THERMODYNAMICS

1 When 430 J of work was done on a system, it lost 120 J of energy as heat. Calculate the
1
value of internal energy change (ΔU) for this process.

ANS: ΔU = –q + w
ΔU = –120 + 430
ΔU = 310 J

2 Predict the sign of ΔS° for the following reaction:

1

ANS: ΔSº, i.e. entropy decreases during the reaction. Hence, the sign of ΔSº will be
negative in the given reaction.

3 Classify the following as extensive and intensive properties:

1
Molar heat capacity, Temperature, Enthalpy and Volume.

ANS: Extensive property: Volume, Enthalpy.

Intensive property: Temperature, Molar heat capacity.

4 Give two examples of state functions. 1

ANS: ΔH (Enthalpy change) and ΔU (Internal energy change) are state functions as
they depend upon initial and final state and not on the path.

5 Give an example of a spontaneous process which is endothermic. 1

ANS:
It is endothermic as well as spontaneous.

6 Name the state variables which remain constant in

1
(i) isobaric process. (ii) isothermal process.

ANS: (i) Isobaric process: In this process, pressure remains constant i.e. Δp = 0.
(ii) Isothermal process: In this process, temperature remains constant i.e. ΔT = 0.

7 What is bond energy? Why is it called enthalpy of atomisation? 1

ANS: Bond energy is the amount of energy released when bonds are formed between
isolated atoms in gaseous state to form one mole of gaseous molecule. It is called
 enthalpy of atomisation because it may also be defined as the amount of energy required
to dissociate bonds present between the atoms of 1 mole of a gaseous molecule into
constituting atoms.

8 Define:
(i) intensive properties. 1
(ii) adiabatic process.

ANS: (i) Intensive properties:

The properties which depend only on the nature of the substance and not on the amount
of the substance are called intensive properties, e.g. density.
(ii) Adiabatic process:
A process during which no heat flows between the system and the surroundings is called
an adiabatic process, i.e.
q = 0.

9 Predict in which of the following, entropy increases/decreases. Give reason:

(i) Temperature of crystalline solid is raised from 0 K to 115 K. 1

ANS: (i) Entropy will increase on increasing the temperature since the particles of solid
move with greater speed at higher temperature.
At 0 K, there is perfect order of the constituent particles, entropy is minimum, tends to
zero.

Entropy will increase because the number of particles of product are double than that of
reactant.

10 When is the entropy of a perfectly crystalline solid zero? 1

ANS: The entropy of a perfectly crystalline solid is zero at absolute zero temperature
i.e., 0 K or –273.15 °C.

11 Which one of the following is not extensive state function?

1
Enthalpy change, Internal energy change and Pressure

ANS: Pressure is not a state function.

12 Write an expression in the form of chemical equation for the standard enthalpy of
1
formation (ΔfH) of CO(g).
 ANS:

13 State a chemical reaction in which ΔH and ΔU are equal. 1

ANS:

14 Which of the following is an intensive property?

1
Surface tension, Mass, Volume, Enthalpy, Density

ANS: Surface tension and density are intensive properties.

15 Will the change in enthalpy of the system be zero in an adiabatic process? 1

ANS: Yes, In adiabatic process, ΔH = 0

16 What happens to the internal energy of the system if:

(i) work is done on the system? 1
(ii) work is done by the system?

ANS: (i) If work is done on the system, internal energy will increase.
(ii) If work is done by the system, internal energy will decrease.

17 What is the value of internal energy for 1 mole of a monoatomic gas? 1

ANS:

18 For the reaction, N2(g) + 3H2(g) 2NH3(g), predict whether the work is done on the
1
system or by the system.

ANS: Volume is decreasing, therefore, work is done on the system.

19 What is the limitation of first law of thermodynamics? 1

ANS: It cannot tell us the direction of the process.

20 Which of the following is an extensive property?
(a) Volume
(b) Surface tension 1
(c) Viscosity
(d) Density

ANS: (a) Volume is an extensive property.

21 Which of the following is not a state function?

ANS: (d) q is not a state function.

22

ANS:

23 Predict ΔH > ΔU or ΔH is less than ΔU or ΔH = ΔU. 1

 ANS: (i) ΔH = ΔU because Δn = 0
(ii) ΔH > ΔU because Δn = 1 [ΔH = ΔU + ΔnRT]

24 What are the ways by which the internal energy of a system can be changed? 1

ANS: (i) Exchanging heat with the surroundings.

(ii) Work done on the system or by the system.

25 State why heat changes in physical and chemical processes are indicated by enthalpy
1
changes and not by internal energy changes.

ANS: Most of the processes are carried out in open container, i.e, at constant pressure.
Therefore, enthalpy changes are indicated and not internal energy changes.

