NCERT Exemplar Solutions for Class 11

Chemistry
Chapter – 6 Thermodynamics

Multiple Choice Questions (Type-I)

1.Thermodynamics is not concerned about ________.
(i) energy changes involved in a chemical reaction.
(ii) the extent to which a chemical reaction proceeds.
(iii) the rate at which a reaction proceeds.
(iv) the feasibility of a chemical reaction.
Ans: Thermodynamics is not concerned about how and at what rate these energy
transformations are carried out but is based on initial and final states of a system
undergoing the change. Laws of thermodynamics apply only when a system is in
equilibrium or moves from one equilibrium state to another equilibrium state.
Hence, option(iii) is the correct answer.

2.Which of the following statements is correct?

(i) The presence of reacting species in a covered beaker is an example of
open system.
(ii) There is an exchange of energy as well as matter between the system and
the surroundings in a closed system.
(iii) The presence of reactants in a closed vessel made up of copper is an
example of a closed system.
(iv) The presence of reactants in a thermos flask or any other closed insulated
vessel is an example of a closed system.
Ans: The presence of reactants in a closed vessel made of conducting material
e.g., copper or steel is an example of a closed system. Hence, option(iii) is the
correct answer.

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3.The state of a gas can be described by quoting the relationship between
_____.
(i) pressure, volume, temperature
(ii) temperature, amount, pressure
(iii) amount, volume, temperature
(iv) pressure, volume, temperature, amount
Ans: Variables like p, V, T are called state variables or state functions because
their values depend only on the state of the system and not on how it is reached.
Hence, option(i) is the correct answer.

4. The volume of gas is reduced to half from its original volume. The specific
heat will _____.
(i) reduce to half
(ii) be doubled
(iii) remain constant
(iv) increase four times
Ans: Specific heat capacity is the quantity of heat required to raise the temperature
of one unit mass of a substance by one degree Celsius (or one kelvin). That is why
it is an intensive property which does not depend on mass. Hence, option(iii) is
the correct answer.

5. During complete combustion of one mole of butane, 2658 kJ of heat is

released. The thermochemical reaction for above change is

(i 2C H) 4 10(g + 13O) 2 (g)→ 8CO2(g + 10H O l ) 2 ( )ΔcH = –

2658.0 kJ mol –1

(ii C H) 4 10 (g + ) 132O g 2 ( )→ 4CO2(g + 5H O g ) 2 ( )ΔcH = –1329.0 kJ

mol–1

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(iii C H) 4 10 (g + ) 132O g2 ( )→ 4CO2(g + 5H O l ) 2 ( )ΔcH = – 2658.0 kJ
mol–1

(iv C H) 4 10 (g +) 132O g2 ( )→ 4CO2(g + 5H O l) 2 ( ) ΔcH = + 2658.0 kJ

mol–1

Ans: Standard enthalpy of combustion is defined as the enthalpy change per mole
(or per unit amount) of a substance when it undergoes combustion and all the
reactants and products being in their standard states at the specified temperature.
Hence, option(iii) is the correct answer.

6. ΔUf e
of formation of CH4 (g) at certain temperature is –393 kJ mol–1.
The value of ΔHf e is

(i) zero

(ii) < ΔUf e

(iii) > ΔUf e

(iv) equal to ΔUf e

Ans: The balanced equation for the combustion of methane is:

CH4(g +2O) 2(g)→CO2(g +2H O l) 2 ()

Therefore, Δng =1−3=−2

ΔHo = ΔUo + Δng RT

ΔHo=−393−2RT

ΔHo< ΔUo

Hence, option (ii) is the correct answer.

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7. In an adiabatic process, no transfer of heat takes place between system
and surroundings. Choose the correct option for free expansion of an ideal
gas under adiabatic condition from the following.

(i) q = 0, ∆T ≠ 0, w = 0
(ii) q ≠ 0, ∆T = 0, w = 0
(iii) q = 0, ∆T = 0, w = 0
(iv) q = 0, ∆T < 0, w ≠ 0

Ans: In free expansion, w=0 because volume is constant, as the process is

adiabatic q = 0 and from first law of thermodynamics.
ΔU=q+w

This means that internal energy remains constant.

Hence, option(iii) is the correct answer.

8. The pressure-volume work for an ideal gas can be calculated by using the
Vf

expression w = -∫ P dVex
Vi

The work can also be calculated from the pV plot by using the area under
the curve within the specified limits. When an ideal gas is compressed
(a) reversibly or (b) irreversibly from volume Vi to V . choose
f

the correct option.

