7

Thermodynamics and
Thermochemistry
Topic 1 Thermodynamics
Objective Questions I (Only one correct option) (a) Cyclic process : q = − W
1. An ideal gas is allowed to expand from 1 L to 10 L against a (b) Adiabatic process : ∆U = − W
constant external pressure of 1 bar. The work done in kJ is (c) Isochoric process : ∆U = q
(2019 Main, 12 April I) (d) Isothermal process : q = − W
(a) − 9.0 (b) + 10.0 (c) − 0.9 (d) − 2.0 8. For silver, C p ( J K −1 mol −1 ) = 23 + 0.01 T. If the
2. The difference between ∆H and ∆U ( ∆H − ∆U ), when the temperature (T) of 3 moles of silver is raised from 300 K to
combustion of one mole of heptane (l) is carried out at a 1000 K at 1 atm pressure, the value of ∆H will be close to
temperature T, is equal to (2019 Main, 10 April II) (2019 Main, 8 April I)
(a) − 4 RT (b) 3 RT (c) 4 RT (d) − 3 RT (a) 62 kJ (b) 16 kJ
(c) 21 kJ (d) 13 kJ
3. A process will be spontaneous at all temperature if
(2019 Main, 10 April I) 9. For a diatomic ideal gas in a closed system, which of the
(a) ∆H > 0 and ∆S < 0 (b) ∆H < 0 and ∆S > 0 following plots does not correctly describe the relation
(c) ∆H < 0 and ∆S < 0 (d) ∆H > 0 and ∆S > 0 between various thermodynamic quantities?
(2019 Main, 12 Jan I)
4. During compression of a spring the work done is 10 kJ and 2
kJ escaped to the surroundings as heat. The change in
internal energy, ∆U (in kJ) is (2019 Main, 9 April II) (a)
Cp
(b)
Cv
(a) 8 (b) −12 (c) 12 (d) −8
5. Among the following the set of parameters that represents p T
path functions, is (2019 Main, 9 April I)
(A) q + W (B) q (C) W (D) H − TS (c) U (d) Cv
(a) (A) and (D) (b) (A), (B) and (C)
(c) (B), (C) and (D) (d) (B) and (C) T V
6. 5 moles of an ideal gas at 100 K are allowed to undergo −
O
reversible compression till its temperature becomes 200 K. 10. The standard electrode potential E and its temperature
−
 dE O 
If CV = 28 JK −1 mol −1 , calculate ∆U and ∆pV for this coefficient  −4
 for a cell are 2V and − 5 × 10 VK at
−1

process. ( R = 8.0 JK −1 mol−1 )  dT 

(2019 Main, 8 April II)
(a) ∆U = 2.8 kJ; ∆ ( pV ) = 0.8 kJ 300 K respectively. The cell reaction is
(b) ∆U = 14 J; ∆ ( pV ) = 0.8 J Zn( s ) + Cu2 + ( aq ) → Zn2 + ( aq ) + Cu( s )
(c) ∆U = 14 kJ; ∆ ( pV ) = 4 kJ −
The standard reaction enthalpy (∆ r H O ) at 300 K in kJ mol −1
(d) ∆U = 14 kJ; ∆ ( pV ) = 18 kJ −1
is, [Use, R = 8 JK mol and F = 96,000 C mol−1 ]
−1
7. Which one of the following equations does not correctly
(2019 Main, 12 Jan I)
represent the first law of thermodynamics for the given
(a) − 412.8 (b) − 384.0
processes involving an ideal gas ? (Assume non-expansion
work is zero) (2019 Main, 8 April I)
(c) 206.4 (d) 192.0
110 Thermodynamics and Thermochemistry

11. The reaction, MgO( s ) + C( s ) → Mg ( s ) + CO( g ), 18 The entropy change associated with the conversion of 1 kg
for which ∆ r H º = + 491.1 kJ mol −1
and of ice at 273 K to water vapours at 383 K is
−1 −1
∆ r S º = 198.0 JK mol , is not feasible at 298 K. (Specific heat of water liquid and water vapour are 4.2 kJ
K −1kg−1 and 2.0 kJK −1 kg−1; heat of liquid fusion and
Temperature above which reaction will be feasible is
(a) 2040.5 K (b) 1890.0 K vapourisation of water are 334 kJ kg−1 and 2491 kJkg−1
(c) 2380.5 K (d) 2480.3 K respectively). (log 273 = 2.436, log 373 = 2.572,
12. The standard reaction Gibbs energy for a chemical reaction log 383 = 2.583 ) (2019 Main, 9 Jan II)
at an absolute temperature T is given by, ∆ r G º = A − BT (a) 9.26 kJ kg −1 K −1 (b) 8.49 kJ kg −1 K −1
Where A and B are non-zero constants. (c) 7.90 kJ kg −1 K −1 (d) 2.64 kJ kg −1 K −1
Which of the following is true about this reaction?
19 Consider the reversible isothermal expansion of an ideal gas
(2019 Main, 11 Jan II)
in a closed system at two different temperatures T1 and T2
(a) Endothermic if, A < 0 and B > 0
(T1 < T2 ). The correct graphical depiction of the dependence
(b) Exothermic if, B < 0
of work done (W) on the final volume (V) is
(c) Exothermic if, A > 0 and B < 0 (2019 Main, 9 Jan I)
(d) Endothermic if, A > 0 T2
|W| T2 |W|
13. For the chemical reaction, X - Y , the standard reaction T1
T1
Gibbs energy depends on temperature T (in K) as
3 (a) (b)
∆ rG ° (in kJ mol–1 ) = 120 − T
8
The major component of the reaction mixture at T is O ln V O ln V
(2019 Main, 11 Jan I)
(a) Y if T = 280 K (b) X if T = 350 K |W| T2 |W| T2
(c) X if T = 315 K (d) Y if T = 300 K
T1 T1
14. Two blocks of the same metal having same mass and at
temperature T1 and T2 respectively, are brought in contact (c) (d)
with each other and allowed to attain thermal equilibrium at
constant pressure. The change in entropy, ∆S , for this O ln V O ln V
process is (2019 Main, 11 Jan I)