26 Under what conditions ΔH and ΔU are equal? 1

ANS: When Δn = 0, ΔH = ΔU

27 Which of the following is an endothermic process?

ANS: kJ is an endothermic process as heat is being

absorbed.

28 CH4(g) + 2O2(g) CO2(g) + 2H2O(l); ΔH = –890 kJ mol–1

1
What is the calorific or fuel value of 1 kg of CH4?

ANS:

29 H2(g) + Cl2(g) 2HCl(g) + 185 kJ. State whether this reaction is exothermic or
1
endothermic and why.
 ANS: It is an exothermic reaction because heat is being evolved.

30 Which of the following are state functions?

(i) Height of a hill
1
(ii) Distance travelled in climbing the hill
(iii) Energy consumed in climbing the hill

ANS: (i) Height of a hill

31 In the equation: what would be the sign of work done? 1

ANS: The sign of work done will be +ve, i.e. work will be done on the system due to
decrease in volume.

32 What is the value of ΔG when ice and water are in equilibrium? 1

ANS: ΔG = 0 at equilibrium.

33 If ΔGº for a reversible reaction is found to be zero, what is the value of its equilibrium
1
constant?

ANS:

34 Why does NH4NO3 dissolve in water spontaneously even when this process is
1
endothermic?

ANS: NH4NO3 dissolves in water spontaneously even when this process is endothermic
because entropy increasing due to free movement of ions on dissolving. ΔS = +ve favours
the process and makes it spontaneous.

35 If ΔH for a reaction has a negative value, how would you know the sign requirement of ΔS
1
for it so that the reaction is spontaneous at low temperatures?

ANS: ΔS must be positive.

36 Which have more entropy, real crystal or ideal crystal and why? 1

ANS: Real crystal has more entropy because it has more disorderness.

37 How is change in entropy during melting of solid related to its melting point? 1

ANS:

38 Why does entropy increase on mixing of two gases? 1

ANS: The disorder increases when two gases are mixed together, that is why entropy
increases.

39 At what temperature, the entropy of a perfect crystalline substance is taken as zero? 1

ANS: 0 kelvin

40 What is the effect of temperature on entropy? 1

ANS: Entropy increases with increase in temperature.

41 How is standard free energy change related to equilibrium constant? 1

ANS:

42 Which has larger absolute entropy per mole?

(i) H2O(l) at 298 K or H2O(l) at 350 K, 1
(ii) N2 or NO both at 298 K

ANS: (i) H2O(l) at 350 K has larger absolute entropy per mole.
(ii) NO at 298 K has greater entropy.

43 Determine the sign of entropy change in

1
N2(g) + O2(g) 2NO(g).

ANS: ΔS = +ve because it is endothermic process and spontaneous.

44 Will entropy increase or decrease in the following changes?
(i) Sugar dissolved in water, 1
(ii) Normal egg to hard boiled egg.

ANS: (i) When sugar dissolves in water, entropy increases.

(ii) Hard boiled egg has more entropy because denatured protein has random coil
structure.

45 Does an aqueous solution of Mg2+ ions have a larger entropy before or after hydration of
1
the ions?

ANS: Mg2+ has more entropy before hydration of ions.

46 The standard absolute entropy of a substance, (S°) is the entropy of the substance in its
standard state at 1 atm, temperature being:
1
(a) 0 K (b) 298 K
(c) 398 K (d) 273 K

ANS: (b) 298 K

47 For a spontaneous process, which of the following is always true?

(a) ΔG > 0
(b) ΔStotal < 0 1
(c) –TΔS > 0
(d) ΔG < 0

ANS: (d) ΔG < 0 is always true for spontaneous process.

48 For which of the following processes ΔS is negative?

ANS: (ii) At higher pressure N2(g) will have less entropy, i.e. ΔS will be –ve.
49 Why is entropy of a solution higher than that of pure liquid? 1

ANS: In solution, there is more disorderness than in pure liquid.

50 Choose the correct answer. A thermodynamic state function is a quantity

(i) used to determine heat changes
(ii) whose value is independent of path 1
(iii) used to determine pressure volume work
(iv) whose value depends on temperature only.

ANS: (ii) Whose value is independent of path

51 For the process to occur under adiabatic conditions, the correct condition is:
1

ANS: (iii) ΔP = 0

52 The enthalpies of all elements in their standard states are:

(i) unity
(ii) zero 1
(iii) < 0
(iv) different for each element.