(i) w (reversible) = w (irreversible)

(ii) w (reversible) < w (irreversible)
(iii) w (reversible) > w (irreversible)
(iv) w (reversible) = w (irreversible) + Pex ∆V

Ans: As the area under the curve is always more in irreversible compression and
this can be explained by the below curves-

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Hence, option(ii) is the correct answer.

9. The entropy change can be calculated by using the expression ΔS = qrevT

. When water freezes in a glass beaker, choose the correct statement amongst
the following :
(i) ∆S (system) decreases but ∆S (surroundings) remains the same.
(ii) ∆S (system) increases but ∆S (surroundings) decreases.
(iii) ∆S (system) decreases but ∆S (surroundings) increases.
(iv) ∆S (system) decreases and ∆S (surroundings) also decreases.
Ans: (iii) ∆S (system) decreases but ∆S (surroundings) increases.

10. On the basis of thermochemical equations (a), (b) and (c), find out which
of the algebraic relationships given in options (i) to (iv) is correct.

(a C) (graphite ) + O2 (g )→CO g ; 2 ( ) Δ H = x kJ molr –1

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 –1
1
(b C ) (graphite) + O g2 ( )→CO g ; ( ) ΔH = y kJ molr
2

(c CO g + O g) ( )2 ( )→CO g ; 2 ( ) Δ H = z kJ molr –1
(i) z = x + y
(ii) x = y – z
(iii) x = y + z
(iv) y = 2z – x
Ans: When we add equations (b) and (c) we will get equation(a) hence, Algebraic
sum of y and z will give x, x =y + z. Hence, option(iii) is the correct answer.

11. Consider the reactions given below. On the basis of these reactions find
out which of the algebric relations given in options (i) to (iv) is correct? (a C
g+4Hg) ( ) ( )→ CH g ;4 ( ) Δ H = x kJ molr –1

(b C )(graphite,s) + 2H g2 ( )→ CH g ; 4 ( ) Δ H = y kJ molr –1
(i) x = y
(ii) x = 2y
(iii) x > y
(iv) x < y
Ans: Same bonds are formed in reaction (a) and (b) but bonds between the
reactant molecules are broken only in reaction (b). Hence option(iii) is the correct
answer.

12. The enthalpies of elements in their standard states are taken as zero. The
enthalpy of formation of a compound-
(i) is always negative

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(ii) is always positive
(iii) may be positive or negative
(iv) is never negative
Ans: The enthalpies of elements in their standard states are taken as zero. The
enthalpy of formation of a compound as the reaction could be exothermic or
endothermic. Hence, option(iii) is the correct answer.

13. Enthalpy of sublimation of a substance is equal to

(i) enthalpy of fusion + enthalpy of vaporisation
(ii) enthalpy of fusion
(iii) enthalpy of vaporisation
(iv) twice the enthalpy of vaporisation
Ans: Enthalpy of sublimation can be shown as

Solid → Liquid →Vapour

Hence, Enthalpy of sublimation of a substance is equal to enthalpy of fusion +
enthalpy of vaporisation. Therefore, option(i) is the correct answer.

14. Which of the following is not correct?

(i) ∆G is zero for a reversible reaction
(ii) ∆G is positive for a spontaneous reaction
(iii) ∆G is negative for a spontaneous reaction
(iv) ∆G is positive for a non-spontaneous reaction
Ans: ΔG positive for a spontaneous reaction. Hence, option(ii) is the correct
answer.

Multiple Choice Questions (Type-II)

In the following questions two or more options may be correct.
15.Thermodynamics mainly deals with

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(i) interrelation of various forms of energy and their transformation from
one form to another.
(ii) energy changes in the processes which depend only on initial and final
states of the microscopic systems containing a few molecules.
(iii) how and at what rate these energy transformations are carried out.

(iv) the system in equilibrium state or moving from one equilibrium state to
another equilibrium state.
Ans: The laws of thermodynamics deal with energy changes of macroscopic
systems involving a large number of molecules rather than microscopic systems
containing a few molecules. Laws of thermodynamics apply only when a system
is in equilibrium or moves from one equilibrium state to another equilibrium state.
Hence, option (i) an (iv) is the correct answer.

16. In an exothermic reaction, heat is evolved, and system loses heat to the
surroundings. For such system

(i) qp will be negative

(ii) Δ H r will be negative

(iii) qp will be positive

(iv) Δ H r will be positive

Ans: In an exothermic reaction, heat is evolved, and system loses heat to the
surroundings. Therefore, qp will be negative and Δ H r will also be negative.
Hence, option(i) and (ii) is the correct answer.

