Thermodynamics and Thermochemistry 439

Free energy and Work function

Heat of reaction
1 d 2 b 3 a 4 b 5 acd
1 b 2 b 3 d 4 d 5 d
6 c 7 c 8 c 9 a 10 a
6 b 7 c 8 a 9 b 10 a
11 d 12 a 13 d 14 d 15 b
11 bcd 12 a 13 d 14 b 15 c
16 d 17 b 18 c 19 d 20 b
16 a 17 b 18 a 19 b 20 c
21 b 22 d 23 b 24 a 25 d
21 c 22 a 23 d 24 c 25 c
26 d 27 a 28 d
26 b 27 b 28 b 29 a 30 c

31 a 32 a 33 d 34 b 35 b Critical Thinking Questions

36 a 37 a 38 d 39 b 40 b
1 b 2 c 3 d 4 b 5 b
41 c 42 c 43 b 44 b 45 b
6 d 7 d 8 b 9 a 10 a
46 b 47 a 48 c 49 e 50 b
11 a 12 c 13 c 14 a 15 a
51 a 52 b 53 c 54 c 55 b 16 a 17 a 18 d 19 b 20 a
56 c 57 c 58 d 59 c 60 b 21 b 22 c 23 c 24 b 25 b
61 d 62 c 63 b 64 a 65 b 26 b 27 e 28 d 29 a 30 c
66 b 67 a 68 c 69 a 70 d 31 a 32 c 33 d 34 ac 35 a
71 a 72 b 73 d 74 c 75 b 36 b 37 c 38 b 39 c 40 a

76 b 77 a 78 d 79 d 80 a 41 b 42 a 43 a 44 a 45 d

81 b 82 b 83 a 84 b 85 b 46 d 47 d 48 b 49 d 50 d

86 c 87 a 88 b 89 d 90 d 51 b 52 a

91 a 92 c 93 b 94 a 95 d
Assertion & Reason
96 d 97 c 98 a 99 c 100 c

101 b 102 c 103 d 104 d 105 c 1 b 2 b 3 b 4 c 5 a

106 a 107 c 108 d 109 d 110 c 6 b 7 b 8 a 9 b 10 a

11 a 12 d 13 a 14 e 15 c
111 a 112 b 113 a 114 a 115 a
16 a 17 c 18 b 19 a 20 e
116 a 117 b 118 c 119 b 120 a
21 c 22 c
121 a 122 a 123 d 124 b 125 b

126 b 127 c 128 d 129 d 130 b

131 d 132 b 133 d 134 a 135 a

136 a 137 d 138 c 139 d 140 b

141 c 142 d 143 c 144 b 145 c

146 d 147 b 148 c 149 b 150 b

151 d 152 a 153 b 154 b 155 b

Basic concepts
156 b 157 a 158 d 159 c 160 d 1. (b) Internal energy of an ideal gas is a function of temperature
only.
161 a 162 c 163 c 164 c 165 c
2. (d) In cyclic process, a system in a given state goes through a
166 b 167 d 168 d 169 c 170 b series of different processes, but in the end returns to its initial
171 a 172 c state.
4. (c) E  0 for isothermal reversible cycle.
Bond energy 5. (c) In isolated system neither exchange of matter nor exchange of
energy is possible with surroundings.

1 b 2 a 3 a 4 d 5 c
9. (c) It is the definition of calorific value.
11. (d) When a real gas is forced through a porous plug into a region
6 c 7 b 8 d 9 b 10 b of low pressure, it is found that due to expansion, the gas on
the side of low pressure gets cooled.
 440 Thermodynamics and Thermochemistry
The phenomenon of producing lowering of temperature when H  E  PV  E  nRT  0  0  0 .
a gas is made to expand adiabatically from a region of high
pressure into a region of low pressure is known as Joule- V2
18. (b) W  2 .303 nRT log
Thomson effect. V1
12. (d) In isothermal reversible process ideal gas has constant volume
20
and so E  0 and H  E  0 .  2.303  1  8.314  10 7  298 log
13. (a) The compressor has to run for longer time releasing more heat 10
to the surroundings.  298  10 7  8.314  2.303 log 2 .
14. (c) This is based on Joule-Thomson effect.
15. (b) Enthalpy is an extensive property. 20. (a) The enthalpies of all elements in their standard state at
16. (b) dV  0 for an isochoric process. 25 o C or 298K are zero.
17. (d) Total energy of an isolated system is constant. 21. (c) E  E P  E R .
v
18. (a) For isochoric process V  0 so q  E i.e. heat given to 22. (c) E  q  w .
v
a system under constant volume is used up in increasing E . 23. (a) E = 0 for reversible isothermal process.
19. (b) The less energy of a system and more is its stability. 25. (b) Hess law includes initial reactants and final products.
20. (b) The functions whose value depends only on the state of a
system are known as state functions. 26. (a) At constant T and P internal energy of ideal gas remains
unaffected.
21. (d) For adiabatic process q  0 .
27. (a) E increases with temperature.
22. (b) The intensive property is mass/volume.
28. (a) H  E  W or H  E  PV .
23. (c) Volume is not an intensive property.
24. (c) An isolated system neither shows exchange of heat nor matter 29. (bc) Heat of neutralisation of a strong acid and strong base is equal
with surroundings. to 13.7 kcal .
25. (d) Q is not a state function. p1
30. (c)  W   2.303 nRT log
26. (c) For adiabatic process Q  0 . p2
27. (c) Work is not a state function as during a process its value
depends on the path followed. The value of enthalpy, internal 10
W  2.303  1  2  300 log  1381.8 cal.
energy and entropy depends on the state and not on the path 1
followed to get that state, hence these are state functions. 31. (b) Joule-Thomson expansion is isoenthalpic.
28. (c) Surface tension is an intensive property which do not depend 32. (c) Here n  0 so, E  H .
upon the quantity of matter present in the system.
33. (b) q  E  W if q  0 for adiabatic process, than E  W .
First law of thermodynamics and Hess law 34. (a) For this reaction n  0 than E  H .
35. (c) As the system is closed and insulated no heat enter or leave the
1. (d) First low of thermodynamics is also known as Law of system, i.e. q  0 ;  E  Q  W  W .
conservation of mass and energy. 37. (c) H  E  nRT ; n  3
2. (b) Formation of CO 2 from CO is an exothermic reaction; heat so, H  E  3 RT .
is evolved from the system, i.e., energy is lowered. Thus, 38. (b) According to Hess’s law. The heat of reaction depends upon
exothermic reactions occur spontaneously on account of initial and final conditions of reactants.
decrease in enthapy of system. Thus, E  H .
39. (d) H  E  nRT
4. (b) H  E  PV .
also, 2 NH 3(g)  N 2(g)  3 H 2(g)
3 1
5. (c) n  1   , As n is negative, thus H  E . n  2 .
g 2 2 g
6. (a) Bomb calorimeter is commonly used to find the heat of 40. (c) n  0 for this reaction so, E  H .
combustion of organic substances which consists of a sealed 41. (d) W = 0 is not true.
combustion chamber, called a bomb. If a process is run in a P
sealed container then no expansion or compression is allowed, 42. (a) W  2 .303 nRT log 2
P1
so w = 0 and ∆U = q.
∆U < 0, w = 0 10
 2.303  1  2  300 log  965.84
9. (b) H  E  nRT 2
Since n  2 at constant temperature, E  0.
Than H  E  2 RT . E  q  w ; q  w  965.84 cal .
10. (d) If n  ve than H  E . 43. (c) q  40 J
12. (c) Hess’s law is an application of first law of thermodynamics . w  8 J (work done by the system)
13. (c) At constant P or T E  q  w  40  8  32 J .
H  U  nRT  n  n p  n R  2  4  2 44. (a) We know that E  Q  W  600  (300)  300 J
 H  U . W  300 , because the work done by the system.
45. (c) Given that
16. (b) It is a combustion reaction, H   ve .
P1  10 atm , P2  1 atm , T  300 K , n  1
17. (c) During isothermal expansion of ideal gas, T  0
 Thermodynamics and Thermochemistry 441