2  (T1 + T2 )1 / 2  2 T1 + T2  20. The combustion of benzene ( l ) gives CO2 ( g ) and H2 O( l ).

(a) C p ln  (b) C p ln 
 T1T2   4T1T2  Given that heat of combustion of benzene at constant volume
is −3263.9 kJ mol −1 at 25° C; heat of combustion (in kJ
 (T + T2 )2
T + T2 
(c) C p ln 1  (d) 2 C p ln 1  mol −1 ) of benzene at constant pressure will be
 4T1T2   2T1T2  (R = 8.314 JK −1 mol −1 ) (2018 Main)
15. The process with negative entropy change is (a) 4152.6 (b) −452.46
(2019 Main, 10 Jan II) (c) 3260 (d) −3267.6
(a) synthesis of ammonia from N 2 and H 2
21. ∆U is equal to (2017 Main)
(b) dissociation of CaSO4 ( s ) to CaO( s ) and SO3 ( g )
(a) isochoric work (b) isobaric work
(c) dissolution of iodine in water
(c) adiabatic work (d) isothermal work
(d) sublimation of dry ice
22. The standard state Gibbs free energies of formation of
16. An ideal gas undergoes isothermal compression from 5 m 3
3 −2 C(graphite) and C(diamond) at T = 298 K are
to 1 m against a constant external pressure of 4 Nm . Heat
released in this process is used to increase the temperature ∆ f G ° [C(graphite)] = 0 kJ mol −1
of 1 mole of Al. If molar heat capacity of Al is 24 J mol−1 K −1 ,
∆ f G ° [C(diamond)] = 2.9 kJ mol −1
the temperature of Al increases by (2019 Main, 10 Jan II)
3 2 The standard state means that the pressure should be 1 bar,
(a) K (b) 1K (c) 2 K (d) K
2 3 and substance should be pure at a given temperature. The
conversion of graphite [C(graphite)] to diamond
17 A process has ∆H = 200 J mol −1 and ∆S = 40 JK −1 mol −1 .
[C(diamond)] reduces its volume by 2 × 10−6 m 3 mol −1 . If
Out of the values given below, choose the minimum
C(graphite) is converted to C(diamond) isothermally at
temperature above which the process will be spontaneous
(2019 Main, 10 Jan I) T = 298K, the pressure at which C(graphite) is in
(a) 20 K (b) 4 K (c) 5 K (d) 12 K equilibrium with C(diamond), is (2017 Adv.)
 Thermodynamics and Thermochemistry 111

[Useful information : 1 J = 1kg m 2 s −2 , Given that ∆S ( A → C ) = 50 eu

1 Pa = 1kg m −1 −2
s ; 1 bar = 10 Pa] 5 ∆S (C → D ) = 30 eu
(a) 58001 bar (b) 1450 bar ∆S (D → B ) = –20 eu where, eu is entropy unit
(c) 14501 bar (d) 29001 bar Then, ∆S ( A → B ) is (2006, 3M)

