Class XI – NCERT – Chemistry Chapter 6

Thermodynamics

NCERT Exercise

Question 1:
Choose the correct answer. A thermodynamic state function is a quantity
(i) used to determine heat changes
(ii) whose value is independent of path
(iii) used to determine pressure volume work
(iv) Whose value depends on temperature only.

Solution 1:
A thermodynamic state function is a quantity whose value is independent of a path.
Functions like p, V, T etc. depend only on the state of a system and not on the path.
Hence, alternative (ii) is correct.

Question 2:
For the process to occur under adiabatic conditions, the correct condition is:
(i) ∆T = 0
(ii) ∆p = 0
(iii) q = 0
(iv) w = 0

Solution 2:
A system is said to be under adiabatic conditions if there is no exchange of heat
between the system and its surroundings. Hence, under adiabatic conditions, q = 0.
Therefore, alternative (iii) is correct.

Question 3:
The enthalpies of all elements in their standard states are:
(i) unity
(ii) zero
(iii) < 0
(iv) different for each element

Solution 3:
The enthalpy of all elements in their standard state is zero. Therefore, alternative (ii)
is correct.

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Question 4:
∆Uθof combustion of methane is - X kJ mol-1. The value of ∆Hθ is
(i) = ∆Uθ
(ii) > ∆Uθ
(iii) < ∆Uθ
(iv) = 0

Solution 4:
Since ∆Hθ = ∆Uθ + ∆ngRT and ∆Uθ = -X kJ mol-1,
∆Hθ = (-X) + ∆ngRT.
⇒ ∆Hθ < ∆Uθ
Therefore, alternative (iii) is correct.

Question 5:
The enthalpy of combustion of methane, graphite and dihydrogen at 298 K
-1 -1 -1
are, -890.3 kJ mol ,-393.5 kJ mol , and -285.8 kJ mol 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.

Solution 5:
According to the question,
(i)
CH4 ( g )  2O2 ( g )  CO2 ( g )  2H2O(l ); c H   890.3 kJ mol 1
(ii)
C(s)  O2 ( g)  CO2 ( g); c H   393.5 kJ mol 1
(ii)
2H2 ( g )  O2 ( g )  2H2O(l ); c H   285.8 kJ mol 1
Thus, the desired equation is the one that represents the formation of CH 4 (g) i.e.,
C(s)  2H2 ( g )  CH4 ( g );  f HCh4 C HC  2 C Hh2 C HCo2

  393.5  2*  285.8   890.3   74.8kJmol 1

 Enthalpy of formation of CH4(g) = -74.8 kJ mol-1
Hence, alternative (i) is correct
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Question 6:
A reaction, A + B  C + D + q is found to have a positive entropy change. The
reaction will be
(i) possible at high temperature
(ii) possible only at low temperature
(iii) not possible at any temperature
(iv) possible at any temperature

Solution 6:
For a reaction to be spontaneous, ∆G should be negative.
∆G = ∆H - T∆S
According to the question, for the given reaction,
∆S = positive
∆H = negative (since heat is evolved) ⇒ ∆G = negative
Therefore, the reaction is spontaneous at any temperature.
Hence, alternative (iv) is correct.

Question 7:
In a process, 701 J of heat is absorbed by a system and 394 J of work is done by the
system. What is the change in internal energy for the process?

Solution 7:
According to the first law of thermodynamics,
U = q + W (i)
Where,
U = change in internal energy for a process
q = heat
W = work
Given,
q = + 701 J (Since heat is absorbed)
W = -394 J (Since work is done by the system
Substituting the values in expression (i), we get
U = 701 J + (-394 J)
U = 307 J
Hence, the change in internal energy for the given process is 307 J.