R  8.314 J / K / mol Thus, we can say that internal energy is partly potential and
partly kinetic.
Now, by using
P2 56. (b) N 2 (g)  O2 (g)  2 NO(g) ; ng  2  2  0
W  2 .303 nRT log10
P1 H  E  ng RT ; H  E  0 ; H  E
1 (d) W   pV ; W  3  (6  4 )
 2.303  1  8.314  300 log10 57.
10
W  6  101.32 ( 1 L atm  101.32 J )
W  5744.1 Joule
46. (c) We know that internal energy of a gas depends upon its W  608 J
pressure and temperature. Thus if a gas expands at constant
temperature and pressure, then its internal energy remains 58. (d) A(s)  3 B(g)  4 C(s)  D(l)
same. ng  0  3  3 ; H  E  ngRT [ E  U]
47. (b) PCl5 (g)  PCl3 (g)  Cl 2 (g)
 H  U  (3)(RT )
For this reaction ng  2  1  1
H  U  3 (RT ) ; H  U  3 RT
ng is positive, i.e., there is an increase in the number of
gaseous moles then H  E
48. (c) Enthalpy (H ) is defined as the sum of internal energy
IInd & IIIrd Law of thermodynamics and Entropy
E  PV , H  E  PV .
2. (d) When S  ve the change is spontaneous.
49. (d) (CH 3 )2 C  CH 2 (g)  6O2 (g)  4 CO 2 (g)  4 H 2 O(l)
3. (d) Heat is always flow from the higher to lower temperature.
ng  4  6  2 (i.e., negative) 4. (b) Mixing of non-reacting gases increases randomness and so
we know that H  E  ngRT increase entropy .
 E  (ng)RT ( ng  ve ) 5. (b) Entropy of the system increases as the process occur
irreversibly and isothermally in an isolated system.
 H  E
50. (b) Given number of moles =1 6. (d) S o  2S HCl
o
 (S Ho 2  S Cl
o
2
)
Initial temperature  27 o C  300 K  2  186.7  (130.6  223.0)  19.8 JK 1mol 1
Work done by the system  3 KJ  3000 K
9. (b) For adiabatic expansion q  0 than according to following
It will be () because work is done by the system.
q
Heat capacity at constant volume (Cv )  20 J / k relation S  , S  0 .
T
We know that work done 10. (c) It is the third law of thermodynamics.
W  nCV (T2  T1 ) ; 3000  1  20 (T2  300) 11. (c) Entropy of gases is highest.
3000  20T2  6000 12. (c) G  H  TS
3000 for spontaneous process G should be negative in option (3)
20T2  3000 ; T2   150 K H  ve and ΔS  ve than
20
51. (a) Internal energy of a system is a state function and extensive G  (ve )  T (ve )   ve
property and is independent of the path by which it is
obtained. 15. (c) For reverse reaction sign will be change.
52. (d) N 2 O4 (g)  2 NO 2 (g) 16. (b) Solid  Gas, S is maximum.
For this reaction ng  2  1  1 17. (d)  ve H and  ve S both oppose the reaction.
ng is positive i.e., there is an increase in the number of 18. (a) S  186.5 / 373  0.5 JK 1 mol 1 .
vap
gaseous moles then H  E
53. (b) 2C  O2  2CO ; H  220 KJ 20. (a) When H = –ve, S = +ve and G = –ve than reaction is
spontaneous .
This reaction does not represent complete combustion of 21. (d) For endothermic process S increases.
carbon, hence heat of combustion of carbon will not be equal 22. (c) Calculation of change in entropy is done at constant
to 110 kJ . The negative sign of H indicates that this temperature and pressure both.
reaction is exothermic. Also, despite being spontaneous 23. (a) When the value of entropy is greater, then ability of work is
reaction, it requires initiation. maximum.
54. (c) W  PV  1  10 5 (1  10 2  1  10 3 ) 24. (d) At equilibrium, G = 0
Hence 0 = H  TS or H  TS .
 1  10 5  9  10 3  900 J H
vap 37.3 KJ mol 1
55. (a) The exact value of internal energy is not known as it includes 25. (c) S vap  
all type of energies of molecules constituting the given mass of T 373 K
matter such as translational, vibrational, rotational. The kinetic
& potential energy of the nuclei & electron with in the  0.1 kJ mol 1 K 1  100 J mol 1 K 1 .
individual molecules and the manner in which the molecule are 26. (d) Solid  Liquid, S increases .
linked together etc.
27. (c) S  ve than process is spontaneous.
E  Etranslational  Erotational  Evibrational 28. (b) S  ve than the system is more disordered.
29. (c) Because solid  solid, S is same and H is –ve.
 442 Thermodynamics and Thermochemistry
H 3 5
vap 386 RT  RT
30. (b) S    1 .2 kJ . 2 2
vap T 298 Thus for mixture of 1 mole each, Cv  and
2
31. (b) Processes (a) and (c) take place with the increase of no. of
5 7
moles of gaseous species and hence the disorder or entropy RT  RT
increases. (b) on increasing pressure, disorder or randomness Cp  2 2
decreases and so also the entropy (d) is endothermic process 2
and S is positive. 3 RT
32. (d) This is the statement of third law of thermodynamics. Therefore, C p / Cv   1 .5 .
2 RT
33. (d) For isothermal expansion of ideal gas, E  0 .
q
(900  18) 51. (c) S  rev  unit of S is JK 1mol 1 .
34. (a) S   43.4 JK 1 mol 1 . T
vap 373
H vap
35. (c) Entropy of the mixture increases due to increase in impurity. 52. (b) H 2 O(l) ⇌ H 2 O(g) , S  ,
37. (c) If H   ve and S   ve than the reaction is non- T
spontaneous i.e. can not occur. H vap.  2.257 KJ / g
38. (a) T2  150  273  423 K or H vap  2.257  18 kJ / mol.  40.7 KJ / mol
T1  25  273  298 K
40.7
Q  500 K hence, S   0.109 kJ /mol/K.
373
W T2  T1  423  298  53. (a) Liquid  Vapour, entropy increases.
 ; W  500   147.7 J .
Q T2  423  54. (c) NaNO 3 is a solid, which is converted to liquid ions.
39. (c) According to III law of thermodynamics.
75
40. (c) When H  ve and S  ve reaction is non- 55. (c) Heat capacity of water per gram   4 .17 J
spontaneous. 18
H fusion 9.2 Q  mst ; 1000  100  4.17  t
41. (c) Tm    1150 K .
S fusion 0 .008 1000
t  2 .4 K .
42. (c) Here: Change in 100  4 .17
Volume (V )  500  300  200cc  0.2 litre, 56. (c) As the work is done on system, it will be positive
i.e. W  462 joule, E  128 joule (heat is evolving)
Pressure (P)  0.6 atm and heat liberated (q) = 10J
From the I law of thermodynamics
st