17. The spontaneity means, having the potential to proceed without the
assistance of external agency. The processes which occur spontaneously are
(i) flow of heat from colder to warmer body.
(ii) gas in a container contracting into one comer.
(iii) gas expanding to fill the available volume.
(iv) burning carbon in oxygen to give carbon dioxide.

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Ans: Gas expands to fill the available space spontaneously and burning of carbon-
to-carbon dioxide is spontaneous. Hence, option(iii) and (iv) is the correct answer.

18. For an ideal gas, the work of reversible expansion under isothermal
Vf .A
condition can be calculated by using the expression w = – nRT ln
Vi
sample containing 1.0 mol of an ideal gas is expanded isothermally and
reversibly to ten times of its original volume, in two separate experiments.
The expansion is carried out at 300 K and at 600 K respectively. Choose the
correct option.
(i) Work done at 600 K is 20 times the work done at 300 K.
(ii) Work done at 300 K is twice the work done at 600 K.
(iii) Work done at 600 K is twice the work done at 300 K.
(iv) ∆U = 0 in both cases.
Ans: For isothermal reversible change, we know

Vf Vf q=-w=nRTIn
=2.303nRTlog
Vi Vi
1
1×R×300KIn
W600K= 10=600=2

W300K 1×R×600KIn 1 300

10
For isothermal expansion of ideal gases, ΔU=0
Since, temperature is constant this means there is no change in internal energy.
Therefore, ΔU=0. Hence, option(iii) and (iv) is the correct answer.

19. Consider the following reaction between zinc and oxygen and choose the
correct options out of the options given below:

2 Zn (s)+ O2 (g) → 2 ZnO (s) ; ∆H = – 693 8. kJ mol –1

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(i) The enthalpy of two moles of ZnO is less than the total enthalpy of two
moles of Zn and one mole of oxygen by 693.8 kJ.
(ii) The enthalpy of two moles of ZnO is more than the total enthalpy of two
moles of Zn and one mole of oxygen by 693.8 kJ.
(iii) 693.8 kJ mol–1 energy is evolved in the reaction.
(iv) 693.8 kJ mol–1 energy is absorbed in the reaction.
Ans: As we know from thermodynamics,

)
Δ H =r o
i ∑a Δ H (products - ∑a b Δ H
if

ii f (reactants)


Since, the above reaction is an exothermic reaction, the enthalpy of reactant is

more than the enthalpy of product. Hence, option(i) and (iii) is the correct answer.

III. Short Answer Type

20. 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 enthalpy
change for vaporising two moles of water under the same conditions? What
is the standard enthalpy of vaporisation for water?
Ans: Enthalpy of a reaction is defined as the energy change per mole for the
process. Therefore,

18 g of HO2 = 1 mole (ΔHVap = 40.79 kJ Mol-1)

Enthalpy change for vaporising 2 moles of HO2 = 2 x 40.79 = 81.58 kJ

ΔH
Vap = 40.79 kJ Mol-1.

21. One mole of acetone requires less heat to vapourise than 1 mol of water.
Which of the two liquids has higher enthalpy of vaporization?

Ans: Due to weak force of attraction between molecules, acetone requires less
heat to vaporise. Hence, water has higher enthalpy of vaporization.

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22. Standard molar enthalpy of formation, ∆ fH- is just a special case of
enthalpy of reaction, ∆ rH- Is the ∆ rH- forhe following reaction same as
∆ fH-? Give reason for your answer.

CaO(s)+CO2(g)→CaCO3(s) ∆ fH-= -178.3KJ/mol

Ans: Standard molar enthalpy of formation,𝛥𝛥rH1- is just a special case of 𝛥𝛥fH2-

, where

one mole of a compound is formed from its constituent elements. In the above
equation, enthalpy of formation and enthalpy of reaction is not the same.

23.The value of ∆HΘ for NH3 is – 91.8 kJ mol-1. Calculate the enthalpy
change for the following reaction :

2NH3(g) →N2(g) + 3H2(g)

Ans: The enthalpy change for the given reaction can be calculated as: -

N2(g) + 3H2(g)→2NH3 (g)

∆ fH=-91.8kg/mol

The enthalpy of the reaction is +91.8 kg/mol. This happens as with the reversal
of reaction, the value of ∆ fH also gets reversed.

