Chapter 4

Thermodynamics

Hints and Solutions

6. Answer (3)
SECTION - A
1. Answer (4) 1
H2 + O  H2O
At constant temperature 2 2

dq  1 
C= [dT = 0] H =  433  (492)   2  464
dt  2 
 C= = (433 + 246) – 928
2. Answer (2) = – 249 kJ/mol
In vacuum, the external pressure is zero. 7. Answer (4)
 w=0 At equilibrium, Ecell = 0
3. Answer (4)
8. Answer (4)
C7H8(l) + 9O2(g)  7CO2(g) + 4H2O(l) at 27°C.
PH3  P + 3H, H = 228 kcal
ng = –2
 qp – qv = ng RT H2P – PH2  2P + 4H, H = 355 kcal
2  8.314  300
= HP – P + 4 × HP – H = 355
1000
= – 5.0 kJ/mol (approx) 228
HP – P + 4 × = 355
 for 0.1 mole of toluene 3

qp – qv = – 0.50 kJ HP – P = 51 kcal

4. Answer (2) 9. Answer (2)
G° = – 2.303 RT log10Kc Hdissolution = Hionisation + Hhydration
 – 2.303 RT log Kc = H° – TS° = 778 – 774.3 = 3.7 kJ mol–1
 S = 3700 J mol–1
 = 8
2.303R
Sdissolution = 43 JK–1
 S° = 8 × 2.303 R
Gdissolution = H – TS
= 18.42 R
= 3700 – 298 × 43
5. Answer (4)
= – 9114 J
The enthalpy of hydration of F– is higher than its
enthalpy of dissociation. or – 9.114 kJ

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Hints & Solutions Thermodynamics 31
10. Answer (3) Work done = P(V2 – V1)
(i) HCl + NH4OH  NH4Cl + H2O H = –51.4 V2 = VH2 and V1 = 0 (for solid + liquid state)
kJ
∵ pH2  VH2  nRT
(ii) CH3COOH + NaOH  CH3COONa + H2O
H = –50.6 kJ nRT
VH2 
(iii) CH3COOH + NH4OH  CH3COONH4 + H2O pH2

H = ? nRT
W = p  nRT
We know pH2
(iv) HCl + NaOH  NaCl + H2O H = –57.2 kJ = 2 × 2 × 300 = 1200 cal

To get (iii) add (i) and (ii) and subtract (iv) 19. Answer (4)
G = H – TS
H = (–51.4) + (–50.6) – (–57.4) = –44.6 kJ
If H < 0 and S > 0, then G < 0 at all
11. Answer (4)
temperature.
Change in internal energy is a state function
20. Answer (2)
 U(A  B) = 60 kJ/mol Coupled reaction, G = negative or positive

` U(B  A) = –60 kJ/mol At eq. G = 0

Cyclic process U = 0
 Net change in internal energy = zero.
21. Answer (4)
12. Answer (1)
H = Breact – BProd
13. Answer (1)
= (194 + 2(99)] + (104)2 – [83 + 6(99)]
Cp = 0.125 cal/g Cv = 0.075 cal/g
600 – 677 = –77 kcal
Cp 0.125
For atomicity  =  = 1.66 22. Answer (3)
Cv 0.075
The reaction for whichn(g) = 0
i.e., gas is monoatomic.
H = E
14. Answer (4)
23. Answer (1)
15. Answer (3)
H2O(l)  H2O(g) H = b
16. Answer (2)
H = Hf(P) – Hf(R)
G° = – 2.303 RT log Kp
24. Answer (4)
= –11.488 kJ  – 11.5 kJ Independent of amount of substance.

17. Answer (4) 25. Answer (1)

G = H – TS Fact

If H = +ve and S = –ve, then G = +ve. 26. Answer (2)

18. Answer (1) Fact

Fe + 2HCl  FeCl2 + H2 27. Answer (3)

112 g 4X + O2  2X2O

112 H = ?
n of Fe = =2
56 H = 4X (– 80) = – 320 kJ
 nH2 formed = 2 28. Answer (3)

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32 Thermodynamics Hints & Solutions