Work done (W )  PV  (0.2  0.6)  0.12 litre atm E  q  w  (128)  (462)  334 Joules.
But 1 litre atm  101.3 J . 57. (a) Gases show highest entropy.
hence W  0.12  101.3  12.156 J . We also know that 58. (b) H  (aq )  OH  (aq )  H 2 O(l)
S o (298 K )K mol 1 10 .7 70
heat is liberated, therefore it would be negative. Thus change in
E  q  W  10  12.16  2.16 J . S (298 K)  S P  S R  70  (10.7  0)
o

43. (c) Formation of CO 2 is, 80.7 JK 1 mol 1

C(s)  O 2(g)  CO 2(g) heat of vaporis ation
59. (d) The entropy change 
S  213.5  5.690  205  2.81 JK
o 1
. temperatur e
Here, heat of vaporisation  540 cal / gm
45. (b) H 2 O(g) ⇌ H 2 O(l)
 540  18 cal mol 1
we know G  H  TS
Temperature of water  100  273  373 K
at equilibrium G  0
540  18
Therefore H  TS .  entropy change   26.06 cal mol 1 K 1
373
46. (a) We know that work done, W  Cv (T1  T2 )
60. (b) Given that, T1  500 K, T2  300 K
3  1000  20 (300  T2 ) ;  3000  6000  20 T2 T1  T2 500  300 200
By using,      0 .4 .
3000 T1 500 500
 T2   150 K .
20 61. (b) It is molar heat capacity.
48. (d) It does not violates the first law of thermodynamics but violates 62. (d) Entropy is the measure of randomness in the molecules.
the II law of thermodynamics. Randomness is maximum in case of gases. Hence, entropy is
maximum for water vapours.
3 5
49. (d) Cv  RT ; C p  RT for monoatomic gas 63. (a) Standard entropy of formation of CO 2 (g) = standard entropy
2 2
of CO 2 (g)  [Standard entropy of C(s)  standard entropy of
5 7
Cv  RT; C p  RT for diatomic gas O 2 (g ) ]
2 2
 213.5  [5.740  205]  2.76 J / K .
 Thermodynamics and Thermochemistry 443
64. (c) Third law of thermodynamics help in calculating entropy of 15. (c) H  ve for exothermic reaction.
different temperatures.
65. (a) In case of gas randomness is maximum therefore entropy is H  ve for endothermic reaction
maximum in case of steam. Enthalpy of fusion is + ve.
66. (c) S system  S surroundin gs  O (for spontaneity) 16. (a) Heat of neutralisation will be less than
57.33 kJ / mole because some amount of this energy will
V2
Because of S  R ln be required for the dissociation of weak base (MgO)
V1
Here the volume of gas increase from V1 to V2 at constant 18. (a) H 2  O2  H 2 O2 H of  188 kJ / mole ….(i)
temperature T. 1
The total increase in entropy of the system and its surrounding H2  O 2  H 2 O H of  286 kJ / mole ….(ii)
2
during the spontaneous process of expansion considered above
eq. (i) – eq. (ii) × 2 gives the required result.
V 
is, thus R ln  2  since V2  V1 it is obvious that the 19. (b) Graphite  diamond H  (x  y) kJ mol 1 .
 V1  t
spontaneous (irreversible) isothermal expansion of a gas is 21. (c) Heats of combustions are always exothermic except oxidation of
accompanied by an increase in the entropy of the system and N as,
its surrounding considered together. 1
S system  S surroundin gs  0 . N2  O 2  N 2 O H   ve
2
67. (b) G  H  TS N 2  O2  2 NO H   ve
at constant temperature and pressure G  0
22. (a) For exothermic reactions H p  H R .
0  T  TS so H  TS
dQrev. 30  10 3 For endothermic reactions H p  H R .
68. (b) dS  ; T ; T  400 K
T 75 23. (d) Aim: 2C  H 2(g)  C 2 H 2(g) .