23. One mole of an ideal gas at 300 K in thermal contact with (a) + 100 eu (b) +60 eu
surroundings expands isothermally from 1.0 L to 2.0 L (c) –100 eu (d) –60 eu
against a constant pressure of 3.0 atm. 30. A monoatomic ideal gas undergoes a process in which the
In this process, the change in entropy of surroundings ratio of p to V at any instant is constant and equals to 1. What
( ∆S surr ) in JK −1 is (1 L atm = 101.3 J) (2016 Adv.) is the molar heat capacity of the gas ? (2006, 3M)
(a) 5.763 (b) 1.013 (c) − 1.013 (d) − 5.763 4R 3R 5R
(a) (b) (c) (d) 0
2 2 2
24. The following reaction is performed at 298K
31. One mole of monoatomic ideal gas expands adiabatically at
2NO( g ) + O2 ( g ) r 2NO2 ( g )
initial temperature T against a constant external pressure of
The standard free energy of formation of NO(g) is
1 atm from 1 L to 2 L. Find out the final temperature
86.6 kJ/mol at 298 K. What is the standard free energy of
(R = 0.0821 L atm K − 1 mol − 1 ) (2005, 1M)
formation of NO2 ( g ) at 298 K? ( K p = 1.6 × 1012 ) (2015 Main) T
(a) T (b)
(a) R( 298 ) ln (1. 6 × 1012 ) – 86600 ( 2 )5 / 3 − 1
(b) 86600 + R( 298 ) ln (1. 6 × 1012 ) 2 2
(c) T − (d) T +
ln (1. 6 × 1012 ) 3 × 0.082 3 × 0.082
(c) 86600 –
R ( 298 ) 32. 2 moles of an ideal gas expanded isothermally and
(d) 0. 5 [ 2 × 86600 – R ( 298 ) ln (1. 6 × 1012 )] reversibly from 1 L to 10 L at 300 K. What is the enthalpy
change? (2004, 1M)
25. For the process, H2 O ( l ) → H2 O ( g )
(a) 4.98 kJ (b) 11.47 kJ (c) –11.47 kJ (d) 0 kJ
at T = 100° C and 1 atmosphere pressure, the correct choice is
33. Spontaneous adsorption of a gas on solid surface is an
(a) ∆S system > 0 and ∆S surrounding > 0 (2014 Adv.)
exothermic process because (2004, 1M)
(b) ∆S system > 0 and ∆S surrounding < 0 (a) ∆H increases for system (b) ∆S increases for gas
(c) ∆S system < 0 and ∆S surrounding > 0 (c) ∆S decreases for gas (d) ∆G increases for gas
(d) ∆S system < 0 and ∆S surrounding < 0
34. One mole of a non-ideal gas undergoes a change of state
26. A piston filled with 0.04 mole of an ideal gas expands (2.0 atm, 3.0 L, 95 K) → (4.0 atm, 5.0 L, 245 K) with a
reversibly from 50.0 mL to 375 mL at a constant temperature change in internal energy, ∆E = 30.0 L-atm. The change in
of 37.0°C. As it does so, it absorbs 208 J of heat. The values enthalpy ( ∆H ) of the process in L-atm is (2002, 3M)
of q and W for the process will be (a) 40.0 (b) 42.0
(R = 8.314 J / mol K, ln 7.5 = 2.01) (2013 Main)
(c) 44.0
(a) q = + 208 J, W = − 208 J
(d) not defined, because pressure is not constant
(b) q = − 208 J, W = − 208 J
(c) q = − 208 J, W = + 208 J 35. Which of the following statements is false? (2001, 1M)
(d) q = + 208 J, W = + 208 J (a) Work is a state function
27. For the process H2 O( l ) (1 bar, 373 K) → H2 O( g ) (b) Temperature is a state function
(c) Change in the state is completely defined when the
(1 bar, 373 K), the correct set of thermodynamic
initial and final states are specified
parameters is (2007, 3M)
(a) ∆G = 0, ∆S = + ve (b) ∆G = 0, ∆S = − ve (d) Work appears at the boundary of the system
(c) ∆G = + ve, ∆S = 0 (d) ∆G = − ve, ∆S = + ve 36. In thermodynamics, a process is called reversible when
(2001, 1M)
28. The value of log 10 K for a reaction A r B is (a) surroundings and system change into each other
(Given : ∆ r H ° 298 K = − 54.07 kJ mol −1 , (b) there is no boundary between system and surroundings
∆ r S ° 298 K = 10 JK −1 mol −1 and R = 8.314 JK−1 mol−1 ; (c) the surroundings are always in equilibrium with the system
2. 303 × 8. 314 × 298 = 5705) (2007, 3M)
(d) the system changes into the surroundings spontaneously
(a) 5 (b) 10 (c) 95 (d) 100 37. For an endothermic reaction, where ∆H represents the
29. The direct conversion of A to B is difficult, hence it is carried enthalpy of the reaction in kJ/mol, the minimum value for
out by the following shown path the energy of activation will be (1992, 1M)
C → D (a) less than ∆H (b) zero
↑ ↓ (c) more than ∆H (d) equal to ∆H
A B
112 Thermodynamics and Thermochemistry

38. The difference between heats of reaction at constant pressure 42. An ideal gas is expanded form ( p1 , V1 , T1 ) to ( p2 , V2 , T2 )
and constant volume for the reaction under different conditions. The correct statement(s)
2C6 H6 ( l ) + 15O2 → 12CO2 ( g ) + 6H2 O( l ) among the following is (are) (2017 Adv.)
at 25° C in kJ is (1991, 1M) (a) The work done by the gas is less when it is expanded
(a) − 7.43 (b) + 3.72 reversibly from V1 to V2 under adiabatic conditions as
compared to that when expanded reversibly form V1 to V2
(c) − 3.72 (d) + 7.43
under isothermal conditions.
(b) The change in internal energy of the gas is (i) zero, if it is
Objective Questions II expanded reversibly with T1 = T2, and (ii) positive, if it is
(One or more than one correct option) expanded reversibly under adiabatic conditions with T1 ≠ T2
39. In thermodynamics, the p-V work done is given by (c) If the expansion is carried out freely, it is simultaneously
both isothermal as well as adiabatic
w = − ∫ dV pext
(d) The work done on the gas is maximum when it is
For a system undergoing a particular process, the work done is compressed irrversibly from ( p2 , V2 ) to ( p1, V1 ) against
constant pressure p1
 RT a
w = − ∫ dV  − 
V − b V 2  43. For a reaction taking place in a container in equilibrium
with its surroundings, the effect of temperature on its
This equation is applicable to a (2020 Adv.)
equilibrium constant K in terms of change in entropy is
(a) system that satisfies the van der Waals’ equation of state described by (2017 Adv.)
(b) process that is reversible and isothermal (a) With increase in temperature, the value of K for
(c) process that is reversible and adiabatic endothermic reaction increases because unfavourable change
(d) process that is irreversible and at constant pressure in entropy of the surroundings decreases
(b) With increase in temperature, the value of K for exothermic
40. Choose the reaction(s) from the following options, for which
reaction decreases because favourable change in entropy of
the standard enthalpy of reaction is equal to the standard the surrounding decreases
enthalpy of formation. (2019 Adv.)
(c) With increase in temperature, the value of K for
(a) 2C( g ) + 3 H2 ( g ) → C2 H6 ( g ) endothermic reaction increases because the entropy change
(b) 2H2 ( g ) + O2 ( g ) → 2H2 O( l ) of the system is negative
(d) With increase in temperature, the value of K for exothermic
3
(c) O2 ( g ) → O3 ( g ) reaction decreases because the entropy change of the system
2 is positive
1 44. An ideal gas in thermally insulated vessel at internal
(d) S8 ( s ) + O2 ( g ) → SO2 ( g )
8 pressure = p1 , volume = V1 and absolute temperature = T1
41. A reversible cyclic process for an ideal gas is shown below. expands irreversibly against zero external pressure, as
Here, p , V and T are pressure, volume and temperature, shown in the diagram. The final internal pressure,
respectively. The thermodynamic parameters q , w , H and U volume and absolute temperature of the gas are p2 , V2
are heat, work, enthalpy and internal energy, respectively. and T2 , respectively. For this expansion
(2018 Adv.)
pext=0