29. Answer (2) x x 2x  x  4 x

 100      x   100
 2 4  4
15
C6H6(l) + O  g   6CO2(g) + 3H2O(l) x = 400 kJ
2 2
41. Answer (3)
0.532
0.532 g C6H6   0.00682 mole 42. Answer (1)
78
43. Answer (2)
22.3 1
228
U   3269.8 kJ mole B.E. P  H   76 kcal mol 1
0.00682 3
H = U + ngRT B.E. P–P = 355 – 4 × (P – H) = 51 kcal mol–1
8.314 44. Answer (2)
 3269.8  1.5   353
1000
For 5 mol of gas at temperature T K
= –3274.2 kJ mol–1
PV1 = 5RT
30. Answer (2)
for 5 mol of gas at temperature (T – 2) K
31. Answer (4)
PV2 = 5R(T–2)
Volume of water is less than the volume of ice and
melting of ice is endothermic. P(V2 – V1) = 5R (T – 2 – T)

32. Answer (3) PV = – 10R

33. Answer (1) or – PV = 10 R

When V = –ve, W = + ve
r1 M2 45. Answer (4)
(1) 
r2 M1
Fact

34. Answer (3) 46. Answer (4)

E = H – nRT = 3 × 10 – 3 × 2 × 10–3 × 500 G = H – TS

 27 kcal 47. Answer (2)

35. Answer (1) 48. Answer (4)

36. Answer (4) 49. Answer (1)

V2 The maximum amount of heat is evolved in the

S  2.303 nR log reaction HF + NaOH because of high hydration
V1
energy of F– ion due to its small size.
20
S  2.303  2  2 log  9.2 cal K–1 mol–1 50. Answer (2)
2
37. Answer (3) G = H – T S

38. Answer (2) If H is –ve and S also –ve then G will be

negative at low temperature.
39. Answer (1)
51. Answer (3)
Hf = –94 + 2 ×(–68) –(–213) = –17 kcal/mol
S = Ssys + Ssurr
40. Answer (4)
x x 400 x  300 x
1 1 =   =  300  400
300 400
A 2  B 2  AB Hf = –100 kJ mol–1
2 2
100 x x
Let bond enthalpy of A2 be ‘x’. =  300  400 =  kJ
1200

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Hints & Solutions Thermodynamics 33
52. Answer (3) 62. Answer (1)
C (graphite) + O2  CO2 (g) ; H = –393.5 kJ
H CO2  C(diamond) + O2 ; H = +395.4 kJ
C Add. C (graphite)  C(diamond); H =1.9 kJ
H C C H
6C (gr) + 3H2 (g)  =1.9 1000 J = 1900 J
H C C H 63. Answer (4)
C
Burning of hydrocarbon in presence of O2 is called
H combustion.
64. Answer (2)
Theoretical heat of formation,
Fact.
= {6HC (gr)  C (g) + 3EH – 3EC–C – 3EC=C – 6EC–H}
2
65. Answer (3)
= 6r + 3y – 3z – 3p – 6q
Standard enthalpy of formation is defined as the
Resonance energy = Observed heat of formation – enthalpy change when 1 mole compound is
Theoretical heat of formation, formed from the elements in their standard state.
= x – 6r – 3y + 3z + 3p + 6q 66. Answer (4)
53. Answer (1) Work done during free expansion of gas is zero
54. Answer (1) 67. Answer (2)
55. Answer (2) Q = mst
56. Answer (1) 68. Answer (2)
HF = HS + HI.E. + HBD.E. + Hv + 2HEA + Fact
HL.E.
69. Answer (4)
57. Answer (2)
Fact.
Isolated 70. Answer (3)
58. Answer (2) 71. Answer (1)
Internal energy C v = Cs × molar mass = 0.313 J g–1 × 40 g mol–1
59. Answer (1) = 12.52 J mol–1
milli moles of HCl = 500 × 0.1 = 50 R = 8.314 J mol–1
milli moles of NaOH = 200 × 0.2 = 40 Cp = Cv + R = 12.52 J mol–1 + 8.314 J mol–1
HCl + NaOH  NaCl + H2O = 20.834 J mol–1
milli moles 50 40 0 0 Cp 20.834
   1.66
left 10 – 40 40 Cv 12.52
water produced = 40 milli moles = 40 × 10 –3 Hence gas is monoatomic.
moles 72. Answer (2)
1 mole H2O produced heat evolved is 57.2 kJ Fact.
 40 × 10–3 produced heat evolved is 73. Answer (4)
= 57.2 × 40 × 10 –3
H = –ve and TS = +ve, hence G will be always
= 2.288 kJ negative.

60. Answer (3) 74. Answer (3)

Fact
qP = qV + nRT
75. Answer (1)
For the reaction, n = 0
Since system is isolated and work is a path
 qP = q V
function. Thus W irr < W rev . Thus, fall in
61. Answer (3) temperature is less in irreversible process as
Fact. compared to reversible path.

