273 
H vapourisation 2491
Sc    6.67
373 373

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 383 
Sa  2 ln    0.05
 373 
S Total  Sa  S b  Sc  Sd  1.22  1.31  6.67  0.05  9.26 kJ kg 1 K 1

15.(D) Vi  5m 3 ; Vf  1m 3

Pext  4 N / m 2

Isothermal  U  0
qW0

q   W     Pext dV  
   P ext dV 
 Pext dV  Pext V  4[1  5]  4  ( 4)  16 J

Heat lost by the system = 16J

16  nCT
16 2
16  (1)(24) T  T  
24 3
16.(A) (A) N 2  3H2  2NH3
Since number of gaseous moles are decreasing hence entropy change S  S products  S reactants is
negative
(B) CaSO4  CaO  SO3
(s) (s) (g )

S : positive, as number of gas moles increases

(C) CO2 (s)  CO2 (g)

S : positive, as number of gaseous moles are increasing

(D) I2 (s)  I2 (aq )

S : positive, as randomness of the system has increased

17.(D) Heat released by one block at T2  Heat absorbed by block at T1

 ms  T  T2   ms  T  T1  (where T2  T1 ) ; T is equilibrium temperature

T1  T2
 T2  T    T  T1  , T 
2
T T  T T  T2
S  C p ln  C p ln  C p ln     S  C p ln
T1 T2 T T  T1 T2
 1 2 
2
 T1  T2 
S  Cp ln
4 T1T2
f
18.(C) Cv  R
2
f 
CP    1 R Where f = degree of freedom at normal temperature.
2 
At normal temperature f = 5 for diatomic gas.
At higher temperature vibrational degree of freedom also becomes active, so the value of f in both
C v and C P will shot up after a particular temperature. Hence graph (C) is incorrect.

19.(A) For the process to be spontaneous G :  ve

G  H   (TS)
At a particular Temperature G  H  TS

Chemistry | Thermodynamics 50 Workbook-2| Solutions

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For spontaneity G  0
H  TS  0
TS  H
T(40) > 200 T = 5K  T>5

20.(D) G  H  TS

A  H 
B  S
For endothermic Reaction H  0
21.(A) The reaction
MgO(s)  C(s)  Mg(s)  CO(g)
 r H   4941.1kJ / mol

 r S   198.0 J K 1 mol 1
G  0 at equilibrium

H 491.1  10 3
T    2480.3 K
S 198.0
22.(A) For spontaneous process
G  ( H  TS) should be negative
 G  0
23.(C) q & w are path functions.
Option (C) is correct
1000 1000
 0.01T 2 
24.(D) H 
 nC dT  3 
P
300
(23  0.01 T )dT  3 23T 
 2

 300

 0.01 0.01(300)2 
 3 23000  (1000)2  23(300)  
 2 2 
 3 23000  5000  6900  450   61950 J  62 kJ
25.(B) According to first law of thermodynamics : U  q  w
For adiabatic process, q  0
Hence, U  w
26.(A) U  q  W
U  (  2)  10  8 kJ
5  28  100
27.(A) U  nCv T   14 kJ
1000
5  8  100
 (pV)  nRT   4 kJ
1000
28.(6.25) U  nC v T
500  4  C v  (500  300)
5000
Cv   6.25JK 1mol 1
4  200
T
dq nCdT
29.(D) S 
T ; S

0
T

Chemistry | Thermodynamics 51 Workbook-2| Solutions

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1
30.(48.00) Work done  Area under the curve  (6  10)  6  48 J
2
31.(–2.70) A ( )  2B(g)
U  2.1 kcal, S  20 cal / k, T  300K
G  H  TS
H  U  ng RT ng  2
G  3300  (300)(20)  3300  6000   2700 cal   2.7 kcal
32.(A) For one mole of an Ideal gas
(a) U and H depends upon temperature
(c) Cp, m  C v, m  R

(d) dU  C v dT for any process.

