Chemical thermodynamics

(PRADEEP SHARMA)
Section A

1 For the reaction at 298 K, 2A + B→ C, 𝛥 H = 400 kJ mol −1 and 𝛥𝑆 = 0.2 kJ K −1 mol −1 . At [1]
what temperature will the reaction become spontaneous considering 𝛥𝐻 and 𝛥𝑆 to be
constant over the temperature range.
a) 3500 K b) 2000 K c) 1500 K d) 2500 K
2 For the reaction, 2Cl(g)→ Cl 2 (g), what are the signs of 𝛥𝐻 and 𝛥𝑆 ? [1]
a) 𝛥𝐻 < 0, 𝛥𝑆 > 0 b) 𝛥𝐻 > 0, 𝛥𝑆 > 0
c) 𝛥𝐻 > 0, 𝛥𝑆 < 0 d) 𝛥𝐻 < 0, 𝛥𝑆 < 0
3 Lattice enthalpies are determined by [1]
a) Hess’ law b) Born - Haber cycle
c) lattice cycl d) endothermic reaction
4 Which of the following, is correct when decrease in entropy has been taken place? [1]
△
a) 2NaHCO 3 (s) → Na 2 CO 3 (s) + CO 2 (g) + H 2 O(g)
b) Temperature of a crystalline solid is raised from 0 K to 115 K
c) A liquid crystallises into a solid
d) H2 (g) → 2H(g)
5 Entropy is a state function and measures [1]
a) the degree of randomness or disorder in the system.
b) the internal energy of the system.
c) the degree of regularity or order in the system.
d) the enthalpy of the system.
6 Maximum entropy will be in which of the following? [1]
a) water vapour b) snow c) liquid water d) Ice
7 For an isolated system,𝛥𝑈 = 0, what will be 𝛥𝑆 ? [1]
a) 𝛥𝑆 > 0 b) 𝛥𝑆 will increase for some time and then reduce
c) 𝛥𝑆 < 0 d) 𝛥𝑆 = 0
8 Change in entropy of a reversible process can be calculated by: [1]
𝑞
a) 𝛥𝑆𝑠𝑦𝑠 = 𝑅𝑇𝑞𝑠𝑦𝑠,𝑟𝑒𝑣 b) 𝛥𝑆𝑠𝑦𝑠 = 𝑠𝑦𝑠,𝑟𝑒𝑣
𝑇
𝑞𝑠𝑦𝑠,𝑟𝑒𝑣
c) 𝛥𝑆𝑠𝑦𝑠 = d) 𝛥𝑆𝑠𝑦𝑠 = 𝑇𝑞𝑠𝑦𝑠,𝑟𝑒𝑣
2𝑇
9 A reaction, A + B → C + D + q is found to have a positive entropy change reaction will be: [1]
a) spontaneous at high temperature
b) spontaneous only at low temperature
c) spontaneous at all temperature
d) non-spontaneous at all temperature
10 The sign of𝛥𝐺 for a spontaneous and non - spontaneous process respectively are [1]
a) positive and negative b) negative and positive
c) zero and positive d) positive and zero
11 Spontaneity in the context of chemical thermodynamics means [1]
a) having the potential to proceed without the assistance of an external agency.
b) having the potential to proceed fast.
 c) having the potential to proceed instantaneously.
d) having the potential to proceed with the assistance of an external agency.
12 Which one is the correct unit for entropy? [1]
a) JK−1 mol b) kJ mol c) JK−1 mol −1 d) KJ mol−1
13 A reaction, A + B→ C + D + q is found to have a positive entropy change. The reaction will be: [1]
a) spontaneous only at high temperature. b) nonspontaneous at all temperature.
c) spontaneous only at low temperature. d) spontaneous at all temperature.
14 Select the incorrect expression from the following. [1]
a) 𝛥𝑆𝑡𝑜𝑡𝑎𝑙 < 0 (spontaneous process) b) 𝛥𝐺 = 𝛥𝐻 - 𝑇𝛥𝑆
𝛥𝐻 𝛥𝐻𝑠𝑦𝑠
c) 𝛥𝑆𝑡𝑜𝑡𝑎𝑙 = 𝛥𝑆𝑠𝑦𝑠𝑡𝑒𝑚 + 𝛥𝑆𝑠𝑢𝑟𝑟 d) 𝛥𝑆𝑠𝑢𝑟𝑟 = 𝑠𝑢𝑟𝑟 = -
𝑇 𝑇
15 Which of the following properties is the measure of the degree of randomness or disorder [1]
in the system?
a) Entropy b) Gibbs free energy c) Internal energy d) Enthalpy
𝑞
16 The entropy change can be calculated by using the expression𝛥𝑆 = 𝑟𝑒𝑣 When water freezes [1]
𝑇
in a glass beaker, choose the correct statement amongst the following :
a) 𝛥𝑆 (system) decreases and 𝛥𝑆 (surroundings) also decreases.
b) 𝛥𝑆 (system) decreases but 𝛥𝑆 (surroundings) increases.
c) 𝛥𝑆 (system) decreases but 𝛥𝑆 (surroundings) remains the same.
d) 𝛥𝑆 (system) increases but 𝛥𝑆 (surroundings) decreases.
ASSERTION-REASON: [1]
a) Both A and R are true and R is the correct explanation of A.
b) Both A and R are true but R is not the correct explanation of A.
c) A is true but R is false.
d) A is false but R is true.