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34 Thermodynamics Hints & Solutions

76. Answer (4) 89. Answer (4)

HNO3 + NaOH  NaNO3 + H2O Fact
1 mol 1mol 90. Answer (1)
0.2 mol 0.2 mol Q = mst 10 dm3 = 10 L = 10,000 g
= 10000 × 4.18 × 70
Heat of neutralisation = 0.2 × 57 kJ
Q = 2926 kJ
= 11.4 kJ
Moles of butane required
77. Answer (4)
2926
= 57.1 × 0.05 = 2.855 kJ =  1.045 mol
2.8  103
78. Answer (2) 91. Answer (1)
1 15
2Cu(s) + O (g) Cu2O(s) C6H6(l)  O2(g)  6CO2(g)  3H2O(l)
2 2
2
339.3 × 2 249.2
n = 6 – 7.5 = –1.5
2Cu(g) O(g) H = U + nRT
2 × 750 –141.4 x – y = –1.5 RT
92. Answer (2)
 (–)
2Cu (g) O (g) G = H – TS
+790.8 G = 0
–– H = T S
O (g)
H 50.50  1000 J
T= =  505 K  232C
S 100 J
 678.6 + 1500 + 249.2 – 141.4 + 790.8 + L.E.
93. Answer (2)
= –166.7 Fact
 L.E. = –3243.9 kJ/mol 94. Answer (4)
79. Answer (4) Higher the temperature higher will be randomness.
80. Answer (3) 95. Answer (1)
Volume is constant. Fact.
81. Answer (3) 96. Answer (1)
Hydration energy of F– ion is high due to small U = q + W; –PV = – 1(0.5 L) atm
size U = q + PV = – 0.5 × 101.35
82. Answer (4) U = 300 – 50.67 = – 50.67 J
U = 249.3 J
H2O(l)  H2O(g) H = y kJ
97. Answer (3)
y = –x – Hf of H2O(l)
83. Answer (1) H2SO 4  2H  SO2–
4

Fact 2H  2OH  2H2O

84. Answer (1) 98. Answer (2)
Fact Extensive properties depends upon mass.
85. Answer (1) 99. Answer (2)
STotal = –Ssystem + Ssurrounding MSO4.5H2O
86. Answer (2) H1 = ? H2 = 2.8
87. Answer (4)
Fact MSO4 MSO4 (aq)
H = 15.9
88. Answer (4) H = H1 + H2
Apply G = H – TS H1 = H – H2 = –15.9 – (2.8) = –18.7 kcal
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Hints & Solutions Thermodynamics 35
100. Answer (3) 115. Answer (2)
Expansion of gas in vacuum is called free expansion. 116. Answer (3)
101. Answer (2) Elements in their standard form is having zero heat
of formation.
ΔG= ΔH – TΔS
117. Answer (2)
=+ve – T ( ΔS )
+ve 1
X2 + 2Y2  XY4
2
For spontaneous, G < 0, H < TS
1 °
102. Answer (1) S°reaction = S°XY4 – S X2 – 2S°Y2
2
Fact.
1
103. Answer (1) = 110 –  30  2  60
2
Factual = 110 – 15 – 120  – 25 JK –1 mole –1
104. Answer (3)
ΔG = ΔH – TΔS = 0
Factual
ΔH –40  1000
105. Answer (4) T=   1600 K
ΔS –25
Factual 118. Answer (4)
106. Answer (2) Fact
Factual 119. Answer (4)
107. Answer (4) Fact
Cyclic process, work done 0 120. Answer (4)
108. Answer (1) 121. Answer (1)

1
H  H  O  O  H  O
2 | + H2  H2
H
Observed value = 3 × H2
x
Hf = z   2y
2
109. Answer (3) + 3H2  H1
110. Answer (1)
Resonance energy = –3H2 + H1
111. Answer (4)
122. Answer (2)
For Isothermal reversible expansion, H = 0
At equilibrium G = 0
112. Answer (4)
H = TS
G = H – TS
H 30
113. Answer (4) T   428.57
S 0.07
Fact.
123. Answer (2)
114. Answer (1)
H H
2H2O 2H2 + O2 N–N H – N = N – H + (H – H)
H H
2×22.4 L 22.4 L
36 g H2O 67.2 L gas produced H = B.ER – B.EP
109 = 4 × 391 + 163 – [x + 2 × 391 + 436]
67.2
100 g H2O   100  186.6 L = 1564 + 163 – [x + 782 + 436]
36
109 = 1727 – [x + 1218]
Work = –PV
109 = 509 – x
= –1 × 186.6 × 101.3 J = –18909 J
= –18.9 kJ –19 kJ  x = 400 kJ/mole

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36 Thermodynamics Hints & Solutions

124. Answer (2) 134. Answer (1)

C2H4 + 3O2 2CO2(g) + 2H2O (g) H = –1411 kJ V 
W  2.303nRT log  2 
∵ 1411 kJ heat is evolved by 3 mol O2  V1 
3  20 
 6226 kJ heat is evolved   6226 mol  2.303  3  8.31 300 log  
1411  2 
= 13.23 mol = –17224.13 J = –17.2 kJ
= 13.23 × 6 × 1023 × 2 atom 135. Answer (4)
= 26.46 NA H+ + OH–  H2O is a neutralisation reaction.