ANS: (ii) zero

53 ΔU° of combustion of methane is –X kJ mol–1. The value of ΔH° is

(i) = ΔU° (ii) > ΔU° 1
(iii) < ΔU° (iv) = 0

ANS:

54 The enthalpy of combustion of methane, graphite and dihydrogen at 298 K are, –890.3 kJ
mol–1, –393.5 kJ mol–1 and –285.8 kJ mol–1 1
respectively. Enthalpy of formation of CH4(g) will be
(i) –74.8 kJ mol–1 (ii) –52.27 kJ mol–1
 (iii) +74.8 kJ mol–1 (iv) +52.26 kJ mol–1

ANS: (i) –74.8 kJ mol–1

55 A reaction, A + B → C + D + q is found to have a positive entropy change. The reaction

will be
(i) possible at high temperature
1
(ii) possible only at low temperature
(iii) not possible at any temperature
(iv) possible at any temperature.

ANS: (iv) Possible at all temperatures.

56 (i) Two litres of an ideal gas at a pressure of 10 atm expands isothermally into a vacuum
until its total volume is 10 litres. How much heat is absorbed and how much work is done
in the expansion?
1
(ii) Consider the same expansion, but this time against a constant external pressure of 1
atm.
(iii) Consider the same expansion, to a final volume of 10 litres conducted reversibly.

ANS:

57 State second law of thermodynamics. 1

ANS: It states “The entropy of universe is continuously increasing due to spontaneous

processes taking place in it’.

58 Write the conditions in terms of ΔH and ΔS when a reaction would be always

1
spontaneous.

ANS: When ΔH is –ve and ΔS is +ve, then ΔG will be –ve and process will always be
spontaneous as ΔG = ΔH – TΔS

59 When ΔH > 0 and ΔS < 0, a reaction is never spontaneous. Explain. 1

 ANS: When ΔH > 0 and ΔS < 0, then ΔG will be +ve at all temperatures, therefore,
process will never be spontaneous.

60 18.0 g of water completely vaporises at 100 °C and 1 bar pressure and the enthalpy
change in the process is 40.79 kJ mol–1. What will be the
1
enthalpy change for vaporising two moles of water under the same conditions? What is
the standard enthalpy of vaporisation for water?

ANS:

61 One mole of acetone requires less heat to vaporise than 1 mole of water. Which of the two
1
liquids has higher enthalpy of vaporisation?

ANS: Water will have high enthalpy of vaporisation than acetone.

62 Standard molar enthalpy of formation, Δ fH° is just a special case of enthalpy of reaction,
ΔrH°.
Is the ΔrH° for the following reaction same as Δ fH°? Give reason for your answer. 1
CaO(s) + CO2(g) CaCO3(s);
–1
Δ f = – 178.3 kJ molH°

ANS: No, because CaCO3(s) is being formed from compounds and not constituting
elements.

63 The value of Δ fH° for NH3 is –45.9 kJ mol–1.

Calculate enthalpy change for the following reaction: 1
2NH3(g) N2(g) + 3H2(g)

ANS:

64 Enthalpy is an extensive property. In general, if enthalpy of an overall reaction: A B

along one route is ΔrH and ΔrH1, ΔrH2, ΔrH3, …, represent enthalpies of intermediate 1
reactions leading to product B. What will be the relation between ΔrH for overall reaction
and ΔrH1, ΔrH2,…, etc. for intermediate reactions?

ANS:
65 The enthalpy of atomisation for the reaction:
CH4(g) C(g) + 4H(g) is 1665 kJ mol–1. 1
What is the bond energy of C—H bond?

ANS:

66 Heat has randomising influence on a system and temperature is the measure of average
chaotic motion of particles in the system. Write the mathematical relation which relates 1
these three parameters.

ANS:

67 Increase in enthalpy of the surroundings is equal to decrease in enthalpy of the system.

Will the temperature of system and surroundings be the same when they are in thermal 1
equilibrium?

ANS: Yes, the temperature of system and surrounding will be same when they are in
thermal equilibrium.

68 At 298 K, Kp for reaction:

1
is 0.98. Predict whether the reaction is spontaneous or not.

ANS:
Since Kp is +ve, ΔrG° will be –ve, therefore, reaction will be spontaneous.

69 A sample of 1.0 mole of a monoatomic ideal gas is taken through a cyclic process of
expansion and compression as shown in the figure. What will be the value of ΔH for the 1
cycle as a whole?

ANS: ΔH = 0 for cyclic process.

70 The standard molar entropy of H2O(l) is 70 J K–1 mol–1. Will the standard molar entropy of
1
H2O(s) be more, or less than 70 J K–1mol–1?

ANS: It will be less because ice is less ordered than liquid water.
71 The molar enthalpy of vaporisation of acetone is less than that of water. Why? 1

ANS: It is because acetone has weak van der Waals’ forces of attraction whereas water
molecules have strong H-bonding, therefore, ΔvapH° of water is more.