24. Enthalpy is an extensive property. In general, if enthalpy of an overall

reaction A→B along one route is ∆ rH and ∆ rH1, ∆ rH2, ∆
rH3……represent enthalpies of intermediate reactions leading to product

B. What will be the relation between ∆ rH for overall reaction and∆ rH1,
∆ rH2, ∆ rH3 etc for intermediate reactions.

Ans: According to Hess’s law, ∆ rH = ∆ rH1+ ∆ rH2+∆ rH3

This is so because during the reaction A→ B, B’s formation undergoes various

intermediate reactions, with the overall value of the enthalpy being ∆ rH.

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25. The enthalpy of atomisation for the reaction CH4(g)→C(g) + 4H (g) is
1665kJ mol-1. What is the bond energy of C-H bond?

Ans: The reaction presented in the question is

CH4(g)→C(g) + 4H (g)

Now, ∆ aH = 1665 kJ mol-1

The mean bond enthalpy of the C-H bond should be used here. For the atomisation
of 4 moles of C-H bonds, the value is 1665 kJ/mol-1. So, per mole energy = 1665/4
= 416.2 kJ / mol-1.

26. Use the following data to calculate ∆ latticeHfor NaBr.

∆ sub H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

Bond dissociation enthalpy of bromine = 192 kJ mol-1

∆ fHfor NaBr (s) = – 360.1 kJ mol-1

Ans: In order to calculate the lattice enthalpy of NaBr,

(i)Na(s) →Na(g) ;∆ subH=108.4 kJ mol-1

(ii) Na→Na+ + e- ; ∆ iH = 496kJ mol-1

1 1 -1
(iii) Br2 → Br, ∆ dissH=96kJ mol
2 2

(iv) Br+e- →Br-; ∆ egH= - 325 kJmol-1

1
∆ fH= ∆ subH+ ∆ dissH+∆ iH+ ∆ egH+ ∆ latticeH 2

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= -360.1 -108.4-96-496+325 = -735.5KJ mol-1

27. Given that ΔH= 0 for mixing of two gases. Explain whether the
diffusion of these gases into each other in a closed container is a spontaneous
process or not?

Ans: It is a spontaneous process. Although enthalpy change is zero, randomness

or disorder (ΔS) increases and ΔS is positive. Therefore, in the equation, ΔG =
ΔH – TΔS, the term TΔS will be negative. Hence ΔG will be negative.

28. Heat has a 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 these three parameters.

Ans: Heat has a randomising influence on a system and temperature is the

measure of average chaotic motion of particles in the system. The mathematical
relation which relates these three parameters is ΔS = qrev/ T

Here, ΔS = change in entropy ^ qrcv = heat of

reversible reaction ‘

T = temperature

29. Increase in enthalpy of the surroundings is equal to decrease in enthalpy

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

Ans: Yes, when the system and the surroundings are in thermal equilibrium, their
temperatures are the same.

30. At 298 K, Kp for the reaction N204(g)⇌ 2N02(g) is 0.98. Predict whether
the reaction is spontaneous or not.

Ans: ΔrG° = -RT ln Kp

= -RT ln (0.98)

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Since In (0.98) is negative

.’. ΔrG° is positive the reaction is non spontaneous

31. A sample of 1.0 mol of a monatomic ideal gas is taken through a cyclic
process of expansion and compression as shown in the figure. What will
be the value of ΔHfor the cycle as a whole?

Ans:

For a cyclic process, ΔH = 0

32. The standard molar entropy of H2O(l) is 70 J K-1 mol-1. Will the standard
molar entropy H2O(s) be more, or less than 70 J K -1 mol-1?
Ans: The standard molar entropy of H20 (1) is 70 J K-1 mol-1. The solid form of
H20 is ice. In ice, molecules of H20 are less random than in liquid water. Thus,
molar entropy of H20 (s) < molar entropy of H20 (1). The standard molar entropy
of H20 (s) is less than 70 J K 1 mol-1.

33. Identify the state functions and path functions out of the following:
enthalpy, entropy, heat, temperature, work, free energy.

Ans: State functions: Enthalpy, entropy, temperature, free energy Path functions:
Heat, work

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34. The molar enthalpy of vaporization of acetone is less than that of water.
Why?

Ans: Molar enthalpy of vaporization is more for water due to hydrogen bonding
between water molecules.