125. Answer (4) 136. Answer (2)

137. Answer (2)
126. Answer (2)
H = U + nRT
Desired equation could be got by subtracting
equation 2 from one. 1
 742.7  8.314  10 3  298
127. Answer (4) 2
= – 742.7 – 1.238
Fact
= – 743.9 kJ
128. Answer (1)
138. Answer (2)
129. Answer (2)
Fact
(i) CCl4 (l)  CCl4 (g); H = 30.5 kJ/mol
139. Answer (1)
(ii) C(s) + 2Cl2(g)  CCl4 (l); H = – 135.5 kJ/mol Fact
(iii) C(s)  C(g); H = 715 kJ/mol 140. Answer (4)
(iv) Cl2(g)  2Cl(g); H = 242 kJ/mol Fact
To find CCl4 (g)  C(g) + 4Cl(g); H = ? 141. Answer (4)
Eq. (iii) + 2[eq. iv] – eq. (i) – eq. (ii) W = –PV
H = 715 + 2(242) – 30.5 – (– 135.5) = –1 × (5 – 2) × 101.3 J
= 1304 kJ/mol = –304 J
Bond enthalpy of C – Cl in CCl4 142. Answer (3)
Fact
1304
  326 kJ / mol 143. Answer (1)
4
144. Answer (2)
130. Answer (2)
Under such conditions G is always negative. H2  Cl2  2HCl
131. Answer (3)
Hf 
 BE (Reactant)   BE (Product)
Fact 2
132. Answer (2)
x  y  2z
133. Answer (1) =
2
1 = 0.5x + 0.5y – z
CO(g)  O2(g)  CO2(g)
2 145. Answer (2)

1 1 146. Answer (4)

n  1  1 
2 2 Fact
H = E + nRT 147. Answer (3)
Fact
1 8.314
H  283.3    290 = – 284.5 kJ 148. Answer (3)
2 1000

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Hints & Solutions Thermodynamics 37
149. Answer (2)
SECTION - B
150. Answer (4)
1. Answer (2)
Fact
151. Answer (4) 2. Answer (3)
152. Answer (3) 3. Answer (3)
153. Answer (3) 4. Answer (2)
154. Answer (3) 5. Answer (2)
C + O2 CO2 ; H° = – aJ
Fact.
1 b 6. Answer (3)
CO + O CO2 ; H° = – J
2 2 2
7. Answer (3)
– – – +
8. Answer (3)
1 (b – 2a)
C + O CO ; H° = 9. Answer (1)
2 2 2
155. Answer (3) Fact
1 g 2.2 kcal 10. Answer (2)
126 g 2.2 × 126 kcal = 277.2 kcal Fact
156. Answer (4) 11. Answer (4)
Fact The chemical change involving breaking and
157. Answer (4) making of equal number of similar bonds has
Fact H = 0.
158. Answer (1) 12. Answer (3)
159. Answer (2) Factual
At equilibrium G = 0 13. Answer (1)
H = TS
Factual
H 179.1 1000 14. Answer (2)
T  = 1118 K
S 160.2
15. Answer (2)
160. Answer (2)
At high pressure equilibrium shift towards melting
PCl5(g)  PCl3(g) + Cl2(g) of ice.
1-0.5 0.5 0.5
16. Answer (4)
0.5  0.5  1.5 1 Enthalpy of formation is given for the formation of
 Kp  
1.5  1.5  0.5 3 1 mole of compound.
 G = – RT ln Kp 17. Answer (3)
1 Density of ice is less than that of water.
= – R × 300 × ln
3 18. Answer (3)
= + 300R ln3
Enthalpy of formation of an element in its standard
161. Answer (1) form is zero.
U° = H° – TS°
19. Answer (1)
–2.303 RT log K = H° – TS°
20. Answer (1)
H° S° G = H – TS; at higher temperature ;
–2.303 log K = 
RT R
H < TS.

‰‰‰

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