72 Which quantity out of ΔrG and ΔrG° will be zero at equilibrium? 1

ANS:

73 Predict the change in internal energy for an isolated system at constant volume. 1

ANS:

74
1
What is the calorific or fuel value of 1 kg of CH4?

ANS:

75 Give reasons for the following:

(i) The enthalpy of neutralisation is always constant, i.e. 57.1 kJ/mol when a strong acid
2
neutralises a strong base.
(ii) Neither q nor w is a state function but q + w is a state function.

ANS: (i) It is because strong acid and strong base are completely ionised in aqueous
solution.
(ii) ΔU = q + w
Since, ΔU is a state function and it is equal to q + w which is state function, because ΔU
depends upon initial and final states and not on path.

76 Define the following terms:

(i) Enthalpy of neutralisation 2
(ii) Hess’s law of constant heat summation
 ANS: (i) Enthalpy of Neutralisation: It is defined as enthalpy change (heat evolved)
when 1 mole of H+ from acid combines with 1 mole of OH– from base to form water.
(ii) Hess’s law of constant heat summation: It states that total enthalpy of reaction remains
the same whether the reaction takes place in one step or several steps.

77 Calculate the bond enthalpy of Cl—Cl bond from the following data:
CH4(g) + Cl2(g) CH3Cl(l) + HCl(l); [ΔH = –100.3 kJ mol–1]
2
Given, bond enthalpies of C—H, C—Cl and H—Cl bonds are 413, 326 and 431 kJ mol –1
respectively.

ANS:

78 Derive the relationship between CP and CV for an ideal gas. 2

ANS:

79 Derive the relationship between isothermal and free expansion of an ideal gas. 2

ANS: Work done in isothermal reversible expansion of an ideal gas

 In free expansion of an ideal gas. w = 0 because ideal gases have negligible force of
attraction,
therefore, work done is zero in free expansion because no external force is acting.

80 Given:

What is the standard enthalpy of formation of NH3 gas?

ANS:

81 In a process, 701 J of heat is absorbed by a system and 394 J of work is done by the
system. 2
What is the change in internal energy for the process?

ANS:

82 Calculate the heat of combustion of glucose from the following data:

2
 ANS:

83 Calculate the heat of reaction of the following reaction:

ANS:

84 1 m3 of C2H4 at STP is burnt in oxygen, according to the thermochemical reaction:

Assuming 70% efficiency, determine how much of useful heat is evolved in the reaction.
 ANS:

85 1 g of graphite is burnt in a bomb calorimeter in excess of oxygen at 298 K and 1

atmospheric pressure according to the equation:

2
During the reaction, temperature rises from 298 K to 299 K. If the heat capacity of the
bomb calorimeter is 20.7 kJ/K, then what is the enthalpy change for the above reaction at
298 K and 1 atm?

ANS:

86 A swimmer coming out from a pool is covered with a film of water weighing about 18 g.
How much heat must be supplied to evaporate this water at 298 K? Calculate the internal
energy of vaporisation at 100 °C. 2

ANS:
87 For oxidation of iron,

entropy change is –549.4 J K–1 mol–1 at 298 K. 2

Inspite of negative entropy change of this reaction, why is the reaction spontaneous?
(ΔrH° for this reaction is –1648 × 103 J mol–1)

ANS:
Since therefore, reaction is spontaneous.

88 The combustion of one mole of benzene takes place at 298 K and 1 atm. After
combustion, CO2(g) and H2O(l) are produced and 3267.0 kJ of heat is liberated. Calculate
2
the standard enthalpy of formation of benzene (Δ fH°).
Δ fH° CO2(g) = – 393 kJ mol–1 and Δ fH° H2O(l) = –285.83 kJ mol–1.

ANS: Combustion of 1 mole of benzene takes place as follows:

89 The reaction of cyanamide, NH2CN(s), with dioxygen was carried out in a bomb
calorimeter and ΔU was found to be –742.7 kJ mol–1 at 2
298 K. Calculate enthalpy change for the reaction at 298 K.
 + H2O(l)

ANS:

90 Calculate the number of kJ of heat necessary to raise the temperature of 60.0 g of

aluminium from 35 °C to 55 °C. Molar heat capacity of 2
Al is 24 J mol–1 K–1.

ANS:

91 Calculate the enthalpy change on freezing of 1.0 mole of water at 10.0 °C to ice at –10.0
°C.

ANS: at 0 °C)
92 Enthalpy of combustion of carbon to CO2 is –393.5 kJ mol–1. Calculate the heat released
2
in the formation of 35.2 g of CO2 from carbon and dioxygen gas.

