THERMODYNAMICS AND THERMOCHEMISTRY 33

EXERCISE – 1: Basic Objective Question

Introduction to Thermodynamics 10. Which of the following quantities is not a state
function?
1. Thermodynamics deals with
(a) Temperature (b) Entropy
(a) Macroscopic properties
(c) Enthalpy (d) Work
(b) Microscopic properties
11. Which of the following is not a state function?
(c) Both Macroscopic & microscopic properties
(a) ∆H (b) ∆U
(d) Neither macroscopic nor microscopic properties
(c) q∆ (d) ∆G
2. Which of the following macroscopic variable is not
12. Which of the following can be used to define the state
measurable?
of a system?
(a) Mass (b) Volume
(a) Pressure (b) Volume
(c) Pressure (d) None of these
(c) Number of mole (d) All of these
3. The state of a thermodynamic system is represented by
13. Which of the following is a state function?
(a) pressure, volume and temperature
(a) q + w (b) Entropy
(b) volume only
(c) Free Energy (d) All of these
(c) pressure only
14. Which of the following is a path function?
(d) number of moles
(a) Internal energy (b) Enthalpy
4. Thermodynamics is not concerned about____.
(c) Work (d) Entropy
(a) energy changes involved in a chemical reaction
15. Which of the following is a state variable?
(b) the extent to which a chemical reaction proceeds
(a) Internal energy (b) heat
(c) the rate at which a reaction proceeds
(c) Work (d) All of these
(d) the feasibility of a chemical reaction
Extensive and Intensive Properties
System, Surrounding and Boundary
16. Which of the following is not an intensive property?
5. Which of the following is an example of open system?
(a) Entropy (b) Pressure
(a) Human body (b) The earth
(c) Temperature (d) Molar volume
(c) Pond (d) All of these
17. Which of the following is a state function and also an
6. Closed system can exchange (with surroundings)
extensive property?
(a) Heat (b) Matter
(a) Internal energy (b) Pressure
(c) Heat and matter (d) Neither heat nor matter
(c) Molar heat capacity (d) Temperature
7. System and surroundings together constitute
18. Which of the following is intensive property?
(a) The earth (b) The solar system
(a) Temperature (b) Heat
(c) Galaxy (d) Universe
(c) Mass (d) Volume
8. Which of the following is true about isolated system?
19. The volume of gas is reduced to half from its original
(a) Heat passes into or out of the system
volume. The specific heat will____.
(b) Matter enters or leaves the system
(a) be reduced to half (b) be doubled
(c) Work can be done on the system
(c) remain constant (d) be increased four times
(d) All are correct
Types of Processes
State and Path Functions
20. Tea placed in thermos flask is an example of
9. Which of the following is not a state function? (a) Open system (b) Close system
(a) Heat (b) Internal energy (c) Isolated system (d) It can’t act as system
(c) Enthalpy (d) Entropy
21. Gaseous system is placed with pressure P1, volume V1 28. In a reaction, all reactant and products are liquid, then
and temperature T1, it has undergone thermodynamic (a)  H   E (b) H   E
changes where temperature is remaining constant, it is (c) H  E (d) Can’t predicted
(a) Adiabatic process (b) Isothermal process
(c) Isobaric process (d) Isochoric process Internal Energy
22. Based on the first law of thermodynamics, which one of
the following is correct? 29. Regarding the internal energy of the molecule, which of
(a) For an isothermal process, q   W the following statement is correct?
(a) Its absolute value can be successfully calculated
(b) For an isochoric process, U  q
(b) Its absolute value cannot be determined
(c) For an adiabatic process, U   W (c) It is the sum of vibrational and rotational energies
(d) For a cyclic process, q   W (d) Both (a) and (c)
23. In ….. process, work is done at the expense of internal 30. Internal energy is the sum of
energy. (a) kinetic energy and potential energy
(a) isothermal (b) isochoric (b) all types of energy of the system
(c) adiabatic (d) isobaric (c) energy of internal system
24. A thermally isolated gaseous system can exchange (d) None of the above
energy with the surroundings. The mode of energy may 31. In an isothermal expansion of an ideal gas
be (a) q = 0 (b) ∆V = 0
(a) Heat (b) Work (c) ∆U = 0 (d) w = 0
(c) Heat and radiation (d) Internal energy 32. A system absorb 10 kJ of heat at constant volume and
its temperature rises from 27°C to 37°C. The value of
First Law of Thermodynamics ∆U is
(a) 100 kJ (b) 10 kJ
25. Which is included in thermodynamic equilibrium from (c) 0 (d) 1 kJ
the following? 33. A system absorbs 10 kJ of heat and does 4 kJ of work.
(a) Pressure equilibrium The internal energy of the system
(b) Chemical equilibrium (a) Decreases by 6 kJ
(c) Thermo equilibrium (b) Increases by 6 kJ
(d) All of these (c) Decreases by 14 kJ
26. U  q  w , is mathematical expression for (d) Increases by 14 kJ
(a) first law of thermodynamics
(b) second law of thermodynamics Concept of Heat and Work
(c) third law of thermodynamics
(d) zeroth law of thermodynamics 34. Two moles of Helium gas undergo a reversible cyclic
27. According to the first law of thermodynamics, process as shown in figure. Assuming gas to be ideal.
U  q  w . In special cases the statement can be What is the work done for the process C to D?

expressed in different ways. Which of the following is

not a correct expression?
(a) At constant temperature: q   w
(b) When no work is done: U  q
(c) In gaseous system: U  q  PV
(d) When work is done by the system: U  q  w
(a) –800 R ln 2 (b) zero
(c) +200 R ln 2 (d) –600 R ln 2
THERMODYNAMICS AND THERMOCHEMISTRY 35

35. E is always positive, when 41. A given mass of gas expands from state A to state B by
(a) system absorbs heat and work is done on it three paths 1, 2, and 3 as shown in the figure:
(b) system emits heat and work is done by it
(c) system emits heat and no work is done on it
(d) system absorbs heat and work is done by it
36. A sample of liquid in a thermally insulated container (a
calorimeter) is stirred by a motor. Taking liquid as a
system for this process choose the appropriate option:
(a) w < 0; q = 0; ∆U = 0 (b) w > 0; q > 0; ∆U > 0
(c) w < 0; q > 0; ∆U = 0 (d) w > 0; q = 0; ∆U > 0
37. An ideal gas is taken around the cycle ABCA as shown
in P-V diagram If w1 , w 2 and w 3 respectively, be the work done by
The net work done by the gas during the cycle is equal
to: the gas along three paths, then
(a) w1  w 2  w 3 (b) w1  w 2  w 3
(c) w1  w 2  w 3 (d) w1  w 2 ; w1  w 3
42. One mole of an ideal gas is initially at 0°C and 1 atm
pressure. If it absorbs 1000 cal heat during a reversible
isothermal expansion, what will be its final volume?
(a) 102.5 L (b) 242.5 L
(c) 22.4 L (d) 141.47 L

Reversible and Irreversible Work

43. The maximum work obtained by an isothermal

(a) 12 P1V1 (b) 6P1V1 reversible expansion of 1 mole of an ideal gas at 27°C
(c) 5P1V1 (d) P1V1 from 2.24 to 22.4 L is (R = 2 cal)
38. An ideal gas receives 10 J of heat in a reversible (a) – 1381.8 cal (b) – 600 cal
isothermal expansion. Then the work done by the gas: (c) –138.18 cal (d) – 690.9 cal
(a) would be more than 10 J 44. Which of the following processes is reversible?
(b) 10 J (a) Isothermal compression
(c) would be less than 10 J (b) Electrical heating of a nichrome wire
(d) cannot be determined
(c) Transfer of heat by radiation
39. The pressure of a gas is 100 kPa. If it is compressed
(d) Transfer of heat by conduction
from 1m3 to 10 dm3, find the work done.
45. Which of the following processes is irreversible?
(a) 990 J (b) 9990 J
(c) 9900 J (d) 99000J (a) Transfer of heat by radiation
40. An ideal gas expands in volume from 1 × 10–3 to (b) Adiabatic changes performed slowly
1 × 10–2 m3 at 300 K against a constant pressure (c) Extremely slow extension of a spring
1 × 105 Nm–2. The work done is (d) Isothermal changes performed slowly
(a) – 900 J (b) – 900 kJ 46. In thermodynamics a process is called reversible when
(c) 270 kJ (d) 900 kJ (a) System and surrounding change into each other
(b) There is no boundary between system and
surrounding
(c) The surroundings are always in equilibrium with the
system
(d) The system changes into the surroundings
spontaneously
36 THERMODYNAMICS AND THERMOCHEMISTRY