35. Which quantity out of ΔrG and ΔrG° will be zero at equilibrium?

Ans: Gibbs energy for a reaction in which all reactants and products are in
standard state. ΔrG° is related to the equilibrium constant of the reaction as
follows

ΔrG = ArG° + RT In K

At equilibrium, 0 = ΔrG° + RT In A– ({ΔrG = 0) or ΔrG° =-RT lnK

ΔrG° = 0 when K= 1

For all other values of K, ArG° will be non-zero.

36. Predict the change in internal energy for an isolated system at constant
volume.
Ans: For an isolated system w = 0, q = 0

Since ΔU= q + w = 0 + 0 = 0, ΔU= 0

37. Although heat is a path function, heat absorbed by the system under
certain specific conditions is independent of path. What are those
conditions? Explain. Ans : At constant volume q = ΔU + (-w)

-w = pΔ q = AU + pΔV

ΔV = 0 (at constant volume)

Hence, qv = ΔU + 0 = ΔU= change in internal energy at constant pressure, qp =

AU + pΔV

Since ΔU + pΔV=ΔH

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=> qp = ΔH change in enthalpy

Hence, at constant volume and at constant pressure, heat change is a state function
because it is equal to ΔU and ΔH respectively which are state functions.

38. Expansion of a gas in vacuum is called free expansion. Calculate the

work done and the change in internal energy when 1 litre of ideal gas
expands isothermally into vacuum until its total volume is 5 litre.

Ans: During free expansion, external pressure is zero, so Work done, w = pextΔV

= -0(5 – 1) = 0

Since the gas is expanding isothermally, therefore, q = 0

ΔU = q + w =0+0=0

39. Heat capacity (CP) is an extensive property but specific heat (c) is an
intensive property. What will be the relation between Cp and c for 1 mol of
water?

Ans: For water, molar heat capacity = 18 x Specific heat or Cp = 18 x c

But, specific heat,

C = 4.18 J g-1 K-1 Heat capacity,

Cp = 18 x 4.18 JK 1 = 75.24 JK-1

40. The difference between Cp and Cv can be derived using the empirical
relation H = U + pV. Calculate the difference between Cp and Cv for 10
moles of an ideal gas.

Ans: Given that, Cv = heat capacity at constant volume,

Cp = heat capacity at constant pressure

Difference between Cp and Cv is equal to gas constant (R).

.’. Cp – Cv = nR (where, n = no. of moles)

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= 10 x 8.314 = 83.14J

41. If the combustion of 1 g of graphite produces 20.7 kJ of heat, what will

be the molar enthalpy change? Give the significance of the sign also.

Ans: Molar enthalpy change for graphite (ΔH)

= enthalpy change for 1 g x molar mass of C = -20.7×12 = -2.48 x 102 kJ mol-1

Since the sign of ΔH = -ve, it is an exothermic reaction.

42. The net enthalpy change of a reaction is the amount of energy required
to break all the bonds in reactant molecules minus the amount of energy
required to form all the bonds in the product molecules. What will be the
enthalpy change for the following reaction?
H2(g) + Br2(g)→2HBr(g)

Given that the bond energy of H2, Br2 and HBr is 4.35 kJ mol-1,192 kJ mol1
and 368 kJ mol -1 respectively.

Ans: ∆ rH=ΣB.E(reactant)-ΣB.E(product)

=B.E.H2 + BEBR2 -2 ×B.E>HBr

= 435+192-2(×368)
= 109KJmol-1

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

Ans: As per the information provided in the question, for one mole of CCl 4(154
g), the heat of vaporisation required is 30.5 kJ/mol .

Hence for the vaporisation of 284 g of CCl4, we require:

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 284
×30.5 154

=56.2 kJ

44. The enthalpy of reaction for the reaction:

2H2 (g) + O2(g) →2H2O(l) ∆ rH= - 572 kJmol-1. What will be the standard

enthalpy of formation of H2O(l) ?

Ans: Standard molar enthalpy of formation is the enthalpy change for the
formation of one mole of a compound from its most stable states or reference
states. As per the given information in the question, the standard enthalpy for the
given equation is – 572 kJ mol–1

Now the enthalpy of formation for H_{2}O will be half the enthalpy of the value
in the given equation. So, now we can calculate that:

1 572 -1
∆ fH= ×∆ yH= =-
286KJmol
2 2

45. What will be the work done on an ideal gas enclosed in a cylinder, when
it is compressed by a constant external pressure, pext in a single step as
shown in Fig. 6.2. Explain graphically.

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Ans: Assumption: Cylinder is filled with one mole gas, and the piston is
frictionless. Let the pressure of gas inside be p and the volume of gas be V_{I}.