ANS:

93 The enthalpies of formation of CO(g), CO2(g), N2O(g) and N2O4(g) are –110, –393, 81 and
9.7 kJ mol–1 respectively. Find the value of ΔrH for the reaction: 2

ANS:

94 Calculate the standard enthalpy of formation of CH3OH(l) from the following data:

2
 ANS:

95

ANS:

96 For an isolated system, ΔU = 0, what will be ΔS? 2

ANS: ΔS will be greater than zero because in isolated system if two gases are allowed
to mix, ΔU = 0 but entropy will increase i.e., ΔS will be greater than zero.

97
2

ANS:
Because the reaction involves formation of bond therefore, it is exothermic. 2 moles of
atoms have more randomness than 1 mole of molecule
98 The equilibrium constant for a reaction is 10. What will be the value of ΔG°?
2
[R = 8.314 J K–1 mol–1, T = 300 K]

ANS:

99 Comment on the thermodynamic stability of NO(g), given

ANS:

10 Calculate the entropy change in surroundings when 1.00 mol of H 2O(l) is formed under
2
0 standard conditions. ΔfH° = –286 kJ mol–1.

ANS: (ii) C2H6(g) will have highest heat of combustion because it has highest molecular
weight and second highest calorific value.
ΔHc = Calorific value in kJ/g × Mol. wt
= 52 × 30 = 1560 kJ/mol

10 Which of the following has the highest heat of combustion out of the following and why?
2
1 (i) C2H6 (ii) C2H4 (iii) C2H2 (iv) CH4

ANS:
10 The heat of combustion of C2H6 is – 368.4 kcal.
2 Calculate heat of combustion of C2H4, heat of combustion of H2 is 68.32 kcal mol–1. ΔH for
the following reaction is –37.1 kcal.
2

ANS:

10 The equilibrium constant at 25 °C for the process Co3+(aq) + 6NH (aq)

3
3 [Co(NH ) ]3+(aq) is 2.5 × 106. Calculate the value of ΔG° at 25 °C
3 6 2
(R = 8.314 J K–1 mol–1). In which direction is the reaction spontaneous under standard
conditions ?

ANS:
The reaction is spontaneous in forward direction under standard conditions.

10 What is the value of equilibrium constant for the following reaction at 400 K?
4 2
–1 –1 –1 –1 –1
ΔH° = 77.5 kJ mol , R = 8.314 J mol K , ΔS = 135 J K mol

ANS:

10 Calculate the standard free energy change ΔG° for the reaction: 2
5

ANS:

10 A 5 litre cylinder contained 10 moles of oxygen gas at 27 °C. Due to sudden leakage
6 through the hole, all the gas escaped into the atmosphere
and the cylinder got empty. If the atmospheric pressure was 1.0 atm, calculate the work 2
done by the gas.
[R = 0.0821 L atm K–1 mol–1; 1 L atm = 101.3 J]

ANS:

10 Calculate the temperature above which the reduction of lead oxide in the following
7 reaction becomes spontaneous:
2

ΔS = 190 J K–1 mol–1]

ANS:
The reaction will become spontaneous above 570.52 K because ΔG is equal to zero at
this temperature and above this temperature, ΔG will become –ve.

10 Starting with the thermodynamic relationship

2
8 G = H – TS, derive the following relationship:
 ΔG= – TΔSTotal

ANS:

10 Calculate the free energy change when 1 mole of NaCl is dissolved in water at 298 K.
9 (Given: Lattice energy of NaCl = –777.8 kJ mol–1, Hydration energy = –774.1 kJ mol–1 and 2
ΔS = 0.043 kJ K–1 mol–1 at 298 K)

ANS:

11 Calculate ΔrG° for conversion of oxygen to ozone, 3/2O2(g) O3 (g) at 298 K, if Kp for
2
0 this conversion is 2.47 × 10–29.

ANS:

11 Find out the value of equilibrium constant for the following reaction at 298 K.
1 2
–1
Standard Gibbs energy change, ΔrG° at the given temperature is –13.6 kJ mol .

ANS:
11 Calculate the electron gain enthalpy of fluorine from the data given below:
2 ΔfH° of KF = –560.8 kJ mol–1, Sublimation energy of K = 87.8 kJ mol–1, Dissociation
2
energy of F2 is 158.9 kJ mol–1, Lattice energy of KF is –807.5 kJ mol–1 and Ionisation
energy of K is 414.2 kJ mol–1.