Reversible and Irreversible Work 55. One mole of an ideal gas expands reversibly and
adiabatically from a temperature of 27°C. If the work
47. Calculate the work done when 1 mol of an ideal gas is done during the process is 3 kJ, then final temperature
compressed reversibly from 1 bar to 4 bar at a constant of the gas is:(CV = 20 J/K)
temperature of 300 K
(a) 100 K (b) 150 K
(a) 4.01 kJ (b) – 8.02 kJ
(c) 195 K (d) 255 K
(c) 18.02 kJ (d) +3.457 kJ
48. 16g of oxygen gas expands isothermally and reversibly Entropy and Spontaneity
at 300 K from 10 dm3 to 100 dm3. The work done is (in
56. When ice melts into water, entropy
J)
(a) become zero (b) decreases
(a) zero (b) – 2875 J (c) increases (d) remains the same
(c) + 2875 J (d) infinite 57. Which one of the following has S greater than zero?
49. The work done during the expansion of a gas from a
(a) CaO  s   CO 2  g   CaCO3  s 
volume of 4dm3 to 6 dm3 against a constant external
pressure of 3 atm is (b) NaCl  aq   NaCl  s 
(a) – 6J (b) – 608 J (c) NaNO3  s   Na   aq   NO3  aq 
(c) + 304 J (d) – 304 J
50. Calculate the work done when 1 mole of an ideal gas is (d) N 2  g   3H 2  g   2NH 3  g 
compressed reversibly form 1 bar to 4 bar at a constant 58. Entropy of the universe is
temperature of 300 K. (a) constant
(a) 3.457 kJ (b) –8.02 kJ (b) zero
(c) 18.02 kJ (d) None of these (c) continuously decreasing
(d) continuously increasing
Enthalpy and Heat Capacity of A System 59. Which of the following expressions regarding entropy
is not correct?
51. The statement “The change of enthalpy of a chemical
q
reaction is same whether the reaction takes place in one (a) Ssystem 
T
or several steps” is
(b)  Ssystem   Stotal  Ssurrounding
(a) Le Chatelier’s law
(b) van’t Hoff’s law (c) S  Sfinal  Sinitial
(c) first law of thermodynamics (d)  S total   Ssystem  Ssurrounding
(d) Hess’s law 60. Which of the following processes is a non-spontaneous
52. Molar heat capacity of water in equilibrium with ice at process?
constant pressure is (a) Dissolution of salt or sugar in water
(a) zero (b)  (b) Mixing of different gases through diffusion
(c) 40.45 kJ K–1mol–1 (d) 75.48 J K–1mol–1 (c) Precipitation of copper when zinc rod is dipped in
53. 1 mole of NH3 gas at 27°C is expanded in reversible aqueous solution of copper sulphate
adiabatic condition to make volume 8 times (γ = 1.33). (d) Flow of heat from a cold body to a hot body in
Final temperature and work done by the gas contact
respectively are: 61. Entropy is a measure of
(a) 150 K, 900 cal (b) 150 K, 400 cal (a) disorder
(c) 250 K, 1000 cal (d) 200 K, 800 cal (b) internal energy
54. In an adiabatic expansion of ideal gas (c) efficiency
(a) W  E (b) W  E (d) useful work done by the system
(c) E  0 (d) W  0
THERMODYNAMICS AND THERMOCHEMISTRY 37

62. Read the following statements regarding spontaneity of 68. When one mole of an ideal gas is compressed to half of
a process and mark the appropriate choice. its initial volume and simultaneously heated to twice its
(i) When enthalpy factor is absent then randomness initial temperature, the change in entropy of gas (∆S) is:
factor decides spontaneity of a process. (a) Cp,m ln2 (b) Cv,m ln2
(ii) When randomness factor is absent then enthalpy (c) R ln2 (d) (Cv,m –R) ln2
factor decides spontaneity of a process.
69. One mole of an ideal diatomic gas (Cv = 5 cal) was
(iii) When both the factors take place simultaneously,
the magnitude of both of factos decide spontaneity transformed from initial 25°C and 1 L to the state when
of a process. temperature is 100°C and volume 10 L. The entropy
(a) Statements (i) and (ii) are correct and (iii) is change of the process can be expressed as (R = 2
incorrect. calories/mol/K)
(b) Statement (iii) is correct, (i) and (ii) are incorrect. 298 373
(a) 3n  2 n10 (b) 5n  2 n10
(c) Statements (i), (ii) and (iii) are correct. 373 298
(d) Statements (i), (ii) and (iii) are incorrect. 373 1 373 1
63. Which of the following statements is not correct? (c) 7n  2 n (d) 5n  2 n
298 10 298 10
(a) For a spontaneous process, ∆G must be negative.
70. A reaction has ∆H = – 33 kJ and ∆S = +58 J/K. This
(b) Enthalpy, entropy, free energy etc. are state
reaction would be :
variables.
(a) spontaneous below a certain temperature
(c) A spontaneous process is reversible in nature. (b) non-spontaneous at all temperature
(d) Total of all possible kinds of energy of a system is (c) spontaneous above a certain temperature
called its internal energy. (d) spontaneous at all temperature
64. Considering entropy (s) as a thermodynamic parameter, 71. The respective examples of extensive and intensive
the criterion for the spontaneity of any process is properties are
(a) Ssystem  Ssurroundings  0 (a) Enthalpy, Entropy
(b) Ssystem  Ssurroundings  0 (b) Entropy, Enthalpy
(c) Entropy, Temperature
(c) Ssystem  0 only
(d) Temperature, Entropy
(d) Ssurroundings  0 only 72. It is impossible for a reaction to take place if
65. Unit of entropy is (a) H is +ve and S is +ve
(a) J K–1 mol–1 (b) J mol–1 (b) H is –ve and S is +ve
–1 –1 –1
(c) J K mol (d) J K mol–1
(c) H is +ve and S is –ve
66. In which case change in entropy is negative?
(d) H is –ve and S is –ve
(a) Expansion of a gas at constant temperature
(b) Sublimation of solid to gas Gibbs Energy and Spontaneity
(c) 2H(g)  H2(g)
73. Pick out the wrong statement
(d) Evaporation of water
(a) The standard free energy of formation of all element
67. The entropy change when two moles of ideal
is zero
monoatomic gas is heated from 200°C to 300°C
(b) A process accompanied by decrease in entropy
reversibly and isochorically?
spontaneous under certain conditions
3  300  5  573  (c) The entropy of a perfectly crystalline substance
(a) R n   (b) R n  
2  200  2  273  absolute zero is zero
 573  3  573  (d) A process that leads to increase in free energy will
(c) 3 R n   (d) R n  
 473  2  473  spontaneous
38 THERMODYNAMICS AND THERMOCHEMISTRY