Piston is moved towards the inside to make the external pressure (P_{ext}) equal
to p. Now, let us assume that this change takes place in a single step, hence, V is
the final volume. The work done by the piston is depicted in the graph shown
below by shading the area.

Pext ∆ V= AV1×(V1-V2)

46. How will you calculate work done on an ideal gas in a compression, when
change in pressure is carried out in infinite steps?

Ans: When a process can be reversed by bringing an extremely small change in

it, we call it a reversible process. The pressure-volume graph can be used to
calculate the work done. The pressure is not constant, and changes in infinitesimal
amounts as compression happens from initial volume Vi to the final volume Vf.
The below graph depicts the work done with the shaded area.

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47. Represent the potential energy/enthalpy change in the following
processes graphically.

(a) Throwing a stone from the ground to roof.

(b) H2(g)+ Cl2(g)→HCl (g) ∆ rHΘ=-92.32kJmol-1

In which of the processes potential energy/enthalpy change is a contributing
factor to the spontaneity?
Ans:

(a) Throwing a stone from ground to roof

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b) the reaction involved is a process where the energy decreases after the reaction.
It can be represented as:

In process b), potential energy/enthalpy change is a contributing factor to the

spontaneity.

48. Enthalpy diagram for a particular reaction is given in Fig. 6.3. Is it

possible to decide spontaneity of a reaction from a given diagram? Explain.

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Ans: No, for the state of spontaneity, the enthalpy change is not the only criteria.
Entropy also needs to be taken into account here.

49. 1.0 mol of a monatomic ideal gas is expanded from state (1) to state (2)
as shown in figure. Calculate the work done for the expansion of gas from
state (1) to state (2) at 298 K.

Ans: We can conclude from the figure that this change is a reversible change.

Now,

p1
W= -2.303 ×nRT log
p2

=-2.303 ×8.314×1×298×log2

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 = -2.303 ×8.314×298×0.3010J
=-1717.46J

50. An ideal gas is allowed to expand against a constant pressure of 2 bar

from 10 L to 50 L in one step. Calculate the amount of work done by the gas.
If the same expansion were carried out reversibly, will the work done be
higher or lower than the earlier case?

(Given that 1 L bar = 100 J)

Ans: We know that the amount of work done =-pext ∆ V

On substituting the values in the formula, we get,

-2bar×(50-10)L=-80Lbar
According to the described problem,1LBar = 100J

Therefore, -80 Lbar=(-80×100)=-8000J

=-8kJ, which is the amount of work done

The significance of the negative sign states that the work is done on the
surroundings of the system. In the case of reversible expansion, the work done
will be more.

In the following questions, more than one correlation is possible between

options of both columns.

51.Match the followings:

A B

(i) Adiabatic process (a) Heat

(ii) Isolated system (b) At constant volume

(iii) Isothermal change (c) First law of thermodynamics

(iv) Path function (d) No exchange of energy and

Class XI Chemistry www.vedantu.com 23

 matter
(v) State function (e) No transfer of heat

(vi) ΔU= q (f) Constant temperature

(vii) Law of conservation of energy (g) Internal energy

(viii) Reversible process (h) Pext=0

(ix) Free expansion (i) At constant pressure

(j) Infinitely slow process which
(x) ΔH=q proceeds through a series of
equilibrium states.
(xi) Intensive property (k) Entropy
(xii) Extensive property (l) Pressure

(k) Specific heat

Ans:

(i)- (e)

(ii)- (d)

(iii)- (f)

(iv)- (a)

(v)- (g)

(k)- (L)

(vi)- (b)

(vii)- (c)

(viii)- (j) (ix)-

(h)

Class XI Chemistry www.vedantu.com 24

(x)- (i)

(xi)- (a), (l), (m)

(xii)- (g), (k)

52. Match the following processes with entropy change:

Reaction Entropy Change

(i) A liquid vapourises (a) ΔS=0

(ii) Reaction is nonspontaneous at all (b) ΔS= positive

temperatures and ΔH is positive.