Heat of reaction eq. (ii) + eq. (iii)  eq. (iv) – eq. (i)
find the required result.
1. (b) C  O2  CO 2  94.2 Kcal. …..(i) 24. (c) Enthalpy of formation of HCl.
25. (c) Heat of neutralisation between strong acid and a strong base is
1
H2  O 2  H 2 O  68.3 Kcal. ….(ii) about 13.7 Kcal.
2
On multiplication of eq. (ii) by 2 and than adding in eq. (i) 26. (b) For endothermic reaction, H  ve .
27. (b) Heat of neutralisation is less than 56.1 Kcal when a strong base
C  2 H 2  2O2  CO 2  2 H 2 O  230.8 Kcal …(iii) and a weak acid reacts.
On subtracting eq. (iii) by following eq. 1
28. (b) Aim: CO  O 2  CO 2
CH 4  2O2  CO 2  2 H 2 O  210.8 Kcal. we get, 2
C  2 H 2  CH 4 H  20 Kcal.  1 
H  H 0f (CO 2 )  H 0f (CO )  H 0f (O 2 )
2. (b) S  16 J mole K 1 1  2 
  94.0  (26.4)  67.6 kcal.
H vapour 6  1000
Tb . p .    375 K 29. (a)
S vapour 16
1
4. (d) Heat of neutralisation between strong acid and a strong base is (i) H2  O2  H 2 O, H  241 kJ
2
about 13.7 Kcal.
17
6. (b) Effect of temperature in heat of reaction is given by Kirchoff’s (ii) C6 H10  O2  6 CO 2  5 H 2 O, H  3800 kJ
equation. 2
7. (c) Heat of neutralisation between strong acid and a strong base is (iii) C6 H12  9O2  6CO 2  6 H 2O, H  3920 kJ
about 13.7 Kcal. C6 H10  H 2  C6 H12
8. (a) For exothermic reactions H p  H R . Eq. (i) + Eq. (ii) – Eq. (iii)
For endothermic reactions H p  H R . H  241  3800  (3920)
9. (b) 78g of benzene on combustion produces  4041  3920  121 kJ
heat = – 3264.6 kJ 30. (c) NH 4 OH is a weak base. Heat of neutralisation < 13.7kcal.
3264.6
 39 g will produce   1632.3 kJ . 31. (a) CH 4 is the best fuel because its calorific value
2
212.8
10. (a) eq. (i ) + eq. (ii ) gives the required result.   13.3 kcal / g is higher among the other gases.
11. (bcd) (b,c,d) are endothermic reactions because they proceeds by 16
the absorption of heat. 32. (a) Find H for CH 4  2O2  CO 2  2 H 2 O .
(g)
12. (a) Change of liquid to vapour takes energy in the form of heat so
it is endothermic reaction. 34. (b) In neutralisation of a strong acid and base only H  and OH 
13. (d) In exothermic reactions heat is evolute. ions react.
 444 Thermodynamics and Thermochemistry
35. (b) When both acid and base are strong than heat of neutralisation 1 1
63. (b) Aim: K(S )  O2  H  KOH (S )
is 57.1 kJ mol 1 . 2 (g) 2 2(g)
eq. (ii) + eq. (i) – eq. (iii) gives
7
36. (a) C2 H 6  O 2  2CO 2  3 H 2 O substitute the values. H  48  (68.39)  (14)  68.39  48  14 .
2 64. (a) By definition of heat of formation.
37. (a) Decomposition is an endothermic process. 68. (c) C D  CG , H  453.5 cal.
38. (d) H for this reaction is Heat of reaction.
i.e. energy of C G is less and thus more stable.
40. (b) One mole of H 2 O is formed from its initial components.
69. (a) H combustion is always negative .
41. (c) One mole of a substance is completely oxidized in air.
70. (d) H reaction  H 0f (N 2 O4 )  2H 0f (NO 2 )
42. (c) S (rhombic)  O2  SO 2 , H  70960 cal. …(i)
 2  2 (8)  14 kcal.
S (monoclinic)  O2  SO 2 H  71030 cal …(ii)
71. (a) H  E  nRT  3  8.314  298
Aim: S (rhombic)  S (monoclinic)
 7432 J  7.43 kJ .
eq. (i) – eq. (ii) gives the required result.
43. (b) When H 2 O is convert to form H 2 O , heat is absorbed 72. (b) Aim: C  C(diamond) ; eq. (i) – (ii) gives the result.
(l) (g ) (graphite)
73. (d) In the formation of a compound, more the heat absorbed, less
hence H1  H 2 . stable is the compound.
44. (b) Out of given substances, kerosene oil has maximum calorific 74. (c) C(graphite)  2 H 2(g)  CH 4 (g) .
value.
75. (b) Heat of formation is the formation of one mole of the
45. (b) C(S )  O2(g)  CO 2 (g) , n  1  1  0 substance from its elements.
g
76. (b) H (reaction)  2H 0f (MgO)  H 0f (SiO2 )
 E  H  94 kcal
 2 ( 34.7)  ( 48.4 )  21 kJ .
E  ECO 2  (EC  EO2 )  ECO 2  (0  0)
77. (a) eq. (i) + eq. (ii) + eq. (iii) gives
or ECO 2  E  94 kcal. X  131  282  242   393 kJ .
46. (b) 0.2 mole will neutralize 0.2 mole of HNO 3 , heat evolved 78. (d) It is the definition of heat of transition.
 57  0.2  11.4 kJ . 79. (d) C(graphite)  C(diamond ), H  1.9 kJ
47. (a) Suppose heat evolved in I case is Q1 and that in the II case it
st nd
C(graphite)  O2  CO 2 , H  H1
1
is Q 2 . Then Q 2  Q1. C(diamond )  O2  CO 2 , H  H 2
2
(  H1 )  (  H 2 )  1.9 kJ or H 2  H1  1.9
But Q1  1000 T1 and Q2  500 T2
For combustion of 6 g, H 2  H1 by 1.9 / 2  0.95 kJ .
1
 500 T2   1000 T1 i.e. T2  T1 .
2 80. (a) H product  H reactant for exothermic reaction.
48. (c) Enthalpy of a compound = Heat of reaction of that compound. 81. (b) Due to high electron affinity of Cl the highest energy is
49. (e) It is the definition of heat of neutralization. evolved.
50. (b) H   ve for exothermic compound.
82. (b) CH 4  2O2  CO 2  2 H 2 O
51. (a) If acid or base or both are strong, heat of neutralization
 13.7 kcal. Molecular weight of CH 4  12  4  16
52. (b) Both NH 4 OH and CH 3 COOH are weak.  On the combustion of 2.0gm of methane = 25.0 kcal
53. (c) 57.1  0.25  14.3 kJ mol 1 .  On the combustion of 16.0 gm  25  16  200 kcal.
2
54. (c) Heat of formation is for 1 mole.
Hence H 0f (HI)  12.40 / 2  6.20 kcal. 83. (a) CH 4  2O2  CO 2  2 H 2 O .
55. (b) Chemical dissociations are reversible and endothermic. 84. (b) C2 H 4  3O2  2CO 2  2 H 2 O
57. (c) Given,
(i) CH 4  2O2  CO 2  2 H 2 O , H  20 kcal H reaction  [2  H of (CO 2 )  2  H of (H 2 O)]
(ii) C  O2  CO 2 , H  40 kcal.  [H of (C 2 H 4 )  3  H of (O2 )]
1
(iii) H 2  O 2  H 2 O , H  10 kcal.  [ 2 (  394)  2 (  286)]  [52  0]  1412 kJ .
2
Aim: C  2 H 2  CH 4 85. (b) C  O2  CO 2  394 kJ .
(ii) + 2 × (iii) – (i) gives. 2C  2O2  2CO 2  788 kJ ….(i)
H  40  2 (10)  ( 20)  80 kcal.
58. (d) For exothermic reaction heat is evolved. 2CO  O2  2CO 2  569 kJ ….(ii)

59. (c)
electrolysis
H 2 O  H 2(g)  O 2(g) .
1 2CO 2  2CO  O2  569 kJ …..(iii)
(l) 2 eq. (i) + eq. (iii) = –109.5 kJ mol .
–1

61. (d) All other are combustion phenomena.