74. Which one of the following is correct? Third Law of Thermodynamics

(a) G  H  TS
(b) H  G  TS 81. Which law states that entropy of all pure crystalline
1 solids is zero at absolute zero?
(c) S   G  H 
T (a) First law of thermodynamics
1 (b) Second law of thermodynamics
(d) S   H  G 
T (c) Third law of thermodynamics
75. For the gas phase reaction, (d) Hess’s law
PCl5  g   PCl3  g   Cl 2  g  82. Identify the correct statement regarding entropy.
Which of the following conditions are correct? (a) At absolute zero of temperature, the entropy of all
(a) H  0 and S  0 crystalline substances is taken to be zero.
(b) H  0 and S  0 (b) At absolute zero of temperature, the entropy of a
perfectly crystalline substance is + ve.
(c) H  0 and S  0
(c) At absolute zero of temperature, entropy of a
(d) H  0 and S  0
perfectly crystalline substance is taken to be zero.
76. G is the net energy available to do useful work and is (d) At absolute zero of temperature, entropy of a
a measure of free energy. If a reaction has positive
perfectly crystalline substance is taken to be zero.
enthalpy change and positive entropy change, under
what conditions will the reaction be spontaneous? Thermochemical Equations
(a) G will be positive at low temperature hence
reaction is spontaneous at low temperature. 83. Enthalpy change for the reaction, 4H(g)  2H2(g) is –
(b) G is negative at high temperature hence reaction is 869.5 kJ. The dissociation energy of H–H bond is
spontaneous at high temperature. (a) +217.4 kJ (b) –434.8 kJ
(c) G is negative at low temperature hence reaction is (c) –869.6 kJ (d) +434.8 kJ
spontaneous at low temperature 84. Thermodynamically, the most stable form of carbon
(d) G is negative at all temperatures hence reaction is
(a) diamond (b) graphite
spontaneous at all temperatures. (c) fullerenes (d) coal
77. 2 moles of ideal gas at 27°C temperature is expanded
85. Which of the following reactions define  G of ?
reversibly from 2 lit. to 20 lit. find entropy change. (R =
2 cal/mol K) (a) C diamond   O2  g   CO2  g 
(a) 92.1 (b) 0 1 1
(c) 4 (d) 9.2 (b) H 2  g   F2  g   HF  g 
2 2
78. In which of the following cases, the reaction is
(c) H4 P2 O7  H 2 O  2H3 PO4
spontaneous at all temperatures ?
(a) ∆H > 0, ∆S > 0 (b) ∆H < 0, ∆S > 0 1
(d) SO 2  g   O 2  g   SO3  g 
(c) ∆H < 0, ∆S < 0 (d) ∆H > 0, ∆S < 0 2
79. The standard free energy change G is related to K 86. For a reaction: X → Y + Z absolute entropies are X =
(equilibrium constant) as 120 JK–1 mol–1 Y = 213.8 JK–1 mol–1 and Z = 197.9 JK–
1
mol–1.
(a) G = –2.303 RT log K
What will be the entropy change at 298 K and 1 atm?
(b) G = 2.303 RT log K
(a) 291.7 JK–1 (b) 255 JK–1
(c) G = RT log K (c) 213.8 JK –1
(d) 257.3 JK–1
(d) None of these 87. In endothermic reactions,
80. Cell reaction is spontaneous when (a) reactants have more energy than products
(a) G is negative (b) reactants have less energy than products
(b) G is positive (c) reactants and products have same energy
(c) Gred is positive (d) reactants have lower temperature than products
(d) Gred is negative
THERMODYNAMICS AND THERMOCHEMISTRY 39

88.  H and E for the reaction, 95. In a reaction P + Q → R + S, there is no change in

Fe 2 O 2  s   3H 2  g   2Fe  s   H 2 O  l  entropy. Enthalpy change for the reaction (∆H) is 12 kJ
mol–1. Under what conditions, reaction will have
at constant temperature are related as
negative value of free energy change?
(a) H  E (b)  H   E  RT
(a) If ∆H is positive
(c) H  E  3RT (d) H  E  3RT
(b) If ∆H is negative
State/Phase Change of Reactants and Products (c) If ∆H is 24 kJ mol–1
(d) If temperature of reaction is high.
89. What is the entropy change in JK–1 mol–1 when one
Standard Enthalpy Change ΔH°
mole of ice is converted into water at 0°C? (The
enthalpy change for the conversion of ice to liquid
96. For the reaction,
water is 6.0 kJ mol–1 at 0°C)
(a) 20.13 (b) 2.013 2H 2 O  g  
 2H 2  g   O 2  g  ∆H = 571.6 KJ
(c) 2.198 (d) 21.98  f H of water is :
90. The enthalpy of vaporisation of a substance is 8400 J
(a) 285.8 kJ (b) –285.8 kJ
–1
mol and its boiling point is –173ºC. The entropy (c) 1143.2 kJ (d) –1143.2 kJ
change for vaporisationis : 97. ∆H for the reaction,
(a) 84 J mol-1 K-1 (b) 21 J mol-1 K-1 1
-1 -1  SO 3  g  ∆H = –98.3 kJ
SO 2  g   O 2  g  
(c) 49 J mol K (d) 12 J mol-1 K-1 2
91. The enthalpy of vaporisation of a compound AB at its If the enthalpy of formation of SO3(g) is –395.4 kJ then
boiling point (127°C) is 6.4 kJ mol-1. Its entropy of the enthalpy of formation of SO2(g) is :
vaporization is (a) –297.1 kJ (b) 493.7 kJ
(a) 2.56 kJmol1K 1 (b) 16 Jmol1K 1 (c) –493.7 kJ (d) 297.1 kJ
98. When 0.5 g of sulphur is burnt to SO2 4.6 kJ of heat is
(c)16 × 10–3 Jmol 1K 1 (d) 1.6 × 103 kJmol1K 1
liberated. What is the enthalpy of formation of
92. The following data is known about the melting of a
sulphurdioxide?
–1
compound AB. ∆H = 9.2 kJ mol . (a) –147.2 kJ (b) +147.2 kJ
–1 –1 (c) +294.4 kJ (d) –294.4 kJ
∆S = 0.008 kJ K mol . Its melting point is :
99. The heat of formation of
(a) 736 K (b) 1050 K
(c) 1150 K (d) 1150°C Fe 2 O 3  s  is –824.2 kJ mol–1. ∆H for the reaction.
93. The densities of graphite and diamond at 298 K are 2.25 2Fe2 O3  s  
 4Fe  s   3O2  g  is:
and 3.31 g cm–3, respectively. If the standard free (a) –412.1 kJ (b) –1648.4 kJ
energy difference is equal to 1895 J mol–1, the pressure (c) –3296.8 kJ (d) 1648.4 kJ
at which graphite will be transformed into diamond at
100. The H  for the reaction,
298 K is
(a) 11.08 × 108 Pa (b) 9.92 × 107 Pa 4S  s   6O 2  g   4SO 3  g 
(c) 9.92 × 106 Pa (d) 11.08 × 106 Pa is –1583.2 kJ. Standard enthalpy of formation of
sulphur trioxide is :
Relationship Between ΔH and ΔU (a) –3166.4 kJ (b) 3166.4 kJ
(c) –395.8 kJ (d) 395.8 kJ
94. Which one of the following is not always negative?
(a) Enthalpy of combustion
(b) Enthalpy of formation
(c) Enthalpy of neutralization
(d) Lattice enthalpy
40 THERMODYNAMICS AND THERMOCHEMISTRY

101. Calculate the heat of formation of PCl5(s) from the 108. When compared to G for the formation of Al2O3, the
following data: G for the formation of Cr2O3 is
2P(s) + 3Cl2 (g)   2PCl3(l) ∆H = –151.8 kcal (a) higher (b) lower
PCl3(l) + Cl2(g) 
 PCl5(s) ∆H = –32.8 kcal (c) same (d) unpredicted
109. In order to decompose 9 g water, 142.5 kJ heat is
(a) –108.7 kcal (b) 108.7 kcal
required. Hence, enthalpy of formation of water is
(c) –184.6 kcal (d) 184.6 kcal
(a) –142.5 kJ (b) +142.5 kJ
102. If S + O2   SO2 ∆H = –298.2 kJ
(c) –285 kJ (d) +285 kJ
1 110. The standard heats of formation of CH4, H2O and
 SO3 ∆H = –98.2 kJ
SO 2  O 2 
2 CH3OH are –76, –242 and –266 kJ/mol respectively.
SO3  H 2 O 
 H 2 SO4 ∆H = –130.2 kJ The enthalpy change for the following reaction is
1 CH 3 OH  l   H 2  g   CH 4  g   H 2 O  l 
H 2  O 2   H 2 O ∆H = –287.3 kJ
2 (a) –4 kJ/mol (b) –556 kJ/mol
the enthalpy of formation of H2SO4 at 298 K will be (c) –318 kJ/mol (d) –52 kJ/mol
(a) –433.7 kJ (b) –650.3 kJ 111. Given that Hf (H) – 218 kJ/mol, express the H–H
(c) +320.5 kJ (d) –813.9 kJ bond energy in kcal/mol
(a) 52.15 (b) 911
Enthalpy of Reactions/Processes
(c) 104 (d) 52153
103. For the reaction : 112. Which of the following pairs has heat of neutralisation
C  s   O 2  g  
 CO 2  g  equal to –57.1 kJ?
(a) ∆H <∆U (b) ∆H >∆U (a) HNO3, KOH (b)HCl, NH4OH
(c) ∆H = ∆U (d) ∆H = 0 (c) H2SO4, NH4OH (d) CH3COOH,NaOH
104. For which of the following reactions, ∆H is greater than 113. Which of the following neutralisation reactions is most
∆U? exothermic ?
(a) N2(g) + 3H2(g)   2NH3(g) (a) HCl and NaOH
(b) HCN and NaOH
(b) CH4(g) + 2O2(g) 
 CO2(g) + 2H2O(l)
(c) HCl and NH4OH
(c) PCl5(g) 
 PCl3(g) + Cl2(g) (d) CH3COOH and NH4OH
(d) HCl(aq) + NaOH(aq) 
 NaCl(aq) + H2O(aq) 114. Which of the following reaction defines H of ?
105. (∆U – ∆H) for the formation of NH3 from N2 and H2 is : (a) C (diamond)  O 2 (g) 
 CO2 (g)
(a) –2 RT (b) 2 RT 1 1
1 (b) H 2 (g)  F2 (g)  HF(g)
(c) RT (d) RT 2 2
2
(c) N 2 (g)  3H 2 (g) 
 2NH3 (g)
106. The difference between heats of reaction at constant
pressure and constant volume for the reaction. 1
(d) CO(g)  O2 (g)  CO2 (g)
2C 2 H 6  l   15O 2  g   12CO 2  g   6H 2 O  l  at 25°C 2
is 115. The enthalpy of combustion of C6H6(l) is –3250 kJ.
(a) –7.43 kJ (b) +3.72 kJ When 0.39 g of benzene is burnt in excess of oxygen in
(c) –3.72 kJ (d) 7.43 kJ an open vessel, the amount of heat liberated is
107. Consider the reaction at 300 K (a) 16.25 J (b) 16.25 kJ
(c) 32.5 J (d) 32.5 kJ
H 2  g   Cl 2  g   2HCl  g  ; H   185 kJ
If 2 mole of H2 completely react with 2 mole of Cl2 to
form HCl. What is ∆U° for this reaction?
(a) 0 (b) –185 kJ
(c) 370 kJ (d) –370 kJ
THERMODYNAMICS AND THERMOCHEMISTRY 41