(iii) Reversible expansion of an ideal (c) ΔS= negative

gas
Ans:

(i) (b)

(ii) (c)

(iii) (a)

53. Match the following parameters with description for spontaneity:

Δ (parameters)
Description
ΔH 0
ΔrS0 ΔrG0
(a) Non-spontaneous at high
+ - +
temperature.
- - + at high (b) Spontaneous at all
temperature temperatures.
(c) Non-spontaneous at all
- + -
temperatures.
Ans: (i)- (c)

Class XI Chemistry www.vedantu.com 25

(ii)- (a)

(iii)- (b)

54. Match the following:

Column I Column II

(i) Entropy of vaporisation (a) decreases

(ii) K for spontaneous process (b) is always positive

(iii) Crystalline solid state (c) lowest entropy

(iv) ΔU in adiabatic expansion
(d) ΔHvap/Tb
of ideal gas.
Ans:

(i)- (b), (d)

(ii)- (b)

(iii)- (c)

(iv)- (a)

In the following questions a statement of Assertion (A) followed by a

statement of reason (R) is given. Choose the correct option out of the choices
given below each question.

55. Assertion (A): Combustion of all organic compounds is an exothermic

reaction.

Reason (R): The enthalpies of all elements in their standard state are zero.

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

(ii) Both A and R are true but R is not the correct explanation of A.

(iii) A is true but R is false.

(iv) A is false but R is true.

Class XI Chemistry www.vedantu.com 26

Ans: (ii)

Explanation: The enthalpy of the reactants is always greater than the enthalpy of
the product in a combustion reaction.

56. Assertion (A): Spontaneous process is an irreversible process and may be

reversed by some external agency.

Reason (R): Decrease in enthalpy is a contributory factor for spontaneity.

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

(ii) Both A and R is true but R is not the correct explanation of A.

(iii) A is true but R is false.

(iv) A is false but R is true.

Ans: (ii)

Explanation: The energy factor for a spontaneous process should be favourable

(i.e., -ve) and the randomness should be positive.

57. Assertion (A): A liquid crystallises into a solid and is accompanied by

decrease in entropy.

Reason (R): In crystals, molecules organise in an ordered manner.

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

(ii) Both A and R are true but R is not the correct explanation of A.

(iii) A is true but R is false.

(iv) A is false but R is true.

Ans:(i)

Explanation: The entropy of a liquid reduces as it crystallises. Because the

molecules are more organised in crystalline form.

Long Answer Type

Class XI Chemistry www.vedantu.com 27

58. Derive the relationship between H and U for an ideal gas. Explain each
term involved in the equation.

Ans: We know that the change in internal energy equals the heat absorbed at
constant volume, i.e., U= qV.m. However, the majority of chemical reactions are
carried out in flasks or test tubes under constant atmospheric pressure U= qp -PV
under constant pressure, where qp is the heat absorbed by the system and -PV is
the expansion work done by the system.

Let's call the beginning state with subscript 1 and the end state with subscript 2.

The above equation can be rewritten as

U2-U1= P(V2-V1)

On rearranging, we get

qp= (U2+pV2) - (U1 + pV1)...........(1)

Now, we can define another thermodynamic function, the enthalpy H [Greek

word enthalpien, to warm or heat content] as:

H = U + pV………(2)

So, equation (1) becomes qp

= H2- H1 = ΔH

Despite the fact that q is a path dependent function, H is a state function because
it is reliant on state functions U, p, and V. As a result, H is path-independent. As a
result, qp is path-independent.

Equation (2) can be written as for finite changes at constant pressure.

ΔH= ΔU + ΔpV

Since, P is constant, we can write:

ΔH = ΔU + PΔV……………(3)

It's worth noting that we're actually measuring changes in the enthalpy when heat
is absorbed by the system at constant pressure. Remember ΔH= qp , heat absorbed
by the system at constant pressure. H is negative for exothermic reactions, which

Class XI Chemistry www.vedantu.com 28

produce heat, and positive for endothermic reactions, which absorb heat from the
environment.

As a result, equation (3) becomes U = qv at constant volume (V=0).

ΔH= ΔU=qv

Let's have a look at a gaseous reaction. If VA is the total volume of gaseous

reactants, VB is the total volume of gaseous products, nA is the number of moles
of gaseous reactants, and nB is the number of moles of gaseous products, then we
write using the ideal gas law.,

PVA = nART

PVB = nBRT

Thus, PVB- PVA = nBRT - nART = (nB-nA)RT

Or, P(VB- VA) = (nB - nA)RT

Or, pΔV = ΔngRT……….(4)

The number of moles of gaseous products minus the number of moles of gaseous
reactants is denoted by ng.

Equation (3) is obtained by substituting the value of PV from equation (4) in

equation (3).