ANS: E.G.E = Δf H – S – 1/2D – I.E. – U

E.G.E.= –560.8 – 87.8 – 1/2 × 158.9
– 414.2 – (–807.5)
E.G.E. = –1142.25 + 807.5 = –334.75 kJ mol–1

11 Use the following thermodynamic data to calculate the enthalpy change for the formation
3 of solid lithium fluoride, LiF(s) from Li (s) and F2(g):

ANS:

11 Explain with the help of example, the difference between bond dissociation energy and
2
4 bond energy.

ANS: Bond dissociation energy is energy required to break 1 mole of bonds

Bond energy is energy released when 1 mole of bonds are formed

In diatomic molecule, both bond dissociation energy and bond energy are equal in
magnitude but opposite in sign.

11 Compound with carbon-carbon double bond, such as ethylene (C2H4) and hydrogen in a
5 reaction is called hydrogenation. 2

Calculate enthalpy change for the reaction using the following combustion data:
 ANS:

11 Comment on the spontaneity of a reaction at constant temperature and pressure in the

6 following cases:

ANS: (i) ΔH < 0 and ΔS > 0; ΔG will be –ve and process will always be spontaneous.
(ii) ΔH > 0 and ΔS < 0; ΔG will be +ve and process will never be spontaneous.
(iii) ΔH < 0 and ΔS < 0; ΔG will be –ve, if ΔH > TΔS and the process will be spontaneous
at low temperature.
(iv) ΔH > 0 and ΔS > 0; ΔG will be –ve, if TΔS > ΔH and the process will be spontaneous
at high temperature.

11
State the third law of thermodynamics. 2
7

ANS: It states ‘The entropy of perfectly crystalline substance is zero at absolute zero
temperature. We can determine absolute entropy of various substances at any other
temperature except at zero kelvin.

11
Explain the term residual entropy. 2
8

ANS: Residual entropy: Mostly entropy of perfectly crystalline substance is zero at 0K.
There are certain
substances which possess some entropy even at absolute zero i.e. at zero kelvin. This
 entropy is known
as residual entropy, e.g., in case of CO, the measured residual entropy is 5 J K –1mol–1. It
is due to some
disorder which is also called frozen disorder.

11 Use the following data to calculate ΔlatticeH° for NaBr.

9 ΔsubH° for sodium metal = 108.4 kJ mol–1 Ionization enthalpy of sodium = 496 kJ mol–1
Electron gain enthalpy of bromine = –325 kJ mol–1 2
Bond dissociation enthalpy of bromine = 192 kJ mol–1
Δf H° for NaBr(s) = –360.1 kJ mol–1.

ANS:

12 Given that ΔH = 0 for mixing of two gases.

0 Explain whether the diffusion of these gases into each other in a closed container is a 2
spontaneous process or not.

ANS: It is spontaneous process because entropy or disorder is increasing.

12 Identify the state functions and path functions out of the following:
2
1 Enthalpy, Entropy, Heat, Temperature, Work, Free energy

ANS: State functions: Enthalpy, Entropy, Temperature, Free Energy

Path functions: Heat, Work

12 Expansion of a gas in vacuum is called free expansion. Calculate the work done and the
2 change in internal energy when 1 litre of ideal gas expands isothermally into vacuum until 2
its total volume is 5 litre.
 ANS:

12 The difference between CP and CV can be derived using the empirical relation H = U +
3 PV. 2
Calculate the difference between CP and CV for 10 moles of an ideal gas.

ANS:

12 If the combusion of 1 g of graphite produces 20.7 kJ of heat, what will be the molar
2
4 enthalpy change? Give the significance of sign also.

ANS: Molar enthalpy change = Enthalpy change for 1 g × Molar mass

= –20.7 kJ × 12
= –248.4 = –2.484 × 102 kJ mol–1

12 The enthalpy of vaporisation of CCl4 is 30.5 kJ mol–1. Calculate the heat required for the
2
5 vaporisation of 284 g of CCl4 at constant pressure (Molar mass of CCl4 = 154 g mol–1).

ANS:
Molar mass of CCl4 = 12 + 4 × 35.5
= 12 + 142 = 154 g mol–1
Heat required for vaporisation of 284 g of CCl4
= No. of moles × ΔvapH°

12 Find out whether it is possible to reduce MgO using carbon at 298 K. If not, at what
6 temperature it becomes spontaneous? For reaction:
3

ANS:
 Since ΔG is +ve, therefore, carbon cannot reduce MgO.

12 Calculate ΔfH° of HCl if bond energy of H—H bond is 437 kJ mol–1, Cl—Cl bond is 244 kJ
3
7 mol–1 and H—Cl is 433 kJ mol–1.

ANS:

12 Calculate bond energy of C—H bond if ΔcH of CH4 is –891 kJ mol–1, ΔcH of C(s) is –394
8 kJ mol–1 Δ,cH of H2(g) is –286 kJ mol–1, 3
heat of sublimation of C(s) is 717 kJ mol–1, heat of dissociation of H2 is 436 kJ mol–1.