17 Assertion (A): The thermodynamic function which determines the spontaneity of a process
is the free energy. For a process to be spontaneous, the change in free energy must be
negative.
Reason (R): The change in free energy is related to the change in enthalpy and change in
entropy. The change in entropy for a process must always be positive if it is spontaneous.

18 Assertion (A): Molar entropy of vaporization of water is different from ethanol. [1]
Reason (R): Water is more polar than ethanol.
19 Assertion (A): An exothermic process, non - spontaneous at high temperature, may [1]
become spontaneous at low temperature.
Reason (R): With decrease in temperature, randomness (entropy) decreases.
20 Assertion (A): Enthalpy and entropy of any elementary substance in the standard state are [1]
taken as zero.
Reason (R): At zero degree absolute, the constituent particles become completely
motionless.
21 Assertion (A): A process for which 𝛥𝑆𝑠𝑦𝑠𝑡𝑒𝑚 > 0 as well as 𝛥𝐻 > 0 passes from non - [1]
spontaneous to spontaneous state as temperature is increased.
Reason (R): At higher temperature, 𝑇𝛥𝑆 exceeds 𝛥𝐻 .
22 Enthalpy of the solution of a substance is the enthalpy change: [1]
a) when one kg of it reacts with a specified amount of solvent.
b) when one kg of it dissolves in a specified amount of solvent.
c) when one mole of it dissolves in a specified amount of solvent.
d) when one mole of it reacts with a specified amount of solvent.
23 Calculate the difference between C 𝑝 and C 𝑣 for 10 moles of an ideal gas. [1]

a) 0.831 J b) 831.4 J c) 83.14 J d) 8.314 J

24 The bond dissociation energies of H2 , Cl 2 and HCl are 104, 58 and 103 kcal mol −1 [1]
respectively. The enthalpy of formation of HCl would be

a) +22 kcal mol−1 b) - 44 kcal mol−1 c) +44 kcal mol−1 d) - 22 kcal mol−1

25 Enthalpies of formation of CO(g), CO2 (g), N 2 O(g),and N 2 O 4 (g) are - 110, –393, 81, and [1]
9.7 kJ mol −1 respectively. Find the value of 𝛥𝑟 𝐻 for the reaction: 𝑁2 𝑂4 (𝑔) + 3𝐶𝑂(𝑔) →
𝑁2 𝑂(𝑔) + 3𝐶𝑂2 (𝑔)