116. The heat change for the following reaction at 298 K and 124. The enthalpy of neutralisation of HCl by NaOH is –
constant pressure is +7.3 kcal. –1
1 57.1 kJ and that of HCN by NaOH is –12.1 kJ mol .
A 2 B  s   2A  s   B2  g  ; H  7.3kcal The enthalpy of ionization of HCN is :
2
The heat change at constant volume would be (a) –69.2 kJ (b) –45.0 kJ
(a) +7.3 kcal (b) more than 7.3 kcal (c) 69.2 kJ (d) 45.0 kJ
(c) less than 7.3 kcal (d) zero 125. Calculate the heat of the reaction
117. Enthalpy change for the process, CH 2  CH 2  g   H 2  g   CH 3 CH 3  g 
H2 O(ice)  H2 O (water)
given that bond energy of C – C, C = C, C – H and
is 6.01 kJ mol–1. The entropy change of 1 mole of ice at H – H is 80, 145, 98 and 103 kcal.
its melting point will be (a) –28 kcal mol-1 (b) –5.6 kcal mol-1
(a) 12JK–1 mol–1 (b) 22 JK–1 mol–1 (c) –2.8 kcal mol -1
(d) –56 kcal mol-1
–1 –1
(c) 100 JK mol (d) 30 JK–1 mol–1 126. For the reaction of one mole of zinc dust with one mole
118. The entropy change for the conversion of 1 mol of
of sulphuric acid in a bomb calorimeter, ∆U and W
α–tin (at 13°C, 1 atm) to 1 mol of β–tin (13°C, 1
corresponds to
atm), if enthalpy of transition is 2.095 kJ mol –1 is:
(a) ∆E < 0, W = 0 (b) ∆E = 0, W < 0
(a) 7.32 J mol-1 K-1 (b) 14.62 J K-1 mol-1
-1 -1 (c) ∆E > 0, W = 0 (d) ∆E = 0, W > 0
(c) 56.3 J mol K (d) 0
127. The bond energies C – C, C = C, H – H and C – H
119. The enthalpies of formation of N2O and NO at 298 K
linkages are 350, 600, 400 and 410 kJ/mol respectively.
are 82 and 90 kJ mol-1. The enthalpy of the reaction:
The heat of hydrogenation of ethylene is
N 2 O  g   ½O 2  g  
 2NO  g  (a) – 170 kJ mol–1 (b) – 260 kJ mol–1
–1
(a) –8 kJ (b) 98 kJ (c) – 400 kJ mol (d) – 450 kJ mol–1
(c) –74 kJ (d) 8 kJ 128. The standard heats of formation of CH4, H2O and
120. The enthalpies of solution of anhydrous CuSO4 and CH3OH are –76, –242 and –266 kJ/mol respectively.
CuSO4.5H2O are –15.89 and 2.80 kcal mol–1 The enthalpy change for the following reaction is
respectively. The enthalpy of hydration of CuSO4 to
CH3OH (l) + H2(g)   CH4(g) + H2O (l)
CuSO4.5H2O is :
(a) –4 kJ/mol (b) –556 kJ/mol
(a) –18.69 kcal (b) 13.09 kcal
(c) –318 kJ/mol (d) –52 kJ/mol
(c) –13.09 kcal (d) 18.69 kcal
129. The heat of combustion of solid benzoic acid at
121. If CH3COOH + OH-   CH3COO- + H2O + x kJ
constant volume is –321.30 kJ at 27ºC. The heat of
H+ + OH- 
 H2O + y kJ combustion at constant pressure is
The enthalpy change for the reaction : (a) –321.30 –300 R (b) –321.30 + 300 R
CH3COOH   CH3COO- + H+ is (c) –321.30 – 150 R (d) –321.30 + 900 R
(a) x + y (b) x – y 130.  H for the reaction,
(c) y – x (d) x – y/2  CH 4 (g) at 298 K
C(graphite)  2H 2 (g) 
122. For the reaction, and 1 atm is – 17900 cal. The  E for the above
2H 2  g   O 2  g   2H 2 O  g  ; H   573.2kJ The conversion would be
heat of decomposition of water per mole is (a) – 17900 cal (b) 17900 cal
(a) 286.6 kJ (b) 573.2 kJ (c) 17308 cal (d) – 17304 cal
(c) –28.66 kJ (d) zero 131. If 150 kJ of energy is needed for muscular work to walk
a distance of one km, then how much of glucose one
123. When 400 mL of 0.2 N solution of a weak acid is
has to consume to walk a distance of 5 km, provided
neutralized by a dilute aqueous solution of sodium
only 30% of energy is available for muscular work.
hydroxide under standard conditions, 4.4 kJ of heat is
(The enthalpy of combustion of glucose is 3000 kJ mol–1
liberated. Therefore, the standard enthalpy of
is)
neutralization of this weak acid (in kJ equivalent–1) is
(a) 75 g (b) 30 g
(a) –11 (b) –44
(c) 180 g (d) 150 g
(c) –55 (d) –22
42 THERMODYNAMICS AND THERMOCHEMISTRY