33.(–13,538)
G  H  TS
H  U  n g RT

  20,000  (8.314  298)   22477.57

G    22477.57  (298  30)   13538 J

34.(C) Free expansion having zero work done

35.(189494)
90 gm H2O  5 moles of H2O
H  U  n  RT

(41  103  5)  U  (5  8.314  373)

U  189494.39 J  189494 J

36.(B) 4M (s)  NO2 (g)  2M2O n (s)

H  (  )ve, S  (  )ve
 G is negative at low temperature values and the oxide will be stable below the temperature, at
which G  0 or it will be changing its sign from negative to positive.
37.(A) T1  298 K T2  373 K

K1  10 K 2  100

K2 H  1 1 
Using, log    
K1 2.303 R  T1 T2 
H 75
log10  
2.303  8.314 373  298
2.303  8.314  373  298
H 
75
H  28.4 kJ mol 1
Now, at T1  298 K at T2  373 K

G1   RT1 ln K1 G2   RT2 ln K 2

G1   8.314  298  ln10 G2   8.314  373  ln100

G1   5.71kJ mol 1 G2   14.29 kJ mol 1

Chemistry | Thermodynamics 52 Workbook-2| Solutions

 Vidyamandir Classes

Daily Tutorial Sheet 1 to 3 JEE Advanced (Archive)

1.(T) I law does not predict about spontaneity of a process

2.(R) C p  C v  R for ideal gas

1 1
3.(900) Total energy  3  nRT  3   1  2  300  900 Cal
2 2
5R 3R
4.(T) C v for diatomic gas  ; C v for monoatomic 
2 2
5. Isolated system  No exchange of mass and energy
6. Enthalpy is mass dependent.

7.(0) Fe (s)  2 HCl (aq)  FeCl 2  H 2 (g)

w 0 (as V  0)
8. 116.4 J
H  nCp T

 Cp
T1 V1 1  T2 V2 1 
Cv
5R 3R
Cp  ; CV  for He Ar
2 2

9.(B) Free isothermal expansion, w  0, U  0  q 0

Volume occupied by molecular of an ideal gas is zero

10.  rG   257.2 kJ  0 ; H   285.4 kJ  0

11. G1  16 kJ ; G2  12.3 kJ

12.(C) H  U  (pv) , H  U  (p2 v 2  p1v1 )

13. (i)

(ii) W  6.14 L atm Q = 6.14 L atm

(iii) All the state functions, U, H and S are zero for cyclic process.
14. He is monatomic, so it has only three degree of freedom (translational only) at all temperature hence,
3
CV value is always R.
2
Hydrogen molecule is diatomic, has three translational, two rotational and one vibrational degree of
freedom. The energy spacing between adjacent levels are in the order of:
Translational < rotational < vibrational
At lower temperature only translational degree of freedom contribute to heat capacity while at higher
temperature rotational and vibrational degree of freedom starts contributing to heat capacity.

H
15.(B) S 
Tb

Chemistry | Thermodynamics 53 Workbook-2| Solutions

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 99 100  100
16.(9.8) H  U  (PV )  (P2 V2  P1V1 )  100  1   98 = 9.8 L-bar
 1000 1000  1000

17.(D) For an irreversible, adiabatic process; 0  C v (T2  T1 )  pe (V2  V1 )

Substituting the values C V (T  T2 )  1(2  1)atm L

1 2 2
 T  T2    T2  T 
CV 3R 3  0.082

R 5R R p
18.(A) Cm  Cv  ; Cm   ; Since 1  pV 1  1
1 x 10 1  ( 1) V
19.(A) Entropy is a state function S A C  SCD  SDB  S A B

20.(B) Catalyst does not alter the equilibrium established in lesser time in the presence of catalyst.