A(p1, V1, T1) C ( p 2 , V 1 , T2 ) pext=0 Irreversible

Volume (V)

p1,V1,T1 p2,V2,T2
B(p2, V2, T1)

Thermal insulation
Temperature (T) (2014 Adv.)
(a) q = 0 (b) T2 = T1
The correct options is (are)
(c) p2V2 = p1V1 (d) p2V2γ = p1V1γ
(a) q AC = ∆U BC and w AB = p2 (V2 − V1 )
(b) wBC = p2 (V2 − V1 ) and qBC = ∆H AC 45. Benzene and naphthalene form an ideal solution at room
(c) ∆HCA < ∆UCA and q AC = ∆U BC temperature. For this process, the true statement(s) is (are)
(2013 Adv.)
(d) qBC = ∆H AC and ∆HCA > ∆UCA (a) ∆G is positive (b) ∆S system is positive
(c) ∆S surroundings = 0 (d) ∆H = 0
 Thermodynamics and Thermochemistry 113

46. The reversible expansion ob an ideal gas under adiabatic What is the ratio of the standard Gibbs energy of the reaction
and isothermal conditions is shown in the figure. Which of at 1000 K to that at 2000 K? (2020 Adv.)
the following statement(s) is (are) correct? (2012)
115

Partial pressure of B (bar)

(p1,V1,T1) 100
Iso
the
p rma
l
Ad

ia
ba (p2,V2,T2)
tic
(p3,V3,T3)
50
V
(a) T1 = T2
(b) T3 > T1 10
(c) Wisothermal > Wadiabatic t′ Time
(d) ∆U isothermal > ∆U adiabatic
47. For an ideal gas, consider only p -V work in going from Assertion and Reason
initial state X to the final state Z. The final state Z can be Read the following questions and answer as per the direction
reached by either of the two paths shown in the figure. given below :
(a) Statement I is true; Statement II is true; Statement II is
p(atmosphere)

X Y
the correct explanation of Statement I
(b) Statement I is true; Statement II is true; Statement II is
Z not the correct explanation of Statement I
(c) Statement I is true; Statement II is false
(d) Statement I is false; Statement II is true
V(litre)
52. Statement I There is a natural asymmetry between
[Take ∆S as change in entropy and W as work done]. converting work to heat and converting heat to work.
Which of the following choice(s) is (are) correct? (2012)
Statement II No process is possible in which the sole result
(a) ∆S X → Z = ∆S X → Y + ∆S Y → Z is the absorption of heat from a reservoir and its complete
(b) W X → Z = W X → Y + WY → Z
conversion into work. (2008, 3M)
(c) W X → Y → Z = W X → Y
(d) ∆S X → Y → Z = ∆S X → Y 53. Statement I For every chemical reaction at equilibrium,
standard Gibbs energy of reaction is zero.
48. Among the following, extensive property is (properties are) Statement II At constant temperature and pressure,
(2010)
(a) molar conductivity (b) electromotive force chemical reactions are spontaneous in the direction of
(c) resistance (d) heat capacity decreasing Gibbs energy. (2008, 3M)

54. Statement I The heat absorbed during the isothermal

49. Among the following, the state function(s) is(are)
expansion of an ideal gas against vacuum is zero.
(a) internal energy (2009)
Statement II The volume occupied by the molecules of an
(b) irreversible expansion work ideal gas is zero. (2000, S, 1M)
(c) reversible expansion work
(d) molar enthalpy Passage Based Questions
50. Identify the intensive quantities from the following. A fixed mass m of a gas is K L
(1993, 1M) subjected to transformation of
(a) enthalpy (b) temperature states from K to L to M to N and Pressure
(c) volume (d) refractive index back to K as shown in the figure.
(2013 Adv.)
Numerical Answer Type Questions N M
Volume
51. Consider the reaction, A B at 1000 K. At time t’, the
q
temperature of the system was increased to 2000 K and the 55. The pair of isochoric processes among the transformation of
system was allowed to reach equilibrium. Throughout this states is
experiment the partial pressure of A was maintained at 1 bar. (a) K to L and L to M (b) L to M and N to K
Given, below is the plot of the partial pressure of B with time. (c) L to M and M to N (d) M to N and N to K
114 Thermodynamics and Thermochemistry