H 44
62. (c) combusion = –ve, so exothermic process. 86. (c) H f  kcal  22 kcal .
2
 Thermodynamics and Thermochemistry 445

87. (a) CaO  H 2 O  Ca (OH )2 is exothermic.

(s) (l)
 32 gm of sulphur on burning produce 64 gm.. of SO 2

88. (b) H  ve in exothermic reaction.  H  (  4.6 kJ )  64   294.4 kJ .

89. (d) According to the definition of heat of formation. 111. (a) 3O 2 ⇌ 2O 3 – energy is given out.
90. (d) Multiplying eq. (ii) by (iii) and eq. (iii) by (vi), and then add 72  1.6
15
112. (b) H per 1.6 g   0.64 kcal .
6 C  3H 2  O 2  6 CO 2  6 H 2 O; H  3218.7 180
2 113. (a) C  O2  CO 2 , H  394 kJ …..(i)
Subtract eq. (i) from the above equation and find the required
result. 2 H 2  O2  2 H 2 O, H  568 kJ ….(ii)
91. (a) HF is more stable than HCl. CH 4  2O2  CO 2  2 H 2 O, H  892 kJ …..(iii)
92. (c) H ( H P  H R )  q p . (i) + (ii) – (iii) and find the required result.

93. (b) H  ve for endothermic reaction. 115. (a) No doubt heat evolved during neutralisation of 250 cm 3 of
each acid and base is five time the heat evolved during
13.95  44
94. (a) H   278.7 kcal . neutralisation of 50 cm 3 of each acid and base but the
2 .2016
quantity if solution taking heat is also five time thus same
95. (d) eq. (i) + eq. (ii) gives the required result.
temperature rise is noticed.
96. (d) Standard molar heat enthalpy (H o ) of a compound is equal to 1
its standard heat of formation from most stable states of initial 116. (a) H2  O 2  H 2 O(l) ; H  285.8 KJ
2
components.
97. (c) In the complete combustion of butanol H  E . H 2 O(l)  H 2 O(g) ; H  44 KJ
98. (a) X – Y and find the required result. 1
 H2  O 2  H 2 O(g) ; H o  241.8 KJ
99. (c) S  O2  SO 2 H  298.2 kJ ….(i) 2
1 117. (b) Given: Weight of iron burnt  4 g; Heat liberated
SO 2  O 2  SO 3 H  98.2 kJ ….(ii)
2  29.28 KJ and atomic weight of iron (Fe)  56 . We know
eq. (i) – (ii) and find the required result. that in ferric oxide (Fe2 O3 ), 2 moles of iron or
100. (c) C  2S  CS 2 H  ?
2  56  112 gram of iron are burnt. We also know that
C  O2  CO 2 H  393.3 kJ ….(i) when 4grams of iron are burnt, then heat liberated =
S  O2  SO 2 H  293.72 kJ …..(ii) 29.28 kJ, therefore when 112 grams of the iron are burnt,
CS 2  3O2  CO 2  2SO 2 H  1108.76 kJ …..(iii) 29.28  112
then heat liberated   819.8 kJ (Minus sign
eq. (ii) × 2 + eq. (i) – (iv) eq. (iii) – eq. (iv) and find required 4
result . due to liberation of heat).
101. (b) Fermentation is exothermic reaction.
118. (c) H   OH   H 2 O, H neutralization  13.7 kcal .
102. (c) CH 4  2O2  CO 2  2 H 2 O .
3.77  56
103. (d) Use H  E  n RT 119. (b) H / mole of FeS   100.5 .
2 .1
H  19  2  2  10 3  300  20.2 kcal ; n  2 . 194
120. (a) Heat of formation   97 kJ .
1 2
104. (d)  20.6  8.8 KJ mol  29.4 kJ .
106. (a) Subtract equation (ii) from (i). 121. (a) H  H ioniz  H neu =  50.6  H ioniz  (55.9)
107. (c) CH 4  2O2  CO 2  2 H 2 O, H   890.4 kJ ….(i) H ioniz   5.3 kJ / mol .
C  O2  CO 2 , H   395.5 kJ …..(ii) 122. (a) Strong acid (HNO 3 ) and strong base (LiOH) .
C  O2  CO 2 , H   395.5 kJ .….(ii) 123. (d) H  E  nRT or E  H  nRT
1 1
H 2  O 2  H 2 O, H   285.8 kJ …..(iii)  E  7.3   0.002  298  7.3  0.298 = 7 kcal.
2 2
from (i), (ii), (iii). 124. (b) Heat evolved during burning of 39 g
H (CH 4 )
comb . 781.0  39
 H f (CO 2 )  2H f (H 2 O)  H f (CH 4 )  2H f (O 2 ) C6 H 6   390.5 kcal mol 1
78
 890.4  395.5  2 (285.5)  H f (CH 4 )  2  0 1
125. (b) By (i) + (ii) ; Na  Cl 2  NaCl, H  196 kcal .
1 2
H f (CH 4 )  76.7 kJ mol .
108. (d) As methanoic acid is weak acid, heat of neutralization < x. 126. (b) C  O2  CO 2(g) , H of  393.5 kJ mol 1 ….(i)
109. (d) Neutralization of a strong acid by a strong base is always same. 1
C O 2  CO (g) , H of  110.5 kJ mol 1 ….(ii)
110. (c) S  O2  SO 2 , H f   4.6 kJ 2
 0.5 gm. of sulphur on burning produce 1gm of SO 2
 446 Thermodynamics and Thermochemistry
1 15 1
H2  O 2  H 2 O(g) , H of  241.8 kJmol 1 ...(iii) n  6  3  1   .
2 2 2
By (ii) + (iii) – (i) 140. (b) By 2 × (i) + (ii) – (iii)
CO 2(g)  H 2(g)  CO(g)  H 2 O(g) , H  41.2 . H of methane  20.0 kcal .
127. (c) More +ve is H s more is heat of solution. 141. (c) Heat of neutralization of strong acid and weak base is less than
128. (d) CS 2 is formed from its initial components carbon and sulphur 13.7 kcal mol 1 .
so, H is heat of formation of CS 2 . 142. (d) E  0 for a cyclic process.
129. (d) H  18500  E  nRT 143. (c) 22.0  2  44 kcal .
or 18500  E  (1)  2  298  19096 cal . 144. (b) 0.3 mole OH  , neutralize 0.3 mole of HNO 3
130. (b) Heat evolved during combustion of 0.39g
Evolved heat,  57.1  0.3  17.13kJ
3250  0.39
C6 H 6   16.25 kJ . 146. (d) Compounds with high heat of formation are less stable because
78 energy rich state leads to instability.
131. (d) By (i) – (ii) : C 
1
O 2  CO ; H  229.2. 445.15  16
2 147. (b) CH 4 required   8 gm .
890.3
132. (b) Strong acid (HCl) and strong base (NaOH ) shows 148. (c) C(s)  2 H 2 (g)  CH 4 (g) …..(i)
H neutralization = –57.3 kJ.
C(s)  O2(g)  CO 2(g) H  94 kcal mol 1 …..(ii)
133. (d) By (i) – (ii) and find required result.
1 1 1 1
134. (a) CO (g)  O 2  CO (g) , n  1  1    H 2( g )  O 2(g)  H 2 O(l) H  68 kcal mol 1 … (iii)
2 (g) 2 2 2
H  E  nRT CH 4  3 / O2  CO 2  2 H 2 O
2
1 8.314
H  283.3    290  284.5 kJ . H  213 kcal mol 1 … (iv)
2 1000
to obtain equation (i) operate-(ii) + 2 × (iii) – (iv).
1
135. (a) H2  O 2  H 2 O H  188 kJ /mole ..…..(i) 149. (b) H  ve for endothermic reactions.
2
150. (b) It pertains to neutralization of strong acid weak base.
H 2  O2  H 2 O2 ; H  286 kJ /mole ..….(ii)
151. (d) Strong base (KOH) and strong acid (HCl)
By 2 × (i) and (ii)
153. (b) This reaction absorbed heat, so it is endothermic reaction.
2 H 2  O2  2 H 2 O ; H  376 kJ /mole …..(iii)
154. (b) C  O2  CO 2 , H   94.3
2 H 2  2O2  2 H 2 O2 H  572 kJ /mole …..(iv)
This is also heat of formation of CO 2
By (iii) – (iv)
1
2 H 2 O2  2 H 2 O  O2 H  196 kJ . C O 2  CO , H  26.0 .
2
136. (a) H for C 2 H 6  341.1 K cal
1
155. (b) X Y .
341.1 2
its calorific value   11.37 kcal / g .
30 157. (a) Molecular weight of NH 4 NO 3  80
H for C 2 H 2  310.0 kcal
Heat evolved  1.23  6.12
310.0  Molar heat capacity  1.23  6.12  C .
its Calorific value   11.92,
26
158. (d) Both X e and F2 are gaseous elements at 25 o C and in their
hence C 2 H 2 is a better fuel.
standard states and form XeF4 (g) hence H (f )  H react