a) - 850 kJ b) - 600kJ c) - 778 kJ d) - 802 kJ

26 Two ideal gases under the same pressure and temperature are allowed to mix in an isolated [1]
system. What will be the sign of entropy change?
27 𝛥
Predict the sign of𝛥 S for the following reaction:CaCO 3 (s) → CaO(s) + CO 2 (g) [1]
28 At 298 K, K𝑝 for the reaction N2 O4 (𝑔) ⇌ 2NO2 (𝑔) is 0.98.Predict whether the reaction is [1]
spontaneous or not.
29 Out of diamond and graphite which has greater entropy?Why? [1]
ℎ𝑒𝑎𝑡
30 Predict the sign of𝛥𝑆 for the following reaction. CaCO3 (s) → CaO(s) + CO2 (g) [1]
31 At what temperature entropy of a substance is zero? [1]
32 What do you mean by entropy? [1]
33 Define spontaneous process. [1]
34 How is entropy of a substance related to temperature? [1]
Section B
35 Calculate the enthalpy change (𝛥 H) of the following reaction. [2]
5
C 2 H 2 (g) + 2 O 2 (g) → 2CO 2 (g) + H 2 O (g)
Given average bond enthalpies of various bonds, i.e. C - H,
C ≡ C, O = O, C = O, O - H as 414, 814, 499, 724 and 640 kJ mol −1 respectively.
36 For the reaction 2 Cl (g)→ Cl 2 (g)what will be the signs of 𝛥 H and 𝛥 S? [2]
37 The𝛥 H and 𝛥 S for 2Ag 2 O(s) → 4Ag(s) + O 2 (g) are given + 61.17kJ mol −1 and [2]
+ 132 Jk −1 mol −1 respectively. Above what temperature will the reaction be spontaneous?
38 What is the condition for spontaneity in terms of free energy change? [2]
39 Calculate the entropy change in surroundings when 1.00 mole of H2 O(l) is formed under [2]
standard conditions and 𝛥𝑓 𝐻 ⊖ = - 286 kJ mol −1 .
40 Predict in which of the following, entropy increases/decreases. Give reason. [2]
 1. Temperature of crystalline solid is raised from 0 K to 115 K.
2. H2 (g) → 2H(g)
41 For a reaction at 298 K [2]
2A + B → C , 𝛥 H = 400 kJ mol −1 and 𝛥 S = 0.2 kJ k −1 mol −1
At what temperature will the reaction become spontaneous considering 𝛥 H and 𝛥 S to
constant over the temperature range?
42 Explain how is enthalpy related to spontaneity of a reaction. [2]
43 The standard molar entropy of H2 O (l) is 70 J K −1 mol −1 . Will the standard molar entropy [2]
of H 2 O(s) be more, or less than 70 J K −1 mol −1 ?
44 The enthalpy of atomization for the reaction CH4 (g) → C(g) + 4H(g)is 1665 kJ mol −1 .What [2]
is the bond energy of C - H bond?
45 For an isolated system,𝛥 U = 0, what will be 𝛥 S? [2]
46 At 0𝑜 C, ice and water are in equilibrium and 𝛥𝐻 = 6.06 kJ mol −1 for the process, H2 O(𝑠) → [2]
H2 O(𝑙 ) .What will be 𝛥𝑆 and 𝛥𝐺 for the conversion of ice into liquid water?
Section C
47 State True or False: [3]
1. Enthalpy, entropy, free energy, etc., are state variables.
2. A spontaneous process is accompained by a decrease in entropy.
3. A spontaneous process is reversible in nature.
48 1. What is a spontaneous process? Mention the conditions for a reaction to be [3]
spontaneous at constant temperature and pressure.
2. Discuss the effect of temperature on the spontaneity of anexothermic reaction.
49 Predict in which of the following, entropy increases/decreases [3]
1. A liquid crystallizes into a solid.
2. The temperature of a crystallize solid is raised from 0 K to 115 K
3. 2NaHCO3 (s) → Na 2 CO 3 (s) + CO 2 (g) + H 2 O(g)
4. H2 (g) → 2H (g)
50 Enthalpy and entropy changes of a reaction are 40.63 kj/mol and 108.8 J/mol [3]
respectively. Predict the feasibility of the reaction at 27 0C.
51 Give reason for the following: [3]
1. Neither q nor w is a state function but q + w is a state function.
2. A real crystal has more entropy than an ideal crystal.
52 1. Why standard entropy of an elementary substance is not zero whereas standard [3]
enthalpy of formation is taken as zero?
2. Under what conditions will the reaction occur, if
a. both𝛥 Hand 𝛥 S are positive
b. both𝛥 H and 𝛥 Sare negative
53 The enthalpy of vaporisation of liquid diethyl ether (C2 H5 )2 O is 26.0 kJ mol −1 at its boiling [3]
point (35.0°C). Calculate 𝛥 S° for the conversion of
1. liquid to vapour and
2. vapour to liquid at 35°C.
Section D
Question No. 54 to 57 are based on the given text. Read the text carefully and answer [2]
the questions:
 Entropy is the measure of degree of randomness or disorderness in an isolated system and
is represented by the symbol S. Greater the degree of randomness, higher is the entropy. In
case of chemical reactions, it shows the rearrangement of atoms or ions from one pattern in
the reactants to another (in the products). If the structure of product is more disordered as
compared to reactants, entropy of the reaction increases and if the structure of reactant is
more disordered as compared to products, it results in decreased entropy.
Entropy is also a state function, i.e. depends only on initial and final states of a system, so
entropy change can be given as :
𝛥𝑆 = S 2 - S 1 = 𝛴𝑆𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 − 𝛴𝑆𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠
54 If the temperature of crystalline solid is raised from 0 K to 115K what is the change in
entropy?
55 Calculate the enthalpy change for the following reaction.
CH 4 (g) + 2O2 (g) → CO2 (g) + 2H2 O(l)
given enthalpies of formation of CH 4 , CO 2 and H 2 O are - 74.8 kJ mol −1 , - 393.5 kJ mol −1
and - 286.2 kJ mol −1 respectively.
56 221.4J is needed to heat 30g of ethanol from 150 C to 18 0 C. Calculate (a) specific heat
capacity, and (b) molar heat capacity of ethanol.
57 10 g of argon is compressed isothermally and reversibly at a temperature of 27∘ C form 10 L
to 5 L. Calculate q, W, 𝛥𝑈 and 𝛥𝐻 for this process 𝑅 = 2.0𝑐𝑎𝑙K −1 mol−1 , log2 = 0.30 . Atomic
weightof Ar = 40.
58 Fill in the blanks: [4]
1. At absolute zero, the entropy of a pure crystal is zero. This is ________ law of
thermodynamics.
2. Entropy is a thermodynamic quantity which is a measure of ________ of the molecules
of the system.
3. All natural processes are spontaneous and ________.
4. All the spontaneous processes are ________ in nature and accompanied with _______ in
entropy.
Section E
Question No. 59 to 63 are based on the given text. Read the text carefully and answer [5]
the questions:
Entropy is the measure of degree of randomness or disorderness in an isolated system and
is represented by the symbol S. Greater the degree of randomness, higher is the entropy. In
case of chemical reactions, it shows the rearrangement of atoms or ions from one pattern in
the reactants to another (in the products). If the structure of product is more disordered as
compared to reactants, entropy of the reaction increases and if the structure of reactant is
more disordered as compared to products, it results in decreased entropy.
Entropy is also a state function, i.e. depends only on initial and final states of a system, so
entropy change can be given as :
𝛥𝑆 = S 2 - S 1 = 𝛴𝑆𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 − 𝛴𝑆𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠

a) Both A and R are true and R is the correct explanation of A.

b) Both A and R are true but R is not the correct explanation of A.
c) A is true but R is false.
d) A is false but R is true.
59 Assertion (A): The phenomenon like flow of water down hill or fall of a stone on to the
ground is an example of a spontaneous process.
Reason (R): There is a net increase in potential energy in the direction of change.
60 Assertion (A): The dissolution of NH 4 CI in water is endothermic but it dissolves in water.
Reason (R): On dissolution of NH 4 CI, entropy increases.
61 Assertion (A): The entropy decreases when the temperature of a crystalline solid is raised
from 0 K to 115 K.
Reason (R): On raising temperature from 0 K to 115 K, the constituent particles begin to
move.
62 Assertion (A): Enthalpy of graphite is lower than that of diamond.
Reason (R): Entropy of graphite is greater than thatof diamond.
63 Assertion (A): Chlorine when solidified does not have zero entropy even at absolute zero.
Reason (R): Chlorine is a pungent smelling gas and is difficult to solidify it.

64. Calculate the enthalpy of formation of carbon disulfide given that the enthalpy of
combustion of it is 110.2 kJ mol–1 and those of sulfur and carbon are 297.4 kJ and 394.5 kJ/g
atoms respectively.

65. Calculate enthalpy of formation of methane (CH4) from the following data :

(i) C (s) + O2 (g)  CO2 (g), ∆rH= -393.5 KJ/mol

(ii) H2 (g) + ½ O2 (g)  H2O (l), ∆rH= -285.8 KJ/mol

(iii) CH4 (g) 2O2 (g)  CO2 (g) + 2H2O (l), ∆rH = - 890-3 kJ/mol

66. The combustion of 1 mole of benzene takes place at 298 K and 1 atm. After combustion,
CO2 (g) and H2O (l) are produced and 326.70 kj of heat is liberated. Calculate the standard
enthalpy of formation, ∆fH0 of benzene. Standard enthalpies of formation of CO2 (g) and
H2O(l) – 393.5 kJ /mol and – 285.83 kJ/mol respectively.
67. Calculate the enthalpy of combustion of ethylene (gas) to form CO 2 (gas) and 298 K and
1 atmospheric pressure. The enthalpies of formation of CO 2 , H2O and C2H4 are H2O (gas) at
- 393.7, - 241.8 + 52.3 kJ per mole respectively.

68. Calculate the enthalpy of hydrogenation of ethylene, given that the enthalpy of
combustion of ethylene, hydrogen and ethane are – 1410.0, - 286.2 and – 1560.6 kj/mol
respectively at 298 K.

69. Calculate the entropy change involved in the conversion of one mole of liquid water at
373 K to vapour at the same temperature (latent heat of vaporization of water ∆ vapH =
2.257 kj/g).

70. Explain the effect of temperature on spontaneity of an endothermic and exothermic

process.