56. The succeeding operations that enable this transformation of Integer Answer Type Question
states are
(a) heating, cooling, heating, cooling 67. One mole of an ideal gas is taken from a to b along two paths
(b) cooling, heating, cooling, heating denoted by the solid and the dashed lines as shown in the
graph below. If the work done along the solid line path is Ws
(c) heating, cooling, cooling, heating
and that along the dotted line path is Wd , then the integer
(d) cooling, heating, heating, cooling
closest to the ratio Wd / Ws is (2010)
4.5
Match the Columns 4.0 a
57. Match the thermodynamic processes given under Column I 3.5

with the expressions given under Column II. 3.0

p 2.5
(atm)
Column I Column II 2.0
1.5
A. Freezing of water at 273 K and 1 atm p. q=0 1.0
B. Expansion of 1 mole of an ideal gas into q. W =0 0.5 b
a vacuum under isolated conditions 0.0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0
C. Mixing of equal volumes of two ideal r. ∆S sys < 0 V (L)
gases at constant temperature and
pressure in an isolated container Subjective Questions
D. Reversible heating of H2 ( g ) at 1 atm s. ∆U = 0 68. For the reaction, 2CO + O2 → 2CO2 ; ∆H = − 560 kJ. Two
from 300 K to 600 K, followed by moles of CO and one mole of O2 are taken in a container of
reversible cooling to 300 K at 1 atm volume 1 L. They completely form two moles of CO2 , the
t. ∆G = 0 gases deviate appreciably from ideal behaviour. If the
pressure in the vessel changes from 70 to 40 atm, find the
58. Match the transformations in Column I with appropriate
magnitude (absolute value) of ∆U at 500 K. (1 L-atm = 0.1 kJ)
options in Column II. (2011) (2006, 3M)

Column I Column II 69. 100 mL of a liquid contained in an isolated container at a

A. CO2 ( s ) → CO2 ( g ) p. Phase transition pressure of 1 bar. The pressure is steeply increased to
100 bar. The volume of the liquid is decreased by 1 mL at
B. CaCO3 ( s ) → CaO( s ) + CO2 ( g ) q. Allotropic change this constant pressure. Find the ∆H and ∆U . (2004, 2M)
C. 2H• → H2 ( g ) r. ∆H is positive 3R 3R
70. CV value of He is always but CV value of H2 is at low
D. P(white, solid) → P(red, solid) s. ∆S is positive 2 2
t. ∆S is negative 5R
temperature and at moderate temperature and more than
2
Fill in the Blanks 5R
at higher temperature. Explain in two or three lines.
2 (2003, 2M)
59. Enthalpy is an ............... property. (1997, 1M)
71. Two moles of a perfect gas undergo the following processes :
60. When Fe(s) is dissolved in aqueous hydrochloric acid in a
(a) a reversible isobaric expansion from (1.0 atm, 20.0 L)
closed vessel, the work done is ................ . (1997)
to (1.0 atm, 40.0 L)
61. The heat content of the products is more than that of the (b) a reversible isochoric change of state from (1.0 atm,
reactants in an .............. reaction. (1993, 1M) 40.0 L) to (0.5 atm, 40.0 L)
62. A system is said to be ........ if it can neither exchange matter (c) a reversible isothermal compression from (0.5 atm,
nor energy with the surroundings. (1993, 1M) 40.0 L) to (1.0 atm, 20.0 L)
63. C p − CV for an ideal gas is ................. (i) Sketch with labels each of the processes on the same
(1984, 1M)
p-V diagram.
64. The total energy of one mole of an ideal monatomic gas at (ii) Calculate the total work (W) and the total heat change
27° C is ..............cal. (1984, 1M) (Q) involved in the above processes.
(iii) What will be the values of ∆ U, ∆H and ∆S for the
True/False overall process? (2002, 5M)
65. First law of thermodynamics is not adequate in predicting 72. When 1-pentyne (A) is treated with 4 N alcoholic KOH at
the direction of a process. (1982, 1M)
175° C, it is converted slowly into an equilibrium mixture of
66. Heat capacity of a diatomic gas is higher than that of a
1.3% 1-pentyne (A), 95.2% 2-pentyne (B) and 3.5% of
monoatomic gas. (1985, 1/2 M)
 Thermodynamics and Thermochemistry 115

1, 2-pentadiene (C). The equilibrium was maintained at Calculate the enthalpy change in this process CV m for argon
175° C. Calculate ∆G° for the following equilibria. is 12.49 JK −1 mol −1 . (2000, 4M)