.
138. (c) For the decomposition of 9gm of water heat required
 142.5 kJ 159. (c) According to Hess low, enthalpy change for a reaction does not
depend on the nature of inter mediate reaction steps.
we know H 2 O  2  16  18
160. (d) By (ii) – (i), C gr  Cdia , H  1.9 .
Therefore heat required for decomposition of 18gm water
18 162. (c) Heat of neutralization of strong acid and strong base is equal
  142.5  285 KJ
9 to the  57.32 KJ mol 1
Than, enthalpy of formation of water is reverse of heat 163. (c) C  O2  CO 2 H  393.5 KJ / mol
required = – 285 kJ.
15  44 gm of CO 2 form by which heat released
139. (d) C6 H 6(g)  O 2(g)  6 CO 2(g)  3 H 2 O(g)
2  393. 5 kJ
 Thermodynamics and Thermochemistry 447

 1 gm of CO 2 form by which heat released  

393.5 H o  3920  2160  160  6240 KJ / mol
44
H o  for 6 moles of octane  6240  6
 35.2 gm (given) of CO 2 form by which heat released
 37440 KJ / mol  37.4 KJ
393.5
  35.2  315 kJ 3
44 171. (d) 2 Fe  O 2  Fe 2 O 3 ; H  193.4 kJ .....(i)
2
164. (c) C(graphite)  2 H 2 (g)  CH 4 (g)
1
165. (c) Heat of formation of a substance is the heat exchanged when Mg  O 2  MgO; H  140.2 kJ .....(ii)
one mole of that substance is formed by its constituent 2
elements. On multiplying eq. (ii) by 3
 Heat evolved when 1 mole (44 g) CO 2 is formed 3
3 Mg  O 2  3 MgO; H  420.6 kJ ......(iiii)
 393 kJ 2
 Heat evolved when 0.156 Kg (156 g) is formed Resulting equation can be obtained by subtracting eq. (i) from
(iii)
393  156
 3
44 3 Mg  O 2  3 MgO; H  420.6 kJ
2
 H for the process  1572 kJ  1572.0 kJ
3
2 Fe  O 2  Fe 2 O 3 ; H  193.4 kJ
166. (b) It is heat of neutralisation (13.7 Kcal) for strong acid and 2
strong base. Subtraction :
167. (d) C(s)  O2 (g)  CO 2 (g) 3 Mg  Fe2 O 3  2 Fe  3 MgO; H  227.2 kJ

H  393.5 KJ mol 1 …..(i) 172. (c) HCl and KOH both are strong

CO(g)  1 / 2O2 (g)  CO 2 (g)