132. The volume of a gas decreases from 500 cc to 300 cc 139. The standard enthalpies of formation of HCl(g), H 2 (g)
when a sample of gas is compressed by an average and Cl2(g) are –92.2, 217.7 and 121.4 kJ mol-1
pressure of 0.6 atm. During this process, 10 J of heat is respectively. The bond dissociation energy of HCl is:
liberated. The change in internal energy is (a) +431.3 kJ (b) 236.9 kJ
(a) –2.16 J (b) 12.156 J (c) –431.3 kJ (d) 339.1 kJ
(c) 2.16 J (d) 101.3 J 140. The enthalpy changes at 25°C in successive breaking of
Bond Dissociation Enthalpy O–H bonds of water are :
H2O(g) 
 H(g) + OH(g) ∆H = 498 kJ mol-1
133. The enthalpy change of a reaction does not depend OH(g) 
 H(g) + O(g) ∆H = 428 kJ mol-1
upon
the bond enthalpy of the O–H bond is :
(a) state of reactants and products
(a) 498 kJ mol-1 (b) 463 kJ mol-1
(b) nature of reactants and products -1
(c) 428 kJ mol (d) 70 kJ mol-1
(c) different intermediate reaction
141. The enthalpy change for the following reaction is 368
(d) initial and final enthalpy change of a reaction
kJ. Calculate the average O–F bond energy.
134. Which of the following does not represent enthalpy
OF2 (g)  O(g)  2F(g)
change during phase transformation?
(a) Standard enthalpy of fusion (a) 184 kJ/mol (b) 368 kJ/mol
(b) Standard enthalpy of vaporisation (c) 536 kJ/mol (d) 736 kJ/mol
(c) Standard enthalpy of sublimation
Hess Law of Constant Heat Summation
(d) Standard enthalpy of formation
135. The enthalpy change for the reaction,
142. Which of the following relationships is not correct?
C 2 H 6  g   2C  g   6H  g  is X kJ. The bond energy (a)  H   E   n g RT
of C–H bond is: (b)  H sub  H fusion   H vap
X X
(a) (b) (c) H0r   H0f  reactants   H0f  products 
2 3
X (d)  H 0r   B.E. of reactants   B.E. of products
(c) (d) data insufficient
6 143. The enthalpies of combustion of carbon and carbon
136. Based on the values of B.E. given, f H of N 2 H 4  g  is: monoxide are –393.5 and –283.0 kJ mol-1 respectively.
The enthalpy of formation of carbon monoxide is :
Given: N–N = 159 kJ mol-1; H–H = 436 kJ mol-1 (a) –676.5 kJ (b) 110.5 kJ
N ≡ N = 941 kJ mol-1, N–H = 398 kJ mol-1 (c) –110.5 kJ (d) 676.5 kJ
(a) 711 kJ mol-1 (b) 62 kJ mol-1
(c) –98 kJ mol-1 (d) –711 kJ mol-1 Gibbs Free Energy Change in Reaction
137. The dissociation energy of CH4 and C2H6 are
respectively 360 and 620 kcal/mole. The bond energy 144. At the sublimation temperature, for the process
of C – C is CO2  s   CO2  g 
(a) 260 k cal/mole (b) 180 k cal/mole
(a) H  0, S  0 and G  0
(c) 130 k cal/mole (d) 80 k cal/mole
138. The bond energy is the energy required to (b) H  0, S  0 and G  0
(a) dissociate one mole of the substance (c) H  0, S  0 and G  0
(b) dissociate bond in 1 kg of the substance
(d) H  0, S  0 and G  0
(c) break one mole of similar bonds
(d) break bonds in one mole of substance
THERMODYNAMICS AND THERMOCHEMISTRY 43

145. A reaction cannot take place spontaneously at any 148. At what temperature liquid water will be in equilibrium
temperature when with water vapour?
(a) Both  H and S are positive (a) 282.4 K (b) 373.6 K
(b) Both H and S are negative (c) 100 K (d) 400 K
(c) H is negative and S is positive 149. Which is the correct relationship between G and
(d) H is positive and S is negative equilibrium constant K p ?
146. For the reaction at 300 K (a) K p   RT log  G 
A(g) + B(g) 
 C(g) G 
(b) K p   e / RT
∆U = –3.0 kcal ∆S = –10.0 cal/K
(c) K p  G  / RT
(R ≈ 2 calmol-1 K-1)
∆G is : (d) K p  e  G  / RT
(a) –600 cal (b) –3600 cal 150. Which of the following is true for the reaction?
(c) 2400 cal (d) 3000 cal  H2O(g) at 100°C and 1 atm pressure
H2O(l) 
147. For a reaction, 2K(g) + L(g) → 2M(g); ∆U° = –10.5 kJ and
∆S° = –44.1 J K–1. Calculate ∆G° for the reaction and (a) ∆S = 0 (b) ∆H = T∆S
predict whether the reaction will be spontaneous or (c) ∆H = ∆U (d) ∆H = 0
non-spontaneous?
(a) If ∆H = + 0.16 kJ, non-spontaneous
(b) If ∆H = – 0.16 kJ, spontaneous
(c) If ∆H = + 2.12 kJ, non-spontaneous
(d) If ∆H = + 2.12 kJ, spontaneous
44 THERMODYNAMICS AND THERMOCHEMISTRY

EXERCISE – 2: Previous Year Questions

1. For the reaction, 7. A reaction occurs spontaneously if
C3 H8 g   5O 2 g   3CO 2 g   4H 2 O l (AIPMT 2005)
(a) TS  H and both H and S are + ve
at constant temperature, H  E is
(b) TS  H and H is +ve and S is –ve
(AIPMT 2003)
(c) TS  H and both H and S are +ve
(a) +RT (b) -3RT
(d) TS  H and both H and S are +ve
(c) +3RT (d) -RT
8. Assume each reaction is carried out in an open
2. The molar heat capacity of water at constant pressure,
container. For which reaction will H = E ?
C, is 75J K-1. When 1.0 kJ of heat is supplied to 100 g
of water which is free to expand, the increase in (AIPMT 2006)
temperature of water is. (a) H 2 (g)  Br2 (g)  2HBr(g)
(AIPMT 2003) (b) C(s)  2H 2 O(g)  2H 2 (g)  CO2 (g)
(a) 1.2K (b) 2.4K (c) PCl5 (g)  PCl3 (g)  Cl2 (g)
(c) 4.8K (d) 6.6K
(d) 2CO(g)  O2 (g)  2CO2 (g)
3. If the bond energies of H–H, Br–Br, and H–Br are 433,
9. Identify the correct statement for change of Gibbs
192 and 364 kJ mol–1 respectively, the H for the
energy for a system ( G system ) at constant temperature
reaction H 2(g)  Br2(g)  2HBr(g) is
and pressure.
(AIPMT 2004) (AIPMT 2006)
(a) –261 kJ (b) +103 kJ (a) If  G system  0 , the process is not spontaneous.
(c) +261 kJ (d) –103 kJ
(b) If  G system  0 , the process is spontaneous.
4. The work done during the expansion of a gas from a
(c) If  G system  0 , the system has attained
volume of 4 dm3 to 6 dm3 against a constant external
pressure of 3 atm is (1 L atm = 101.32J) equilibrium.
(AIPMT 2004) (d) If  G system  0 , the system is still moving in a
(a) –6 J (b) –608 J particular direction.
(c) +304 J (d) –304 J 10. The enthalpy and entropy change for the reaction:
Br2(l)  Cl2(g)  2BrCl(g)
5. The densities of graphite and diamond at 298 K are 2.25
and 3.31 g cm–3, respectively. The standard free energy are 30 kJ mol–1 and 105JK–1 mol–1 respectively. The
temperature at which the reaction will be in equilibrium
difference ( G ) is equal to 1895 J mol–1, the pressure
is
at which graphite will be transformed into diamond at (AIPMT 2006)
298 K is (a) 300 K (b) 285.7 K
(AIPMT 2004) (c) 273 K (d) 450 K
(a) 9.92 × 108 Pa (b) 9.92 × 107 Pa 11. Consider the following reaction
(c) 9.92 × 106 Pa (d) 9.92 × 105 Pa (i) H (aq)  OH (aq)  H 2 O(l) ,  H   X1 kJ mol –1
6. The absolute enthalpy of neutralisation of the reaction: (ii) H 2(g)  1/ 2 O 2(g)  H 2 O(l) ,  H   X 2 kJ mol –1
MgO(g)  2HCl(g)  MgCl 2(aq)  H 2 O (l) (iii) CO 2(g)  H 2(g)  CO (g)  H 2 O(l) ,
Will be  H   X 3 kJ mol –1
(AIPMT 2005) (iv) C 2 H 2(g)  5 / 2 O 2(g)  2 CO 2(g)  H2 O(l) ,
(a) –57.33 kJ mol–1
 H   X 4 kJ mol –1
(b) greater than –57.33 kJ mol–1
Enthalpy of formation of H2O(l) is
(c) less than –57.33 kJ mol–1
(AIPMT 2007)
(d) 57.33 kJ mol–1 –1 –1
(a) +X3 kJ mol (b) –X4 kJ mol
(c) +X1 kJ mol–1 (d) –X2 kJ mol–1
THERMODYNAMICS AND THERMOCHEMISTRY 45