B r A, ∆G°1 = ? 75. A gas mixture of 3.67 L of ethylene and methane on

B r C, ∆G° 2 = ? complete combustion at 25° C produces 6.11 L of CO2 . Find
out the amount of heat evolved on burning 1 L of the gas
From the calculated value of ∆G°1 and ∆G° 2 indicate the
mixture. The heat of combustion of ethylene and methane
order of stability of (A), (B) and (C). Write a reasonable
are − 1423 and − 891 kJ mol −1 at 25°C. (1991, 5M)
reaction mechanism showing all intermediates leading to
(A), (B) and (C). 76. An athlete is given 100 g of glucose (C6 H12 O6 ) of energy
(2001, 10M)
equivalent to 1560 kJ. He utilizes 50 per cent of this gained
1
73. Show that the reaction, CO( g ) + O2 ( g ) → CO2 ( g ) at energy in the event. In order to avoid storage of energy in the
2
body, calculate the weight of water he would need to
300 K, is spontaneous and exothermic, when the standard
perspire. The enthalpy of evaporation of water is 44 kJ/mol.
entropy change is − 0.094 kJ mol −1 K −1 . The standard (1989, 2M)
Gibbs’ free energies of formation for CO2 and CO are
77. Following statement is true only under some specific
–394.4 and –137.2 kJ mol −1 , respectively. (2000, 3M) conditions. Write the conditions for that in not more than
74. A sample of argon gas at 1 atm pressure and 27° C expands two sentences
reversibly and adiabatically from 1.25 dm3 to 2.50 dm3 . “The heat energy q, absorbed by a gas is ∆H.’’ (1984, 1M)

Topic 2 Thermochemistry
Objective Questions I (Only one correct option) 1
(iii) CO ( g ) + O2 ( g ) → CO2 ( g ); ∆ r H È = z kJ mol− 1
1. Lattice enthalpy and enthalpy of solution of NaCl are 788 kJ 2
mol −1 and 4 kJ mol −1 , respectively. The hydration enthalpy Based on the above thermochemical equations, find out
of NaCl is (2020 Main, 5 Sep II)
which one of the following algebraic relationships is correct?
(2019 Main, 12 Jan II)
(a) −780 kJ mol −1 (b) 780 kJ mol −1 (a) y = 2 z − x (b) x = y − z
(c) −784 kJ mol −1 (d) 784 kJ mol −1 (c) z = x + y (d) x = y + z
2. The variation of equilibrium constant with temperature is 5. Given, C(graphite) + O2 ( g ) → CO2 ( g );
given below: (2020 Main, 6 Sep I)
∆ r H ° = − 393.5 kJ mol − 1
Temperature Equilibrium constant
1
T1 = 25° C K 1 = 10 H2 ( g ) + O2 ( g ) → H2 O( l ); ∆ r H ° = − 285.8 kJ mol −1
2
T2 = 100° C K 2 = 100 CO2 ( g ) + 2 H2 O( l ) → CH4 ( g ) + 2O2 ( g );
The values of ∆H °, ∆G° at T1 and ∆G° at ∆ r H ° = + 890.3 kJ mol −1
T2 (in kJ mol −1 ) respectively, are close to
Based on the above thermochemical equations, the value of
[use R = 8.314 JK −1 mol −1 ] ∆ r H ° at 298 K for the reaction, (2017 Main)
(a) 28.4, − 714
. and − 5.71 C(graphite) + 2 H2 ( g ) → CH4 ( g ) will be
(b) 0.64, − 714
. and − 5.71
(c) 28.4, − 5.71 and − 14. 29 (a) + 78 .8 kJ mol − 1 (b) + 144.0 kJ mol − 1
(d) 0.64, − 5.71 and − 14. 29 (c) − 74 .8 kJ mol − 1 (d) − 144.0 kJ mol − 1
−1
3. Enthalpy of sublimation of iodine is 24 cal g at 200°C. If
6. The heats of combustion of carbon and carbon monoxide are
specific heat ofI2( s) andI2 (vap.) are 0.055 and 0.031 cal g −1 K −1
− 393.5 and − 283.5 kJ mol−1 , respectively. The heat of
respectively, then enthalpy of sublimation of iodine at 250°C
formation (in kJ) of carbon monoxide per mole is
in cal g −1 is (2019 Main, 12 April I) (2016 Main)
(a) 2.85 (b) 5.7 (c) 22.8 (d) 11.4 (a) 676.5 (b) −676.5
4. Given : (c) −110.5 (d) 110.5
(i) C(graphite) + O2 ( g ) → CO2 ( g ); ∆ r H È = x kJ mol− 1 7. For the complete combustion of ethanol,
C2 H 5 OH( l ) + 3O2 ( g ) → 2CO2 ( g ) + 3H2 O( l ), the
1
(ii) C(graphite) + O2 ( g ) → CO2 ( g ); amount of heat produced as measured in bomb
2
calorimeter, is 1364.47 kJ mol −1 at 25°C. Assuming
∆ r H È = y kJ mol− 1
116 Thermodynamics and Thermochemistry

ideality the enthalpy of combustion, ∆C H, for the reaction 16. The thermal dissociation of equilibrium of CaCO3 ( s ) is
will be (R = 8.314 J K–1 mol –1 ) (2014 Main) studied under different conditions. (2013 Adv.)
(a) − 1366. 95 kJ mol −1 (b) − 1361. 95 kJ mol −1 CaCO3 ( s ) r CaO( s ) + CO2 ( g )
(c) − 1460. 50 kJ mol −1 (d) − 1350. 50 kJ mol −1 For this equilibrium, the correct statement(s) is/are
(a) ∆H is dependent on T
8. The standard enthalpies of formation of CO2 ( g ), H2 O( l ) and (b) K is independent of the initial amount of CaCO3
glucose(s) at 25°C are − 400 kJ/mol, − 300 kJ/mol and (c) K is dependent on the pressure of CO2 at a given T
− 1300 kJ/mol, respectively. The standard enthalpy of (d) ∆H is independent of the catalyst, if any
combustion per gram of glucose at 25°C is (2013 Adv.)
(a) + 2900 kJ (b) − 2900 kJ Subjective Questions
(c) − 16. 11 kJ (d) + 16.11kJ 17. In a constant volume calorimeter, 3.5 g of a gas with
9. Using the data provided, calculate the multiple bond energy molecular weight 28 was burnt in excess oxygen at 298.0 K.
−1
(kJ mol ) of a C≡≡ C bond C2 H2 . That energy is (take the The temperature of the calorimeter was found to increases
from 298.0 K to 298.45 K due to the combustion process.
bond energy of a C  H bond as 350 kJ mol −1 ) (2012) Given that the heat capacity of the calorimeter is 2.5 kJ K − 1 ,
2C( s ) + H2 ( g ) → C2 H2 ( g ) ; ∆H = 225 kJ mol −1 the numerical value for the enthalpy of combustion of the
2C( s ) → 2C( g ) ; ∆H = 1410 kJ mol −1 gas in kJ mol − 1 is (2009)