ANS:
Reversing (ii), Multiplying (iii) by 2 and reversing and Multiplying (v) by 2 and then adding
all together we get:

Now, energy required to break 4 C—H bond = 1664 kJ

Therefore, energy required to break 1 C—H bond
12 Calculate the standard Gibbs energy change for the formation of propane at 298 K.
9

ANS:

13 (i) Classify the following processes as reversible or irreversible:

0 (a) Dissolution of sodium chloride
(b) Evaporation of water at 373 K and 1atm pressure
(c) Mixing of two gases by diffusion
3
(d) Melting of ice without rise in temperature.
(ii) When an ideal gas expands in vacuum, there is neither absorption nor evolution of
heat.
Why?

ANS: (i) (a) Reversible (b) Irreversible

(c) Irreversible (d) Reversible
(ii) It is because no work is done.
13 State the law of thermodynamics that was first formulated by Nernst in 1906. What is the
1 utility of this law? The equilibrium constant for the
reaction A B is 1.8 × 10–7 at 298 K. 3
–1 –1
Calculate the value of ΔG° for the reaction [R = 8.314 JK mol ]. Predict the feasibility of
the reaction under standard states.

ANS: According to Nernst, at absolute zero, the entropy of a perfectly crystalline

substance is taken as zero at zero kelvin. This is also known as third law of
thermodynamics.
It helps us to calculate the absolute entropies of pure substances at different
temperatures.

Since ΔG° is +ve, therefore, reaction is not feasible at this temperature, i.e., reaction is
non-spontaneous.

13 Why is the entropy of a substance taken as zero at 0 K?

2 Calculate the standard Gibbs free energy change for the reaction:
3
5 –1 –
The value of equilibrium constant for the above reaction is 6.6 × 10 . [R = 8.314 J K mol
1
]

ANS: The entropy of all substances at absolute zero (0 K) is taken as zero because of
complete order in the system, i.e. the atoms or molecule do not move at all in the perfectly
crystalline state.

13 How is the third law of thermodynamics useful in calculation of the absolute entropies?
3 Calculate the value of ΔS° for the following reaction at 400 K: 3
 if the value of equilibrium constant for the reaction at 400 K is 1.958 × 10 –4 and ΔH° = 77.2
kJ mol–1 (R = 8.314 J K–1 mol–1).

ANS:

If we measure the energy required to raise the temperature of a crystalline substance from
0 K to 298
K, we can determine entropy change. The entropy ST at 298 K is called absolute entropy.

= –2.303 × 8.314 J K–1mol–1 × 400 K log 1.958 × 10–4

13 Explain the term ‘standard molar free energy of formation’ of a compound. Calculate the
4 equilibrium constant for the reaction:

ANS: Standard free energy of formation of compound is defined as free energy change
when a compound is formed from its constituting elements at 298 K and 1 atm pressure.
13 (i) Using the data given below, calculate the value of equilibrium constant for the reaction
5 at 298 K.

(ii) Based on your calculated value, comment whether this process can be recommended
as a practical method for making benzene.

ANS:
(ii) Yes, this process can be recommended as a practical method for making benzene as
value of K is very high.

13 (i) State Hess’s Law of constant heat summation. How does it follow from the first law of
3
6 thermodynamics.
 ANS: (i) Hess’s law states enthalpy change remains the same whether the reaction
takes place in one step or in several steps.
It follows from Ist law of thermodynamics that energy can neither be created nor be
destroyed.
It can change from one form to another. The total energy of universe remains constant.

13 (i) Define the following:

7 (a) First law of thermodynamics.
(b) Standard enthalpy of formation.
(ii) Standard heat of formation of hydrazine [N2H4(l)], hydrogen peroxide [H2O2(l)] and 3
water [H2O(l)] are –50.4, –193.2 and –242.7 kJ/mole respectively. Calculate the standard
heat of formation for the following reaction:
N2H4(l) + 2H2O2(l) N2(g) + 4H2O(l)

ANS: (i) (a) First Law of Thermodynamics. It states that energy can neither be created
nor be destroyed. It can change from one form to another. The total energy of universe
remains constant.
(b) Standard Enthalpy of Formation. It is defined as enthalpy change when 1 mole of
compound is formed from its constituting elements.
13 Calculate the lattice enthalpy of MgBr2, given that
8 Enthalpy of formation of MgBr2 = –524 kJ mol–1
Sublimation energy of Mg = 148 kJ mol–1
Ionization energy of Mg = 2187 kJ mol–1 3
Vaporisation energy of Br2(l) = 31 kJ mol–1
Dissociation energy of Br2(g) = 193 kJ mol–1
Electron gain enthalpy of Br(g) = 331 kJ mol–1

ANS:

13 Although heat is a path function but heat absorbed by the system under certain specific
3
9 conditions is independent of path. What are those conditions? Explain.