21.(B) G  H  TS ; G  2.303RT log10 k

22.(A) At equilibrium G  0
Liquid  Gas S   ve
23.(D) At equilibrium G  0 Gº  0
As G decreases reaction becomes more spontaneous.

24.(B) II law of thermodynamics

25.(AD) Reversible or irreversible both expansion work are path function.

2
26.(2) Work done along dashed path |  W | pV  4  1.5  1  1   2.5  8.65 L atm
3
Work done along solid path
V2 V2 5.5
 W  nRT ln  p1V1 ln  2  2.3 log  2  2.3 log11  4.79
V1 V1 0.5

Wd 8.65
   1.80  2
Ws 4.79

nRT 0.1  0.08  273

27.(7) V   7
p 1  0.68 
28. [A  p, r, s] [B  r, s] [C  t] [D  p, q, t]
(A) CO2 (s)  CO2 (g)

It is just a phase transition (sublimation) as no chemical change has occurred. Sublimation is

always endothermic. Product is gas, more disordered, hence  S is positive.
(B) CaCO3 (s)  CaO(s)  Co2 (g)
It is a chemical decomposition, not a phase change. Thermal decomposition occur at the expense
of energy, hence endothermic. Product contain a gaseous species, hence, S  0 .
(C) 2H  H2 (g)
A new H–H covalent bond is being formed, hence, H  0 . Also, product is less disordered than
reactant, S  0 .
(D) Allotropes are considered as different phase, hence P(white,solid)  P(red,solid is a phase transition

as well as allotropic change.

Also, red phosphorus is more ordered than white phosphorus, S  0 .

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29. [A  r, t] [B  p, q, s] [C  p, q, s] [D  p, q, s, t]
In freezing of water entropy decreases and due to equilibrium condition G  0 .
Adiabatic expansion against vaccum is isothermal q = 0, w = 0, U  0 .
In case of isolated condition q  0 w  0 U  0
In case of D, path (reversible heating and reversible cooling) & state (300 K, 1 atm) both are same
therefore change in state function or path function would be zero.

30.(AC) Entropy is a state function, it does not depend on path.

31.(ACD) In adiabatic expansion temperature always decreases. In case of expansion Wisothermal  Wadiabatic
32.(C) L  M At constant V —isochoric, N  K
1
33.(B) Plan By Boyle’s law at constant temperature, P 
V
By Charles’ law at constant pressure, V  T
Process taking place at
Constant temperature – isothermal, Constant pressure – isobaric
Constant volume-isochoric, Constant heat – adiabatic
K L At constant p, volume increases Thus, heating
L M At constant V, pressure decreases Thus, cooling
M N At constant p, volume decreases Thus, cooling
N K At constant V, pressure increase Thus, heating

34.(ABC) Adiabatic expansion against zero external pressure is isothermal process.

35.(B) For reversible process Ssystem  Ssurroun  0

36.(B) 
X 2 (g)  2X(g)
t0 1 
eq
t  t eq 1 eq
2
2
 
 2 
 eq 
 eq      
1      1  eq 
2  eq 2  22eq  82 
px  2 px  2  ; Kp    
eq 
2  eq   eq   eq   2 
 4  2eq 
 1    1   1   1  eq  
 2   2  2 
2 4
 eq 
 1  
 2 
37.(C) (A) 
It is true statement X 2 (g)  2X(g)
If P is decreased then reaction will move in forward direction according to Le-Chatelier's
principle.
(B) It is true statement
At start of reaction Q = 0
 G  G  RT ln Q
If Q=0
Then G   ve ; reaction is spontaneous
(D) It is true statement
G   ve
RT ln K P  G  K p  1 since K c  K p  K C is also less than 1.