ΔH = ΔU + ΔngRT…………(5)

59. Extensive properties depend on the quantity of matter but intensive

properties do not. Explain whether the following properties are extensive or
intensive. Mass, internal energy, pressure, heat capacity, molar heat
capacity, density, mole fraction, specific heat, temperature and molarity.
Ans: A contrast is drawn in thermodynamics between extensive and intense
qualities. An extensive property is one whose value is proportional to the amount
or size of matter in the system. Extensive properties include mass, volume,
internal energy, enthalpy, and heat capacity, to name a few.

Properties that are independent of the amount or size of matter present are known.

Class XI Chemistry www.vedantu.com 29

As though they were intensive properties Temperature, density, and pressure, for
example, are intense properties. A molar property, 𝝌𝝌m, is the value of an
extensive property of the system for 1 mol of the substance. If n is the amount of
matter, 𝝌𝝌m = 𝝌𝝌/n, is independent of the amount of matter. An intensive
property is always the ratio of two extensive properties.

Extensive/Extensive = Intensive

E.g., Mole Fraction = Moles / Total number of moles = Extensive/Extensive

60. The lattice enthalpy of an ionic compound is the enthalpy when one mole
of an ionic compound present in its gaseous state, dissociates into its ions. It
is impossible to determine directly by experiment. Suggest and explain an
indirect method to measure lattice enthalpy of NaCl(s).

Ans: The enthalpy change that occurs when one mole of an ionic compound
dissociates into its ions in a gaseous state is called the lattice enthalpy of an ionic
compound.

Na+ + Cl- (s) → Na+ (g) + Cl- (g)

Δlattice H0 → +788 KJmol-1

Let us now calculate the lattice enthalpy of Na+Cl- (s) by following steps given
below:

Class XI Chemistry www.vedantu.com 30

1. Na (s) → Na (g), sublimation of sodium metal, ΔsubH0 = 108.4 KJmol-1

2. Na (g) → Na+ (g) + e- (g) the ionization sodium atoms, ionization enthalpy.

ΔiH0 = 496 KJ/mol

3. ½ Cl2 (g) → 2Cl (g), the dissociation of chlorine, the reaction enthalpy is half
the bond dissociation enthalpy.

1/2 Δbond H0 = 121 KJ/mol

4. Cl (g) + e- → Cl- (g) electron gained by chlorine atoms. The electron gain
enthalpy,

Δe.g H0 = -348.6 KJ/mol.

5. Na+(g) + Cl- (g) → Na+Cl- (s)

61. ΔG is net energy available to do useful work and is thus a measure of

“free energy”. Show mathematically that ΔG is a measure of free energy.
Find the unit of ΔG. If a reaction has positive enthalpy change and positive
entropy change, under what condition will the reaction be spontaneous?

Ans: We know,

ΔStotal = ΔSsys + ΔSsurr

When a system is in thermal equilibrium with its surroundings, the surroundings'

temperature is the same as the system's. Furthermore, a rise in the enthalpy of the
surroundings equals a decrease in the system's enthalpy. As a result of the entropy
shift in the environment,

ΔSsurr = ΔHsurr/T = -ΔHsys/T

ΔStotal = ΔSsys = (-ΔHsys/T)

Rearranging the above equation:

ΔStotal = TΔSsys - ΔHsys

For spontaneous process,

Class XI Chemistry www.vedantu.com 31

ΔStotal > 0, so

TΔSsys - ΔHsys> 0

⇒ ( - ΔHsys - TΔSsys) > 0

The above equation can be written as

- ΔG > 0

ΔG = ΔH - TΔS < 0

ΔHsys is the enthalpy change of a reaction, TΔSsys is the energy which is not
available to do

useful work. As a result, G is a measure of 'free energy,' as it is the net energy

available to conduct beneficial work. As a result, it's also known as the reaction's
free energy. At constant pressure and temperature, G gives a set of conditions for
spontaneity,

(i) If ΔG is negative (<0), the process is spontaneous.

(ii) If ΔG is positive (>0), the process is nonspontaneous.

• Unit of ΔG is Joule.

• The reaction will be spontaneous at high temperature.

62.Graphically show the total work done in an expansion when the state of
an ideal gas is changed reversibly and isothermally from (Pi, Vi) to (Pf, Vf) .
With the help of a pV plot compare the work done in the above case with
that carried out against a constant external pressure Pf.

Class XI Chemistry www.vedantu.com 32

Ans: (i) Reversible work is represented by the combined areas and

(ii) Work against constant pressure, P is represented by the area

f

Work (i) > Work (ii).

Class XI Chemistry www.vedantu.com 33