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Question 8:
The reaction of cyanamide, NH2CN(s) with dioxygen was carried out in a bomb
calorimeter and U was found to be -742.7 KJ mol-1 at 298 K. Calculate the
enthalpy change for the reaction at 298 K.
3
NH2CN(g) + O2 (g)  N2g +CO2g +H2Ol
2

Solution 8:
Enthalpy change for a reaction (∆H) is given by the expression,

H  U  ng RT
Where,
∆U = change in internal energy
∆ng = change in number of moles
For the given reaction,
n g = n g (products) - ng (reactants)
= (2 - 1.5) moles
ng = +0.5 moles
And, ∆U = -742.7 kJ mol-1
T = 298 K
R = 8.314 × 10-3 kJ mol-1 K-1
Substituting the values in the expression of ∆H:
∆H = (-742.7 kJ mol-1) + (+0.5 mol) (298 K) 8.314 × 10-3 kJ mol-1 K-1
= -742.7 + 1.2
∆H = -741.5kJ mol-1

Question 9:
Calculate the number of kJ of heat necessary to raise the temperature of 60 g of
aluminium from 35oC to 55oC. Molar heat capacity of Al is 24 J mol-1 K-1.

Solution9:
From the expression of heat (q),
q = m. c. ∆T
Where,
c = molar heat capacity
m = mass of substance
∆T = change in temperature
Substituting the values in the expression of
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 60 
q=  mol   24 J mol 1K 1   20K 
 27 
q = 1066.7J
q= 1.07 kJ

Question 10:
Calculate the enthalpy change on freezing of 1.0 mol of water at 10.0oC to ice
at - 10.0oC. ,∆fus H = 6.03 KJ mot -1 at 0oC.
Cp [H2O(l) ] = 75.3 J mol-1 K-1;
Cp [H2O(s) ] = 36.8 J mol-1 K-1.

Solution 10:
Total enthalpy change involved in the transformation is the sum of the following
changes:
(a) Energy change involved in the transformation of 1 mol of water at 10°C to 1
molof water at 0°C.
(b) Energy change involved in the transformation of 1 mol of water at 0° to 1 mol of
ice at 0°C.
(c) Energy change involved in the transformation of 1 mol of ice at 0°C to 1 mol of
ice at 10°C.
Total H  Cp  H2O l  T  H freezing  Cp  H2O  s  T
= (75.3 J mol-1 K-1) (0 - 10)K + (-6.03 × 103 J mol-1) + (36.8 J mol-1 K-1) (-10 - 0)K
= -753 J mol-1 - 6030 J mol-1 - 368 J mol-1
= -7151 J mol-1
= -7.151 kJ mol-1
Hence, the enthalpy change involved in the transformation is -7.151 kJ mol-1

Question 11:
Enthalpy of combustion of carbon to carbon dioxide is -393.5 kJ mol-1
Calculate the heat released upon formation of 35.2 g of CO2 from carbon and
dioxygen gas.

Solution 11:
Formation of CO2 from carbon and dioxygen gas can be represented as
C( s )  O2( g )  CO2( g ) ; H  393.5 kJ mol 1
(1mole=44g)
Heat released in the formation of 44 g of CO2 = 393.5 KJmol-1
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Heat released in the formation of 35.2 g of

CO2 =(393.5KJ)×(35.2g)/(44g)=314.8 KJ

Question 12:
Enthalpies of formation of CO(g), CO2(g), N2O(g)and N2O4(g) are -110 ,-393, 81 kJ
and 9.7 kJ mol-1 respectively. Find the value of ∆rH for the reaction:
N2O4(g) + 3CO(g) 
 N2O(g) + 3CO2(g)

Solution 12:
∆rH for a reaction is defined as the difference between ∆ fH value of products and
∆fH value of reactants.
r H  f H  product   f H  reac tan t 
For the given reaction,
N2O4(g) + 3CO(g) 
 N2O(g) + 3CO2(g)
r H  { f H  N2O  3 f H CO2 }  { f H  N2O   3 f H CO }
Substituting the values of ∆fH for N2O, CO2, N2O4, and CO from the question, we
get:
r H  {81kJ mol 1  3 393 KJ mol 1}  {9.7kJ mol 1  3 110 KJ mol 1}

r H  777.7kJmol 1
Hence, the value of ∆rH for the reaction is 777.7kJmol 1 .