12. Given that bond energies of H – H and Cl – Cl are 430 18. The heat liberated when 1.89 g of benzoic acid is burnt
kJ mol–1 and 240 kJ mol–1 respectively and Hf for in a bomb calorimeter at 25oC increases the
HCl is-90 kJ mol–1 bond enthalpy of HCl is temperature of 18.94 kg of water by 0.632oC. If the
(AIPMT 2007)
specific heat of water at 25oC is 0.998 cal/g-deg, the
(a) 380 kJ mol–1 (b) 425 kJ mol–1
value of the heat of combustion of benzoic acid is
(c) 245 kJ mol–1 (d) 290 kJ mol–1
(AFMC 2010)
13. For the gas phase reaction,
(a) 881.1 kcal (b) 771.4 kcal
PCl5(g)  PCl3(g)  Cl2(g) (c) 981.1 kcal (d) 871.2 kcal
Which of the following conditions are correct? 19. Three moles of an ideal gas expanded spontaneously
(AIPMT 2008) into vacuum. The work done will be
(a) H  0 and S  0 (b) H  0 and S  0 (AIPMT 2010)
(c) H  0 and S  0 (d) H  0 and S  0 (a) infinite (b) 3 Joules
(c) 9 Joules (d) zero.
14. Bond dissociation enthalpy of H2 Cl2, and HCl are 434, 20. The following two reactions are known
242 and 431 kJ mol respectively. Enthalpy of formation Fe2O3(s) + 3CO(g) → 2Fe(s) + 3CO2(g); ∆H = –26.8 kJ
of HCl is FeO(s) + CO(g) → Fe(s) + CO2(g); ∆H = – 16.5 kJ
(AIPMT 2008) The value of ∆H for the following reaction
(a) –93 kJ mol–1 (b) 245 kJ mol–1 Fe2O3(s) + CO(g) → 2FeO(s) + CO2(g) is
(c) 93 kJ mol–1 (d) –245 kJ mol–1 (AIPMT 2010)
15. From the following bond energies: (a) + 10.3 kJ (b) – 43.3 kJ
H — H bond energy : 431.37 kJ mol–1 (c) – 10.3 kJ (d) + 6.2 kJ
C == C bond energy : 606.10 kJ mol–1 21. Standard entropies of X2, Y2 and XY3 are 60, 40 and 50
C — C bond energy : 336.49 kJ mol–1 J K–1 mol–1 respectively. For the reaction
C — H bond energy : 410.50 kJ mol–1 1/2X2 + 3/2Y2 ⇌ XY3, ∆H = –30 kJ, to be at
Enthalpy for the reaction, equilibrium, the temperature should be
(AIPMT 2010)
(a) 750 K (b) 1000 K
(c) 1250 K (d) 500 K
22. For vaporization of water at 1 atmospheric pressure, the
will be values of ∆H and ∆S are 40.63 kJ mol–1 and 108.8 J K–1
(AIPMT 2009) mol–1, respectively.
(a) – 243.6 kJ mol–1 (b) – 120.0 kJ mol–1 The temperature when Gibbs energy change (∆G) for
(c) 553.0 kJ mol–1 (d) 1523.6 kJ mol–1 this transformation will be zero, is
16. Which of the following are not state functions? (AIPMT 2010)
(I) q + w (II) Q (a) 273.4 K (b) 393.4 K
(III) w (IV) H – TS (c) 373.4 K (d) 293.4 K
(AIPMT 2009) 23. Enthalpy change for the reaction, 4H(g)  2H 2 (g) is –
(a) (I), (II) and (III) 869.6 kJ. The dissociation energy of H–H bond is
(b) (II) and (III) (AIPMT 2011)
(c) (I) and (IV) (a) +217.4 kJ (b) – 434.8 kJ
(d) (II), (III) and (IV)
(c) –869.6 kJ (d) +434.8 kJ
17. The values of H and S for the reaction, 24. Which of the following is correct option for free
C(graphite)  CO 2(g)  2CO (g) expansion of an ideal gas under adiabatic condition?
Are 170 kJ and 170 JK–1, respectively. This reaction (AIPMT 2011)
will be spontaneous at (a) q = 0, ∆T ≠ 0, w = 0
(AIPMT 2009) (b) q ≠ 0, ∆T = 0, w = 0
(a) 910 K (b) 1110 K (c) q = 0, ∆T = 0, w = 0
(c) 510 K (d) 710 K (d) q = 0, ∆T < 0, w ≠ 0
46 THERMODYNAMICS AND THERMOCHEMISTRY

25. Consider the following processes: 31. Three thermochemical equations are given below:
∆H (kJ/mol) (i) C(graphite) + O2(g) → CO2(g); ∆rH° = x kJ mol–1
1/2A → B +150 (ii) C(graphite) + ½O2(g) → CO(g); ∆rH° = y kJ mol–1
3B → 2C + D –125 (iii) CO(g) + ½O2(g) → CO2(g); ∆rH° = z kJ mol–1
E + A → 2D +350 Based on the above equations, find out which of the
For B + D → E + 2C, ∆H will be relationship given below is correct.
(AIPMT 2011) (a) z = x + y (b) x = y + z
(a) 525 kJ/mol (b) –175 kJ/mol (c) y = 2z – x (d) x = y – z
(c) –325 kJ/mol (d) 325 kJ/mol (Karnataka NEET 2013)
26. If the enthalpy change for the transition of liquid water 32. When 5 litres of a gas mixture of methane and propane
to steam is 30 kJ mol–1 at 27°C, the entropy change for is perfectly combusted at 0°C and 1 atmosphere, 16
the process would be litres of oxygen at the same temperature and pressure is
(AIPMT 2011) consumed. The amount of heat released from this
(a) 10 J mol–1 K–1 (b) 1.0 J mol–1 K–1 combustion in
(c) 0.1 J mol–1 K–1 (d) 100 J mol–1 K–1 kJ (∆Hcomb (CH4) = 890 kJ mol–1,
27. Equal volumes of two monatomic gases, A and B at ∆Hcomb. (C3H8) = 2220 kJ mol–1) is
same temperature and pressure are mixed. The ratio of (Karnataka NEET 2013)
specific heats (CP/CV) of the mixture will be (a) 38 (b) 317
(AIPMT 2012) (c) 477 (d) 32
(a) 0.83 (b) 1.50 33. A reaction having equal energies of activation for
(c) 3.3 (d) 1.67 forward and reverse reactions has
28. Standard enthalpy of vaporisation H ovap for water at (NEET 2013)
(a) ∆H = 0 (b) ∆H = ∆G = ∆S = 0
100°C is 40.66 kJ mol–1. The internal energy of
(c) ∆S = 0 (d) ∆G = 0
vaporisation of water at 100°C (in kJ mol–1) is
34. Which of the following statements is correct for the
(AIPMT 2012)
(a) +37.56 (b) – 43.76 spontaneous adsorption of a gas?
(c) + 43.76 (d) + 40.66 (AIPMT 2014)
(a) ∆S is negative and, therefore ∆H should be highly
(Assume water vapour to behave like an ideal gas)
positive.
29. In which of the following reactions, standard reaction
(b) ∆S is negative and therefore, ∆H should be highly
entropy change (∆S°) is positive and standard Gibbs
negative.
energy change (∆G°) decreases sharply with increasing
(c) ∆S is positive and therefore, ∆H should be negative.
temperature?
(d) ∆S is positive and therefore, ∆H should also be
(AIPMT 2012)
highly positive.
1
(a) C(graphite) + O2(g) → CO(g) 35. For the reaction, X2O4(l) → 2XO2(g)
2
∆U = 2.1 kcal, ∆S = 20 cal K–1 at 300 K
1 Hence, ∆G is
(b) CO(g) + O2(g) → CO2(g)
2 (AIPMT 2014)
1 (a) 2.7 kcal (b) – 2.7 kcal
(c) Mg(s) + O2(g) → MgO(s)
2 (c) 9.3 kcal (d) – 9.3 kcal
1 1 1 36. The heat of combustion of carbon to CO2 is –393.5
(d) C(graphite) + O2(g) → CO2(g)
2 2 2 kJ/mol. The heat released upon formation of 35.2 g of
30. The enthalpy of fusion of water is 1.435 kcal/mol. The CO2 from carbon and oxygen gas is
molar entropy change for the melting of ice at 0°C is (AIPMT 2015)
(AIPMT 2012) (a) + 315 kJ (b) – 630 kJ
(a) 10.52 cal/(mol K) (b) 21.04 cal/(mol K) (c) – 3.15 kJ (d) – 315 kJ
(c) 5.260 cal/(mol K) (d) 0.526 cal/(mol K)
THERMODYNAMICS AND THERMOCHEMISTRY 47