Bond energy
1
H  283 KJ mol …..(ii)
1. (b) XY  X (g)  Y(g) ; H  a kJ / mole ……….(i)
On substracting equation (ii) from equation (i)
We get X 2  2 X ; H  a kJ / mole ………. (ii)
C(s)  O 2 (g)  CO(g) ; H  110.5 KJ mol 1 Y 2  2Y ; H  0.5 a kJ / mole ……….(iii)
The enthalpy of formation of carbon monooxide per mole
1 1
 110.5 KJ mol 1  (ii)  (iii)- (i), gives
2 2
168. (d) 1 mole (i.e.,) 16 gm of methane on combustion liberate 1 1
X 2  Y 2  XY ;
890 kJ 2 2
890  3 .2  a 0.5 
 3.2 gm will liberate   178 KJ H     a  a  kJ / mole
16  2 2 
169. (c) C  O 2  CO 2 ; H  q a 0 .5 a
   a  200
2 2
C  1 / 2O 2  CO ; H  12 …..(i)
a  800
CO  1 / 2O2  CO 2 ; H  10 …..(ii)
2. (a) 4 g H 2  2 moles. Bond energy for 1 mole of
adding equation (i) and (ii) we can get H 2  208 / 2  104 kcal.
H  12  (10)  22 4. (d) By definition of Hess’s law.
170. (b) C  O2  CO 2 ; H F  490 KJ / mol – (I) 1 1
5. (c) Aim: H 2  Cl 2  HCl
H 2  1 / 2O2  H 2 O; H F  240 KJ / mol – (II) 2 2
H   B. E.   B. E.
8 C  18 H  C8 H18 ; H F  160 KJ / mol – (III) (Products) (Reactants)
applying 1 1 
 B. E.( HCl )   B. E.( H 2 )  B. E.(Cl 2 )
(I) 8  (II) 9  (III) 2 2 

25 1 1 
C 8 H 18  O 2  8 CO 2  9 H 2 O  103   (  104 )  (  58)
2  2 2 
 103  (  52  29 )  22 kcal .
 448 Thermodynamics and Thermochemistry
6. (c) First ionization potential of Li  5.4 eV 14. (d) Spontaneous change shows G  ve .
Electron affinity of Cl  3.61eV 15. (b) G  H  TS , T  25  273  298 K
We have H  I.P.  E. A.  11.7  10 3  298  (105)  19590 J  19.59kJ
22
 5.4  3.61  1.80eV  1.80  1.6  10 kJ 18. (c) If G  ve reaction is spontaneous.
22
H  2.86  10 kJ , 20. (b) (dS )V , E  0, (dG)T , P  0 .
for 1mol Avogadro’s number  6.02  10 23
. 21. (b) Only high pressure favours the conversion.
22. (d) By 2× (ii) – (i) – (iii)
H  2.86  10 22  6.02  10 23  170 kJ / mole.
H 2(g)  2C(s)  C 2 H 2(g) , G   209 kJ .
166
7. (b)  41.5 kJ / mole .
4 23. (b) G  2.303 RT log K  , Here R  2 cal, T  300 K

1 1 10  15
8. (d) H 2  Cl 2  HCl, H  90 KJ K   10 ; G  2.303  2  300  log10 10
2 2 35
1 1  2.303  2  300  1  1381.8 cal
 H  E H  H  ECl Cl
2 2 24. (a) G  H  TS (Gibb’s free energy equation)
1 1 25. (d) G  H  TS
or  90   430   240  E HCl
2 2 G  382.64  (145.6)  10 3  298
 E H Cl  425 kJ mol 1 .  339.3 KJ mol 1
9. (b) CH 4  C  4 H , H  320 26. (d) G  H  TS ; G  E  PV  TS
For spontaneity (G  ve )
EC  H  90 cal
 G  ve , E  ve
C2 H 6  2C  6 H, H  360
27. (a) G  H  TS  31400  1273  32
 360  EC  C  6 EC  H  31400  40736  9336 cal
 EC  C  360  320  40 cal . 28. (d) G  H  TS
0  30.558  T  0.066
10. (b) H  H  Br  Br  2 H  Br
30.558
433  192 2  364 or T   463 K
0 .066
625 728
If (dG)T , P  0 sign ' ' mean. If is reversible process
Energy absorbed = Energy released
Net energy released  728  625  103 kJ
Critical Thinking Questions
i.e.,  H  103 KJ
1. (b) Due to randomness of particles is reduced since entropy
decreases.
Free energy and Work function
2. (c) H  nCp T
1. (d) G at equilibrium = 0. The process is isothermal therefore
2. (b) For spontaneous change G  ve . G  0 ;  H  0
3. (a) When G  ve than the reaction is spontaneous in nature.
3. (d) 13.7 kcal  57 kJ  5.7  10 4 J .
5. (acd)When H  ve and S  ve than the reaction is non-
spontaneous. 4. (b) When strong acid and strong base neutralize each other than the
value of heat generated is about 13.7 kcal.
7. (c) Because the reaction is spontaneous .
5. (b) Due to fall in temperature.
8. (c) G = –ve.
6. (d) q  H .
P p
9. (a) GT  nRT ln 2 .
P1 V2 V
7. (d) w  2 .303 RT log . As it involves the ratio 2 , volume
V1 V1
10. (a) G  0 for equilibrium.
can be used in any units. (R should be in joules).
11. (d) At equilibrium G  0 .
dQ dQ
12. (a) G o   2.303 RT log K 8. (b)   ; dE  dW  dQ ; dW  dQ  dE
dW dQ  dE
 4.606   2.303  0.002  500 log K nc p dT cp
 
log K  2, K  100 . nc p dT  ncv dT (c p  c v )
 Thermodynamics and Thermochemistry 449

7R 7R 26. (b) Heat required to rise the temperature of a body by 1 K called

 {for diatomic of gas c p  } thermal capacity of the body.
2R 2
9. (a) C 2 H 2 (g)  H 2 (g)  C 2 H 4 (g) 27. (e) Mechanical work is important only in gases as they undergo
appreciable change in volume.
ng  1  2  1 ; H  0.31 KJ mol 1 28. (d) It is Lavoisier and Laplace law. This is another law of
thermochemistry which was put forward before Hess's law.
P  1.5 atm , V  50 mL  0.050 L
29. (a) It is also known as "constant heat summation" law. It state that
H  E  PV the total amount of heat evolved or absorbed in a reaction is
same whether the reaction takes place in one step or in a
0.31  E  0.0076 ; E  0.3024 KJ number of steps.