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G 2.9 kJmol 1 2.9  10 3 Jmol 1

38.(A) P    1.45  10 9 Nm 2
V 2  10 6 m 3 mol 1 2  10 6 m 3mol 1

1.45  109
P bar  1.45  10 4 bar  14500 bar
105

39.(BD) G    RT n K , G  H  TS

H  1  S
RTn K  H  TS , nK   
R T R
 
H  0, S  0  K decreases with increase in T ;

H  0, S   0  K increases with increase in T

H  0, S   0  K decreases with increase in T ;

H  0, S   0  K decreases with increase in T

q sys
Ssurr 
Tsurr

S surr favourable means S surr is positive while S surr unfavourable means S surr is negative.
If value of K increases with increase in temperature for endothermic reaction it means reaction shift
toward forward direction because of unfavourable change in entropy of the surrounding decreases.
Similarly if value of K for exothermic reaction decreases with increase in temperature it means reaction
shift toward backward direction due to decrease in favourable change in entropy of surrounding.

Expansion
40.(ACD) State 1  State  2
 p1,V1,T1   p2 ,V2,T2 
 Work done in reversible compression process is smaller than the work done in irreversible
compression process.
 U  0 for reversible isothermal expansion.
U  0 for reversible adiabatic expansion.
 For free expansion q  0 , w  0 and U  0 hence it is simultaneously both isothermal
( U  0) as well as adiabatic (q = 0).
 Work done in reversible adiabatic expansion is less than the work done in reversible isothermal
expansion as shown in figure.

41.(C) G  H  TS
RTnk  H  TS
H S
nk  
RT R
H
Slope is
R
Since H is  ve
 Slope is positive.

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42.(B) U AB  q  W  2  5   3 kJ / mol

U  0  U AB  U BC  U CA

 0   3  5  UCA  UCA  8 kJ / mol

U CA  q  W
 8  q CA  3  q CA  5 kJ / mol

43.(BC)
A(P 1 V1 T 1) C (P2 V1 T 2)
Volume (V)

B(P 2V 2T 1 )

Temperature (T)
Path AB BC CA
Process Isothermal Isobaric Isochoric
U  0 U  nC V (T2  T1 ) U  nC V (T1  T2 )

H  0 H   nC p(T2  T1 ) H  nC p ( T1  T2 )

V2 W  P2 (V1  V2 ) W 0
W  nRT ln
V1

V2 q  nC V (T2  T1 )  P2 (V1  V2 ) q  nC V (T1  T2 )

q  nRTE ln
V1

q AC  U AC  nC V [T2  T1]  UBC

V2
WAB  nRT1 ln
V1

WBC  P2 [V1  V2 ]  P2[V2  V1]

q BC  BC  nCP [T2  T1]  H AC

HCA  nCP [T1  T2 ]

UCA  nC V [T1  T2 ]
HCA  UCA because both are negative and T1  T2

44.(AC) As the concentration of product decreases by increasing temperature H  0 .

ln  K1  T2 Also
as given 
ln  K 2  T1
and T2  T1   P 
  1
  A   eq
 K eq  1
As we know
G   RT ln K
 as K eq  1 
( G)1   RT1 ln K1  T can 't be  ve 
 
( G)2   RT2 ln K 2  G   0

G1  RT1 ln K1

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G2  RT2 ln K 2
 ln K1 
 
G1 T1 ln K1 G1  ln K 
 2 
  
G1 T2 ln K 2 G2  T2 
 
T 
 1
G1  ln K1 T 
1 as  2
G2  ln K 2 T1 

Since G  0

So, G1  G2 because G increases on increase in temperature

As G  on increases Temp

G  H  TS and H  0
So S  0

45.(ABC) For Vander waal’s gas equation

 an 2 
P   (v  nb)  nRT

 v 2 

For one mole of Vander Waal’s gas

 a   a  RT RT a
P   (V  b)  RT  P    P 
 v 2   V 2  V b Vb V2
  

For Reversible isothermal and reversible adiabatic process, work done is

 RT a 

w   P dv  w 

 
 V  b V2
 dv



Chemistry | Thermodynamics 58 Workbook-2| Solutions