37. For a sample of perfect gas when its pressure is 43. Under isothermal conditions, a gas at 300 K expands
changed isothermally from pi to pf, the entropy change from 0.1 L to 0.25 L against a constant external
is given by. pressure of 2 bar. The work done by the gas is
[Given that 1 L bar = 100 J]
(NEET-II 2016)
(NEET 2019)
p  p  (a) 30 J (b) –30 J
(a) ∆S = nR ln  f  (b) ∆S = nR ln  i 
p
 i  pf  (c) 5 kJ (d) 25 J
p  44. Reversible expansion of an ideal gas under isothermal
p 
(c) ∆S = nRT ln  f  (d) ∆S = RT ln  i  and adiabatic conditions are as shown in the figure.
p
 i   pf 
38. The correct thermodynamic conditions for the
spontaneous reaction at all temperatures is
(NEET-I 2016)
(a) ∆H < 0 and ∆S > 0 (b) ∆H < 0 and ∆S < 0
(c) ∆H < 0 and ∆S = 0 (d) ∆H > 0 and ∆S < 0
39. Consider the following liquid-vapour equilibrium. AB → Isothermal expansion
Liquid ⇌ Vapour AC → Adiabatic expansion
Which of the following relations is correct? Which of the following options is not correct?
(NEET-I 2016)
d ln P H v d ln P H v (Odisha NEET 2019)
(a)  (b) 
dT 2 T2 dT RT 2 (a) ∆Sisothermal > ∆Sadiabatic
d ln G H v d ln P H v (b) TA = TB
(c)  (d) 
dT 2 RT 2 dT RT (c) Wisothermal > Wadiabatic
40. A gas is allowed to expand in a well-insulated container (d) Tc > TA
against a constant external pressure of 45. An ideal gas expands isothermally from 10–3 m3 to 10–2
2.5 atm from an initial volume of 2.50 L to a final m3 at 300 K against a constant pressure of 105 N m–2.
volume of 4.50 L. The change in internal energy U of The work done on the gas is
the gas in joules will be (Odisha NEET 2019)
(NEET 2017) (a) +270 kJ (b) –900 J
(a) – 500 J (b) – 505 J (c) +900 kJ (d) –900 kJ
(c) + 505 J (d) 1136.25 J 46. In which case change in entropy is negative?
41. For a given reaction, ∆H = 35.5 kJ mol–1 and ∆S = 83.6 (NEET 2019)
J K–1 mol–1. The reaction is spontaneous at (Assume (a) 2H(g) → H2(g)
that ∆H and ∆S do not vary with temperature.) (b) Evaporation of water
(c) Expansion of a gas at constant temperature
(NEET 2017) (d) Sublimation of solid to gas
(a) T > 425 K (b) all temperatures 47. The correct option for free expansion of an ideal gas
(c) T > 298 K (d) T < 425 K under adiabatic condition is.
42. The bond dissociation energies of X2, Y2 and XY are in (NEET 2020)
the ratio of 1 : 0.5 : 1. ∆H for the formation of XY is – (a) q = 0, ∆T = 0 and w = 0
200 kJ mol–1. The bond dissociation energy of X2 will (b) q = 0, ∆T < 0 and w > 0
(c) q < 0, ∆T = 0 and w = 0
be
(d) q > 0, ∆T > 0 and w > 0
(NEET 2018)
(a) 100 kJ mol–1 (b) 800 kJ mol–1
(c) 200 kJ mol–1 (d) 400 kJ mol–1
48 THERMODYNAMICS AND THERMOCHEMISTRY

48. For the reaction, 2Cl(g) → Cl2(g), the correct option is

(NEET 2020)
(a) ∆rH > 0 and ∆rS > 0 (b) ∆rH > 0 and ∆rS < 0
(c) ∆rH < 0 and ∆rS > 0 (d) ∆rH < 0 and ∆rS < 0

49. Which one among the following is the correct option

for right relationship between CP and CV for one mole (c)
of ideal gas?
(NEET 2021)
(a) CP = RCV (b) CV = RCP
(c) CP + CV = R (d) CP – CV = R
50. For irreversible expansion of an ideal gas under
isothermal condition, the correct option is (d)
(NEET 2021)
(a) ΔU = 0, ΔStotal ≠ 0
(b) ΔU ≠ 0, ΔStotal = 0
(c) ΔU = 0, ΔStotal = 0
(d) ΔU ≠ 0, ΔStotal ≠ 0
51. Which of the following p-V curve represents
maximum work done? (NEET 2022)

(a)

(b)
THERMODYNAMICS AND THERMOCHEMISTRY 49

EXERCISE – 3: Achiever’s Section

7. A liquid which is confined inside an adiabatic piston is
Single Choice Questions suddenly taken from state 1 to state 2 by a single stage
process. If the piston comes to rest at point 2 as shown.
1. Which thermodynamic parameter is not a state Then the enthalpy change for the process will be:
function?
(a) q at constant pressure
(b) q at constant volume
(c) W at adiabatic
(d) W at isothermal
2. Which of the following is intensive property?
(a) Enthalpy (b) Entropy 2P0 V0 3P0 V0
(c) Specific heat (d) Volume (a) H  (b) H 
 1  1
3. Which of the following are extensive properties?
(c) H = – P0 V0 (d) None of these
(a) Volume and enthalpy
(b) Volume and temperature 8. A diatomic gas at pressure P, compressed adiabatically
(c) Volume and specific heat to half of its volume, what is the final pressure?
(d) Pressure and temperature (a) (2)1,4P (b) P/(2)1.4
5/3
4. A system undergoes a 3-step process. In step 1, (c) (2) P (d) P/(2)5/3
25 J of work is done by the system as its internal energy 9. If one monoatomic gas is expanded adiabatically from
(U) decreases by 50 J. In step 2, w = -15J and q = +40J. 2L to 10L at 1 atm external pressure then the value of
In step 3 at constant volume, the system gives off 50 J U (in atm L) is
of heat to the surroundings. What is the net internal (a) -8 (b) 0
energy change in J as a result of these three steps? (c) -66.7 (d) 58.2
(a) -50 (b) -75 10. The magnitudes of enthalpy changes for irreversible
(c) -125 (d) +100 adiabatic expansion of a gas from 1L to 2L is H1 and
5. A system undergoes a 2-step process. In step 1, for reversible adiabatic expansion for the same
15 J of work is done on the system as its internal energy expansion is H2. Then
increases by a total of 30 J. In step 2, at constant
(a) H1>H2
volume, the system decreases its internal energy by 20
J. Which statement is true about these changes? (b) H1<H2
(a) The system losses 10J of internal energy as a result (c) H1 = H2, enthalpy being a state function
of the net heat flow in steps 1 & 2 (d) H1 = E1& H2 = E2 where E1& E2 are
(b) 20 J of work is done on the surroundings in Step 2.
magnitudes of change in internal energy of gas in
(c) q = + 45 J in step 1
these expansions respectively.
(d) q = +20 J in step 2
H  T  W
6. 1 mole of an ideal gas expands isothermally reversibly
11. The heat liberated when 1.89g of benzoic acid is burnt
from 2 litre to 4 litre and 3 moles of the same gas
in a bomb calorimeter at 25oC and it increases the
expands from 2 litre to x litre and doing same work,
temperature of 18.94 kg of water by 0.632oC. if the
what is ‘x’?
specific heat of water at 25oC is 0.998 cal/g- oC, the
(a) (8)1/3 (b) (4)2/3
value of the heat of combustion of benzoic acid is
(c) 2 (d) 4
(a) 881.1 kcal (b) 771.124 kcal
(c) 981.1 kcal (d) 871.2 kcal
50 THERMODYNAMICS AND THERMOCHEMISTRY