10. (a) Since process is exothermic then heat is evolved due to this 30. (c) In this reaction n  2  4  2 so H  E .
temperature of water increases. 18.94  0.632  0 .998  122
31. (a) Q = 771.1 Kcal
11. (a) Because randomness is decreases. 1.89
12. (c) Conversion of graphite into diamond is an endothermic 32. (c) H  Ea for forward reaction  Ea for backward reaction
reaction. So, heat of diamond is higher than that of graphite.  19  9  10 kJ .
But S would be negative for the conversion of graphite into
diamond. 33. (d) Q  18.94  0.632  0.998  1000

13. (c) H and S both are ve for spontaneous change, and 57.4  x  12.13
H  ve for endothermic reaction. x  45.2
14. (a) G  H  TS is negative for spontaneity. 34. (c) Thermodynamics is a reversible process in which surroundings
are always equilibrium with system.
15. (a) Entropy (a measure of disorder) of universe is increasing
toward maximum. This is II law of thermodynamics. 4 .18
35. (a) 1 cal  4.18 J  4.18  10 7 erg   10 19 eV .
16. (a) For a pure substance TA and TB represent the same 1.602
temperature. Hence A is a correct choice. 36. (b) Order of bond energy : Cl 2  Br2  F2  I2 .
17. (a) For endothermic reaction enthalpy of products (H P ) > 37. (c) Heat energy is also involved when one allotropic form of an
element is converted in to another. graphite is the stabler
enthalpy of reactant (H R ) allotrope because the heat of transformation of
Hence, change in enthalpy, C(diamond )  C(graphite) .
H  H P  H R  Positive (i) C(dia)  O2(g)  CO 2(g)H  94.5kcal
18. (d) Suppose the no. of gm, 1gm for each case so the max. no of (ii) C(graphite)  O2(g)  CO 2(g)H  94.0 k cal
mole expected for SO 2 (g) which has to expected maximum
entropy. H transforma tion  94.5  (94.0)

3  0.5k cal .
19. (b) 2 Al  O 2  Al2 O3 , H  1596 kJ …..(i)
2 38. (b) The compound Y possess less energy than the X and thus Y is
3 more stable than X.
2Cr  O 2  Cr2 O3 , H  1134 kJ …..(ii)
2 39. (c) Both H and p are positive.
By (i) – (ii)
40. (a) For equilibrium G o  0 .
2 Al  Cr2 O3  2Cr  Al2 O3 , H  462 kJ . 41. (b) Equilibrium constant is decreases with temperature and H
20. (a) Bomb calorimeter is used to measure heat of reaction. is also decreases so it is –ve.
21. (b) Larger the number of C and H atoms, greater is the heat of 42. (a) The fusion temperature of napthalene is minimum, because it
combustion. is non-polar covalent compound and has less fusion
temperature.
22. (c) The bomb calorimeter is used to measure E .
43. (a) The bond energy of C  H bond is y kcal mol 1 .
H
|
E E > H N  N  3 H  H  2N  H
Enthalpy

23. (c)
a
44. (a)
H
a

945  3  436 |
H
Energy absorbed 2 (3  391 )  2346

Energy released

Energy Net. energy released = 2346 – 2253 = 93 kJ

24. (b) H Neutralization  57.1 kJ  13.7 kcal . i.e. ΔH = – 93 kJ .
25. (b) Backmann thermometer is used to measure low temperature.
 450 Thermodynamics and Thermochemistry
45. (d) If E  ve than the cell reaction will be spontaneous. angular and show some polarity which is higher than that of
ethanol so both assertion and reason are correct but reason is
46. (d) All are the correct statements. not explaination assertion.
47. (d) CH 2  CH 2(g)  H 2(g)  H 3 C  CH 3(g) 8. (a) The assertion that the increase in internal energy for the
vaporisation of one mole of water at 1 atm and 373 K is zero is
414  4  1656 414  6  2484 true and this is because that for all isothermal process internal
energy is zero.
615  1  615 347  1  347
9. (b) N 2 (g)  O 2 (g) ⇌ 2 NO (g)
435  1  435 2831
2706
We know that H  E  nRT
H  2706  2831  125 kJ n  2  2  0 hence, nRT  0
48. (b) It means that the heat absorbed when one gram molecule of Therefore, H  E
HCl is formed from its elements at 298 K is 10. (a) The enthalpies of neutralisation of strong acids and strong
 22.060 k cal . bases are same they are 13.7 Kcal. The reason is that it is heat
of formation of water from H and OH  ions.
49. (d) eq. (i) + eq. (ii) find the required result and divide by 2.  
H  OH  H 2 O, H  13.7 Kcal . Thus, both assertion
50. (d) For complete neutralization of strong acid and strong base and reason are true.
energy released is 57.32 KJ / mol 11. (a) Zeroth (law of temperature) can also be summarized as two
objects at different temperature in thermal contact with each
0.2  50
No. of mole of H 2 SO 4   10 2 other tend to move towards the same temperature.
1000
12. (d) Photo chemical reactions have ve G .
1
No. of mole of KOH   50  5  10 2
1000

So  57.32  10 2  0.5732 KJ  573.2 Joule .

51. (b) For Combustion reaction, H is negative,

n  (16  18)  (25  2)  7 , so S is ve , reaction is
spontaneous, hence G is –ve.

52. (a) G  H  TS , T  27  273  300 K

G  (285.8)  (300)(0.163)  236.9 kJ mol 1

Assertion & Reason

1. (b) Assertion and reason show, reaction at equilibrium state in
which G  0 , S  0 , H  0 .
2. (b) It is correct that on touching the ice we feel cold because ice
absorb heat from our hand.
3. (b) Entropy of ice is less than water because water molecules in
solid state lose kinetic energy and hence their tendency of
movement minimise. Hence entropy decrease in solid state. The
reason that ice have cage like structure is also correct but
reason is not or correct explanation for assertion.
4. (c) During isothermal expansion of an ideal gas against vacuum is 14. (e) Heat absorbed in a reaction at constant temperature and
zero because expansion is isothermal. The reason, that volume constant volume (Qv)  E .
occupied by the molecules of an ideal gas is zero, is false.
15. (c) Values of state functions depend only on the state of the
5. (a) it is fact that absolute values of internal energy of substances system and not on how it is reached.
can not be determined. It is also true that to determine exact
values of constituent energies of the substance is impossible. 16. (a) The properties whose magnitude depends upon the quantity of
matter present in the system are called extensive properties.
6. (b) Mass and volume are extensive properties. mass/volume is also an
extensive parameter. Here, both assertion and reason are true. 17. (c) Combustion reactions are always accompanied by the evolution
of heat therefore, for such reactions the value of H is always
7. (b) The molar entropy of vaporization of water it differ from negative.
ethanol due to hydrogen bonding according to VSEPR theory
water molecule having two lone pair of electron by which it
 Thermodynamics and Thermochemistry 451

18. (b) In an isothermal process change in internal energy (E) is

zero (as it is a fucntion of temperature).  According to first
law of thermodynamics
 q  w  E , hence Q  W (if E  0)

If a system undergoes a change in which internal energy of the

system remains constant (i.e., E  0 ), then W  Q .
This means that work done by the system equals the heat
absorbed by the system.
20. (e) If a refrigerator’s door is kept open room gets heated as heat
energy is released to the surroundings.
21. (c) Enthalpy is zero but entropy is not zero. Vibrational motion
exists even at absolute zero.
22. (c) It may involve increase or decrease in temperature of the
system. Systems in which such process occur, are thermally
insulated from the surroundings.