ANS: At constant volume, according to first law of thermodynamics,

At constant volume and pressure, heat change is a state function because it is equal to
ΔU and ΔH which are state functions and depend upon initial and final states of the
system and not on path.

14 What is meant by entropy? Predict the sign of entropy change in each of the following:
0

3
 (iv) Crystallization of copper sulphate from its saturated solution

ANS: Entropy is defined as the degree of randomness or disorder.

14 (i) State Hess’s law.

1 (ii) Give a brief note on the following thermodynamic terms:
(a) Standard enthalpy of combustion,
(b) Standard enthalpy of formation.
(iii) For the reaction: 5

Calculate ΔG° for the reaction and predict whether the reaction may occur spontaneously.

ANS: (i) Hess’s Law: The total amount of heat evolved or absorbed in a reaction is the
same whether the reaction takes place in one step or in number of steps. In other words,
the total amount of heat change in a reaction depends only upon the reactants and the
products and is independent of the path taken.
(ii) (a) Standard enthalpy of combustion is the amount of heat evolved when one mole of a
substance under standard condition is completely burnt to form product also under
standard conditions.
(b) Standard enthalpy of formation is the enthalpy change accompanying the formation of
one mole of a substance from its constituent element in their standard state, e.g.
standard enthalpy of formation of CO2 may be represented as

14 (i) For the reaction at 298 K:

2
5
At what temperature will the reaction become spontaneous considering ΔH and ΔS to be
constant over the temperature range.
 (ii) State the first law of thermodynamics.
(iii) Give one point to differentiate the following thermodynamic terms:
(a) Extensive properties and intensive properties,
(b) Isothermal process and isobaric process.

ANS:
(ii) First law of thermodynamics states that the total energy of the universe remains
constant, although it may undergo transformation from one form to another.

14 (i) Define standard enthalpy of formation.

3 Explain why the enthalpy changes for the reaction given below are not enthalpies of
formation of CaCO3 and HBr:

5
(ii) Calculate the standard enthalpy change (ΔrH°) and standard internal energy change
(ΔrU°) for the following reaction at 300 K:
OF2(g) + H2O(g) O2(g) + 2HF(g)
Standard enthalpy of formation (Δf H°) of various species are given below:
Δf H°/kJ mol–1 : OF2(g) = 23.0,
H2O (g) = –241.8, HF(g) = –268.6,
R = 8.314 J K–1 mol–1

ANS: (i) Standard enthalpy of formation is defined as enthalpy change when 1 mole of
compound is formed from the constituting elements in their standard states.
(a) is not enthalpy of formation of CaCO3 because it is not being formed from constituting
elements.
(b) is not enthalpy of formation of HBr because 2 moles of HBr are being formed.
14 (i) State the first law of thermodynamics. Heat (q) and work done (w) individually are not
4 state functions but their sum is always a state function. Explain why.
(ii) Use the bond enthalpies listed below to determine the enthalpy of reaction:

ANS: (i) First Law of Thermodynamics states that energy can neither be created nor be
destroyed. It can
change from one form to another. The total energy of universe remains constant. ‘q’ is not
a state function because it depends upon path.
‘w’ is not a state function because it depends upon path.
q + w = ΔU which is a state function because it is independent of path.

ΔH = Bond energy of reactants – Bond energy of products

14 (i) Define enthalpy of neutralization. The enthalpy of neutralisation of strong acid and
5
5 strong base is constant, why?
 (ii) What is the basis of Hess’s Law?
(iii) For a gaseous reaction
2A2(g) + 5B2(g) 2A2B5(g) at 27 °C,
the heat change at constant pressure is found to be –50.16 kJ. Calculate the value of
internal energy change (ΔU).
Given: R = 8.314 J K–1 mol–1.

ANS: (i) Enthalpy of Neutralization is defined as heat evolved when 1 mole of H+ from
acid combines with 1 mole of base to form water. It is because strong acids and bases are
completely ionised in aqueous solution.
(ii) Law of conservation of energy is the basis of Hess’s law.

14 (i) Derive the mathematical expression for first law of thermodynamics.

6 (ii) q and w are not state function but their sum is state function, why?
(iii) Calculate the ΔrH° for the reaction:
H2(g) + Br2(g) 2HBr(g)
5
Bond enthalpy are given as,
H—H = 436 kJ mol–1,
Br—Br = 192 kJ mol–1 and
H—Br = 368 kJ mol–1

ANS: (i) If U1 is initial internal energy, ‘q’ is heat supplied, w is work done on the
system, then final internal energy