Question 13:
Given
 2NH3 g  ; r H  = -92.4 kJ mol -1
N2 g   3H2 g  
What is the standard enthalpy of formation of NH3 gas?

Solution 13:
Standard enthalpy of formation of a compound is the change in enthalpy that takes
place during the formation of 1 mole of a substance in its standard form from its
constituent elements in their standard state.
Re-writing the given equation for 1 mole of NH3(g),
1 3
N2 g   H 2 g  
 2 NH3 g 
2 2
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Standard enthalpy of formation of NH3(g)

= ½ ∆rHθ
= ½ (-92.4 kJ mol-1)
= -46.2 kJ mol-1

Question 14:
Calculate the standard enthalpy of formation of CH3OH(l) from the following data:
3
CH3OH(l )  O2 ( g )  CO2( g )  2H2Ol  ; r H   -726 kJ mol -1
2
 CO2( g ) ; c H   -393 kJ mol -1
C( g ) + O2( g ) 
1
H2( g )  O2( g )  H 2O(l ) ; f H   -286 kJ mol -1 .
2

Solution 14:
The reaction that takes place during the formation of CH3OH(l) can be written as:
1
C(s) + 2H2O(g) + O2(g)   CH3OH(l) (1)
2
The reaction (1) can be obtained from the given reactions by following the algebraic
calculations as:
Equation (ii) + 2 × equation (iii) - equation (i)
∆fHθ [CH3OH(l)] = ∆cHθ + 2∆fHθ [H2O(l)] - ∆rHθ
= (-393 kJ mol-1) + 2(-286 kJ mol-1) - (-726 kJ mol-1)
= (-393 - 572 + 726) kJ mol-1
∆fHθ [CH3OH(l)] = -239 kJ mol-1

Question 15:
Calculate the enthalpy change for the process
CCl4(g) → C(g) + 4Cl(g)
and calculate bond enthalpy of C-Cl in CCl4(g).
∆ Hθ (CCl ) = 30.5 kJ mol-1.
vap 4

∆fHθ (CCl4) = -135.5 kJ mol-1.

∆aHθ (C) = 715.0 kJ mol-1, where ∆aHθ is enthalpy of atomisation
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∆aHθ (Cl2) = 242 kJ mol-1

Solution 15:
The chemical equations implying to the given values of enthalpies are:
CCl4 g  vap H   30.5kJ mol 1
(i) CCl4l  
C g  a H   715.0 kJ mol 1
(ii) C s 
 2Cl g  a H   242 kJ mol 1
(iii) Cl2 g  
CCl4 g   f H  135.5 kJ mol 1
(iv) C g   4Cl g  
Enthalpy change for the given process CCl4 g  
C g   4Cl g  can be calculated
using the following algebraic calculations as:
Equation (ii) + 2 × Equation (iii) - Equation (i) - Equation (iv)
∆H = ∆aHθ(C) + 2∆aHθ (Cl2) - ∆vapHθ - ∆fH
= (715.0 kJ mol-1) + 2(242 kJ mol-1) - (30.5 kJ mol-1) - (-135.5 kJ mol-1)
∆H = 1304 kJ mol-1
Bond enthalpy of C-Cl bond in CCl4 (g)
1304
 kJ mol 1
4
= 326 kJ mol-1

Question 16:
For an isolated system, ∆U = 0, what will be ∆S?

Solution 16:
∆S will be positive i.e., greater than zero.
Since ∆U = 0, ∆S will be positive and the reaction will be spontaneous.