H2 ( g ) → 2H( g ) ; ∆H = 330 kJ mol −1 18. Diborane is a potential rocket fuel which undergoes
combustion according to the reaction
(a) 1165 (b) 837 (c) 865 (d) 815
B2 H6 ( g ) + 3O2 ( g ) → B2 O3 ( s ) + 3H2 O ( g )
10. The species which by definition has zero standard molar
From the following data, calculate the enthalpy change for
enthalpy of formation at 298 K is (2010)
the combustion of diborane. (2000, 2M)
(a) Br2 ( g ) (b) Cl 2 ( g ) (c) H2 O( g ) (d) CH4 ( g )
3
11. The bond energy (in kcal mol −1 ) of C— C single bond is 2B ( s ) + O2 ( g ) → B2 O3 ( s ) ; ∆H = − 1273 kJ mol −1
2
approximately (2010)
1
(a) 1 (b) 10 (c) 100 (d) 1000 H2 ( g ) + O2 ( g ) → H2 O ( l ) ; ∆H = − 286 kJ mol –1
2
12. ∆H vap = 30 kJ/mol and ∆S vap = 75 Jmol –1 K –1 . Find the
H2 O ( l ) → H2 O ( g ) ; ∆H = 44 kJ mol −1
temperature of vapour, at one atmosphere (2004, 1M)
(a) 400 K (b) 350 K (c) 298 K (d) 250 K 2B ( s ) + 3H2 ( g ) → B2 H6 ( g ) ; ∆H = 36 kJ mol −1
19. Estimate the average S–F bond energy in SF6 . The values of
13. Which of the following reactions defines ∆H f° ?
standard enthalpy of formation of SF6 (g), S( g ) and F( g )
(2003, 1M)
(a) C(diamond) + O2 ( g ) → CO2 ( g ) are : – 1100, 275 and 80 kJ mol –1 respectively. (1999, 3M)
1 1 20. From the following data, calculate the enthalpy change for
(b) H2 ( g ) + F2 ( g ) → HF( g )
2 2 the combustion of cyclopropane at 298 K. The enthalpy of
(c) N2 ( g ) + 3H2 ( g ) → 2NH3 ( g ) formation of CO2 ( g ), H2 O ( l ) and propane (g) are –393.5,
1 −285.8 and 20.42 kJ mol −1 respectively. The enthalpy of
(d) CO ( g ) + O2 ( g ) → CO2 ( g ) isomerisation of cyclopropane to propene is −33.0 kJ mol −1 .
2
(1998, 5M)
14. The ∆H f° for CO2 ( g ),CO( g ) and H2 O ( g ) are 21. Compute the heat of formation of liquid methyl alcohol in
− 393.5, − 110.5 and −241.8 kJ mol −1 respectively. The kJ mol −1 , using the following data. Heat of vaporisation of
−1 liquid methyl alcohol = 38 kJ/mol. Heat of formation of
standard enthalpy change (in kJ mol ) for the reaction
CO2 ( g ) + H2 ( g ) → CO( g ) + H2 O( g ) is gaseous atoms from the elements in their standard states :
(2000, 1M)
H = 218 kJ/mol, C = 715 kJ/mol, O = 249 kJ/mol.
(a) 524.1 (b) + 41.2
Average bond energies: (1997, 5M)
(c) −262.5 (d) − 41.2
C— H = 415 kJ/mol, C— O = 356 kJ/mol,
Objective Question II O— H = 463 kJ/mol
(One or more than one correct option) 22. The standard molar enthalpies of formation of
cyclohexane (l) and benzene (l) at 25° C are −156 and
15. The following is/are endothermic reaction(s) (1999, 3M)
+ 49 kJ mol −1 respectively. The standard enthalpy of
(a) Combustion of methane
hydrogenation of cyclohexene (l) at 25° C is −119 kJ mol −1 .
(b) Decomposition of water
Use these data to estimate the magnitude of the resonance
(c) Dehydrogenation of ethane to ethylene
energy of benzene. (1996, 2M)
(d) Conversion of graphite to diamond
 Thermodynamics and Thermochemistry 117