12. For the reaction of one mole of zinc dust with one mole 18. Match List I with List II and select the correct answer
of sulphuric acid in a bomb calorimeter, U and w using the codes given below the lists:
correspond to List – I List – II
(a) U  0, w  0  G  1. 
A.  
(b) U  0, w  0  P T
(c) U  0, w  0  G  2. T
B.  
(d) U  0, w  0  T P
13. When 1 mol of an ideal gas is compressed to half of its 3. -S
 H 
volume, its temperature becomes double; then the C.  
 S  P
change in entropy (S) would be:
(a) CVln 2 (b) CPln 2  T  4. P
D.  
(c) CV R ln 2 (d) (CV– R) ln 2 × CP  P H
14. Consider the reaction below at 298 K: 5. V
C (graphite) + 2H2 (g)  CH4 (g) →fHº (kJ/mol) – (a) A → 5; B → 1; C → 2; D → 4
(b) A → 5; B → 3; C → 2; D → 4
74.9 S0m(J/K/mol + 5.6 + 130.7 Which statement
(c) A → 3; B → 5; C → 2; D → 1
below is correct ? (d) A → 5; B → 3; C → 2; D → 1
(a) rG0 is – 50.8 kJ and the reaction is driven by 19. Bond dissociation energy of CH4 is 360 kJ/mol and
enthalpyonly. C2H6 is 620 kJ/mol. Then bond dissociation energy of C
(b) rG0 is – 50.8 kJ and the reaction is driven by – C bond is
entropyonly. (a) 170 kJ/mol (b) 50 kJ/mol
(c) rG0 is + 50.8 kJ and the reaction is driven by (c) 80 kJ/mol (d) 220 kJ/mol
bothenthalpy and entropy. Assertion-Reason Type Questions
(d) rG0 is – 50.8 kJ and the reaction is driven by
bothenthalpy and entropy. 20. Assertion: The extensive properties of a single pure
15. What is the entropy change in 2 mol N2, when its substance will not only depend upon the number of
temperature is taken from 400 K to 800 K. at constant moles of the substance present but also on any two of
pressure? the three variables.
(a) 30 J/K (b) 60 J/K Reason: Any extensive property if expressed as per
(c) 40 J/K (d) 20 J/K mole or per gram becomes an intensive property.
16. In an isobaric process, when temperature changes from (a) A (b) B
T1 to T2 , S is equal to (c) C (d) D
(a) 2.303 Cp log (T2/T1) 21. Assertion: There is no change in internal energy for an
(b) 2.303 Cp ln (T2/T1) ideal gas at constant temperature.
(c) Cp ln (T1/T2) Reason: Internal energy of an ideal gas is a function of
(d) Cv ln (T2/T1) temperature only.
(a) A (b) B
H
17. For which of the following cases S  ? (c) C (d) D
T
22. Assertion: In isothermal process, whole of heat energy
(a) A process for which CP = 0 but CV = 0 supplied to the system is converted into internal energy.
(b) An adiabatic process Reason: According to the first law of thermodynamics
(c) An isobaric or isothermal process U =q - w
(d) An isothermal reversible phase transition process (a) A (b) B
(c) C (d) D
THERMODYNAMICS AND THERMOCHEMISTRY 51

23. Assertion: For an isolated system, q is zero. and by  r G    RT ln K eq.

Reason: In an isolated system, change in U and V is Consider the following reaction:
zero.
CO  g   2H 2  g   CH 3 OH  g 
(a) A (b) B
(c) C (d) D Given:  f H  CH 3 OH, g   201 kJ / mol;
24. Assertion: Addition of Q and w gives ΔU.  f H  CO, g   144 kJ / mol
Reason: Addition of two path functions cannot give
state function. S  CH 3OH, g   240J / mol  K;S  H 2 , g 
(a) A (b) B  29 JK 1 mol 1
(c) C (d) D S  CO, g   198 J / mol K;Cop.m  H 2 
25. Assertion: A process is called adiabatic if the system
 28.8 J / mol  K
does not exchange heat with the surroundings.
Reason: It does not involve increase or decrease in Cop.m  CO   29.4 J / mol  K; Cop.m  CH 3OH 
temperature of the system  44 J / mol  K
(a) A (b) B
 320 
(c) C (d) D and ln    0.06, all data at 300 K.
26. Assertion: A reaction which is spontaneous and  300 
accompanied by decrease of randomness must be 29. Find  r S at 320 K for the reaction is:
exothermic. (a) 152.6 J/K-mol
Reason: All exothermic reactions are accompanied by (b) 181.6 J/K-mol
decrease in randomness. (c) -16 J/K-mol
(a) A (b) B (d) -18.58
(c) C (d) D 30. Find  r H at 320 K for the reaction is:
27. Assertion: Entropy is always constant for a closed (a) -87 kJ/mol
system. (b) 87 kJ/mol
Reason: Closed system is always reversible. (c) -87.86 kJ/mol
(a) A (b) B (d) -315 kJ/mol
(c) C (d) D
28. Assertion: Entropy of system increases for a
spontaneous reaction.
Reason: Enthalpy of reaction always not decreases for
spontaneous reaction.
(a) A (b) B
(c) C (d) D

Comprehension
Standard Gibbs energy of reaction   r G   a at a certain
temperature can be compound as
 r G   r H  T. r S and the change in the value of
r H and r S for a reaction with temperature can be
computed as follow:
 r H or2   t H oT2   t Cop  T2  T1 

T 
 r Sor2   t Sor2   t Cop ln  2 
 T1 
 r G   t H  T. r S
128 ANSWER KEY

Answer Key
CHAPTER - 10: THERMODYNAMICS AND THERMOCHEMISTRY
Exercise - 1: Basic Objective Questions

1. (a) 2. (d) 3. (a) 4. (b,c) 77. (d) 78. (b) 79. (a) 80. (a)
5. (d) 6. (a) 7. (d) 8. (c) 81. (c) 82. (c) 83. (d) 84. (b)
9. (a) 10. (d) 11. (c) 12. (d) 85. (b) 86. (a) 87. (b) 88. (d)
13. (d) 14. (c) 15. (a) 16. (a) 89. (d) 90. (a) 91. (b) 92. (c)
17. (a) 18. (a) 19. (c) 20. (c) 93. (a) 94. (b) 95. (b) 96. (b)
21. (b) 22. (d) 23. (c) 24. (b) 97. (a) 98. (d) 99. (d) 100. (c)
25. (d) 26. (a) 27. (d) 28. (c) 101. (a) 102. (d) 103. (c) 104. (c)
29. (b) 30. (b) 31. (c) 32. (b) 105. (b) 106. (a) 107. (d) 108. (a)
33. (b) 34. (a) 35. (a) 36. (d) 109. (c) 110. (d) 111. (c) 112. (a)
37. (c) 38. (b) 39. (d) 40. (a) 113. (a) 114. (b) 115. (b) 116. (c)
41. (b) 42. (d) 43. (a) 44. (a) 117. (b) 118. (a) 119. (b) 120. (a)
45. (a) 46. (c) 47. (d) 48. (b) 121. (c) 122. (a) 123. (c) 124. (d)
49. (b) 50. (a) 51. (d) 52. (b) 125. (a) 126. (a) 127. (a) 128. (d)
53. (a) 54. (b) 55. (b) 56. (c) 129. (c) 130. (d) 131. (d) 132. (c)
57. (c) 58. (d) 59. (b) 60. (d) 133. (c) 134. (d) 135. (d) 136. (b)
61.(a) 62. (c) 63. (c) 64. (a) 137. (d) 138. (c) 139. (a) 140. (b)
65. (a) 66. (c) 67. (c) 68. (d) 141. (a) 142. (c) 143. (c) 144. (d)
69. (b) 70. (d) 71. (c) 72. (c) 145. (d) 146. (a) 147. (a) 148. (b)
73. (d) 74. (d) 75. (b) 76. (b) 149. (d) 150. (b)
ANSWER KEY 129

Exercise - 2: Previous Year Questions Exercise - 3: Achiever’s Section

1. (b) 2. (b) 3. (d) 4. (b) 1. (d) 2. (c) 3. (a) 4. (b)

5. (a) 6. (c) 7. (c) 8. (a) 5. (a) 6. (b) 7. (c) 8. (a)
9. (c) 10. (b) 11. (d) 12. (b) 9. (a) 10. (b) 11. (b) 12. (a)
13. (d) 14. (a) 15. (b) 16. (b) 13. (b) 14. (a) 15. (c) 16. (a)
17. (b) 18. (b) 19. (d) 20. (d) 17. (d) 18. (d) 19. (c) 20. (b)
21. (a) 22. (c) 23. (d) 24. (c) 21. (a) 22. (d) 23. (b) 24. (c)
25. (b) 26. (d) 27. (d) 28. (a)
25. (c) 26. (c) 27. (d) 28. (a)
29. (a) 30. (c) 31. (b) 32. (b)
29. (d) 30. (c)
33. (a) 34. (b) 35. (b) 36. (d)
37. (b) 38. (a,c) 39. (b) 40. (b)
41. (a) 42. (b) 43. (b) 44. (d)
45. (b) 46. (a) 47. (a) 48. (d)
49. (d) 50. (a) 51. (b)