Question 17:
For the reaction at 298 K,
2A + B → C
∆H = 400 kJ mol-1 and ∆S = 0.2 kJ K-1 mol-1
At what temperature will the reaction become spontaneous considering ∆H and ∆S
to be constant over the temperature range?

Solution 17:
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From the expression,

∆G = ∆H - T∆S
Assuming the reaction at equilibrium, ∆T for the reaction would be:
1
T   H  G 
S
H
=
S
(∆G = 0 at equilibrium)
400kJ mol 1

0.2kJ K 1mol 1
T = 2000 K
For the reaction to be spontaneous, ∆G must be negative. Hence, for the given
reaction to be spontaneous, T should be greater than 2000 K.

Question 18:
For the reaction,
2Cl ( g )  Cl2  g 
what are the signs of ∆H and ∆S ?

Solution 18:
∆H and ∆S are negative
The given reaction represents the formation of chlorine molecule from chlorine
atoms. Here, bond formation is taking place. Therefore, energy is being released.
Hence, ∆H is negative.
Also, two moles of atoms have more randomness than one mole of a molecule. Since
spontaneity is decreased, ∆S is negative for the given reaction.

Question 19: For the reaction 2A(g) + B(g) → 2D(g)

2 A  g   B  g   2D  g 
∆Uθ = -10.5 kJ and ∆Sθ= -44.1 JK-1.
Calculate ∆Gθ for the reaction, and predict whether there action may occur
spontaneously.

Solution 19:
For the given reaction,
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Thermodynamics

2 A  g   B  g   2D  g 
∆ng = 2 - (3)
= -1 mole
Substituting the value of ∆Uθ in the expression of ∆H:
∆Hθ = ∆Uθ + ∆ngRT
= (-10.5 kJ) - (-1) (8.314 × 10-3 kJ K-1 mol-1) (298 K)
= -10.5 kJ - 2.48 kJ
∆Hθ = -12.98 kJ
Substituting the values of ∆Hθ and ∆Sθ in the expression of ∆Gθ:
∆Gθ = ∆Hθ - T∆Sθ
= -12.98 kJ - (298 K) (-44.1 J K-1)
= -12.98 kJ + 13.14 kJ
∆Gθ = + 0.16 kJ
Since ∆Gθ for the reaction is positive, the reaction will not occur spontaneously.

Question 20:
The equilibrium constant for a reaction is 10. What will be the value of ∆Gθ? R =
8.314 JK-1 mol-1, T = 300 K.

Solution 20:
From the expression,
∆Gθ = -2.303 RT logKeq
∆Gθ for the reaction,
= (2.303) (8.314 JK-1 mol-1) (300 K) log10
= -5744.14 Jmol-1
= -5.744 kJ mol-1

Question 21:
Comment on the thermodynamic stability of NO(g), given
1 1
NO  g   O2  g   NO2  g  : r H   90 kJ mol 1
2 2

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1
 O2 g  : r H   74 kJ mol 1
NO g   O2 g  
2

Solution 21:
The positive value of ∆rH indicates that heat is absorbed during the formation of
NO(g). This means that NO(g) has higher energy than the reactants (N2 and O2).
Hence, NO(g) is unstable.
The negative value of ∆rH indicates that heat is evolved during the formation of
NO2(g) from NO(g) and O2(g). The product, NO2(g) is stabilized with minimum
energy.
Hence, unstable NO(g) changes to unstable NO2(g).

Question 22:
Calculate the entropy change in surroundings when 1.00 mol of H 2O(l) is formed
under standard conditions. ∆fHθ = -286 kJ mol-1.

Solution 22:
It is given that 286 kJ mol-1 of heat is evolved on the formation of 1 mol of H2O(l).
Thus, an equal amount of heat will be absorbed by the surroundings.
qsurr = +286 kJ mol-1
qSurr
Entropy change (∆Ssurr) for the surroundings =
7
286kJ mol 1

298k
∆Ssurr = 959.73 J mol-1 K-1

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