23. The polymerisation of ethylene to linear polyethylene is 29. The standard molar heat of formation of ethane, carbon
represented by the reaction, dioxide and liquid water are −21.1, −94.1 and − 68.3 kcal
n [CH2 == CH2 ] → [ CH2 — CH2
]n respectively. Calculate the standard molar heat of
combustion of ethane. (1986, 2M)
where, n has large integral value. Given that the average
enthalpies of bond dissociation for C == C and C  C at 30. The bond dissociation energies of gaseous H2 ,Cl 2 and HCl
298 K are +590 and +311 kJ/mol respectively, calculate the are 104, 58 and 103 kcal/mol respectively. Calculate the
enthalpy of polymerization per mole of ethylene at 298 K. enthalpy of formation of HCl gas. (1985, 2M)
(1994, 2M) 31. Given the following standard heats of reactions
24. In order to get maximum calorific output, a burner should (i) heat of formation of water = − 68.3 kcal
have an optimum fuel to oxygen ratio which corresponds (ii) heat of combustion of acetylene = − 310.6 kcal
to 3 times as much oxygen as is required theoretically (iii) heat of combustion of ethylene = − 337.2 kcal
for complete combustion of the fuel. A burner which has been
Calculate the heat of reaction for the hydrogenation of
adjusted for methane as fuel (with x litre/hour of CH4 and
acetylene at constant volume (25° C).
6x litre/hour of O2 ) is to be readjusted for butane, C4 H10 . (1984, 4M)

In order to get the same calorific output, what should be the 32. The molar heats of combustion of C2 H2 ( g ), C (graphite) and
rate of supply of butane and oxygen? Assume that losses due H2 ( g ) are 310.62 kcal, 94.05 kcal and 68.32 kcal
to incomplete combustion etc., are the same for both fuels respectively. Calculate the standard heat of formation of
and that the gases behave ideally. Heats of combustions: C2 H2 ( g ) . (1983, 2M)

CH4 = − 809 kJ/mol, C4 H10 = − 2878 kJ/mol (1993, 3M) 33. The standard heats of formation of CCl 4 ( g ), H2 O( g ),
25. Determine the enthalpy of the reaction, CO2 ( g ) and HCl( g ) at 298 K are −25.5, −57.8 , −94.1 and
C3 H8 ( g ) + H2 ( g ) → C2 H6 ( g ) + CH4 ( g ), at 25° C, using −22.1 kcal/mol respectively. Calculate ∆H ° (298 K) for the
reaction
the given heat of combustion values under standard conditions.
CCl 4 ( g ) + 2H2 O ( g ) → CO2 ( g ) + 4 HCl ( g ) (1982, 2M)
Compound : H2 ( g ) CH4 ( g ) C2 H6 ( g ) C(graphite)
∆H ° (kJ/mol): −285.8 − 890.0 −1560.0 −393.0 34. The enthalpy for the following reactions ( ∆H ° ) at 25°C are
The standard heat of formation of C3 H8 ( g ) is −103 kJ/mol. given below
1 1
(1992, 3M) (i) H2 ( g ) + O2 ( g ) → OH( g ) ∆H ° = − 10.06 kcal
26. Using the data (all values are in kilocalories per mol at 2 2
25° C) given below, calculate the bond energy of C  C and (ii) H2 ( g ) → 2H( g ) ∆H ° = 104.18 kcal
C  H bonds. (iii) O2 ( g ) → 2O( g ) ∆H ° = 118.32 kcal
C( s ) → C( g ); ∆H = 172
H2 ( g ) → 2H ( g ); ∆H = 104 Calculate the O — H bond energy in the hydroxyl radical.
(1981, 2M)
1
H2 ( g ) + O2 ( g ) → H2 O( l ); ∆H = − 68.0
2
Passage Based Questions
C( s ) + O2 ( g ) → CO2 ( g ); ∆H = − 94.0
When 100 mL of 1.0 M HCl was mixed with 100 mL of 1.0 M
Heat of combustion of C2 H6 = −372.0
NaOH in an insulated beaker at constant pressure, a temperature
Heat of combustion of C3 H8 = −530.0 (1990, 5M)
increase of 5.7°C was measured for the beaker and its contents
27. The standard enthalpy of combustion at 25° C of hydrogen, (Expt. 1). Because the enthalpy of neutralisation of a strong acid
cyclohexene (C6 H10 ) and cyclohexane (C6 H12 ) are − 241, with a strong base is a constant ( −57.0 kJ mol−1 ), this experiment
− 3800 and − 3920 kJ/mol respectively. Calculate the heat could be used to measure the calorimeter constant. In a second
of hydrogenation of cyclohexene. (1989, 2M) experiment (Expt. 2), 100 mL of 2.0 M acetic acid
28. An intimate mixture of ferric oxide, Fe2 O3 , and aluminium, ( K a = 2.0 × 10−5 ) was mixed with 100 mL of 1.0 M NaOH (under
Al, is used in solid fuel rockets. Calculate the fuel value per identical conditions to Expt. 1) where a temperature rise of 5.6°C
gram and fuel value per cc of the mixture. Heats of was measured.
formation and densities are as follows: 35. Enthalpy of dissociation (in kJ mol−1 ) of acetic acid
H f (Al 2 O3 ) = − 399 kcal/mol obtained from the Expt. 2 is
H f (Fe2 O3 ) = − 199 kcal/mol (a) 1.0 (b) 10.0 (c) 24.5 (d) 51.4
Density of Fe2 O3 = 5.2 g/cc, Density of Al = 2.7 g/cc 36. The pH of the solution after Expt. 2 is
(1989, 2M) (a) 2.8 (b) 4.7 (c) 5.0 (d) 7.0