NCERT Solutions for Class 11

Chemistry
Chapter 6 - Thermodynamics

NCERT Exercise

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

a. used to determine heat changes
b. whose value is independent of path
c. used to determine pressure volume work
d. whose value depends on temperature only.
Ans: A thermodynamic state function is a quantity whose value is independent of
the path. Functions like p, V, T etc. depend only on the state of a system and not on
the path.
Hence, alternative (b) is correct.

2. For the process to occur under adiabatic conditions, the correct condition
is:
a. ΔT=0
b. Δp=0
c. q=0
d. w=0
Ans: A system is said to be under adiabatic conditions if there is zero exchange of
heat between the system and its surroundings. Hence, under adiabatic conditions,
q  0 . Therefore, alternative (c) is correct.

3. The enthalpies of all elements in their standard states are:

(i) unity
(ii) zero
(iii) < 0
(iv) different for each element
Ans: The enthalpy of all elements in their standard state is zero. Therefore,
alternative (ii) is correct.

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4. ΔUθ of combustion of methane is -XkJ mol -1 . The value of ΔH is
(i) = ΔUθ
(ii) > ΔUθ
(iii) < ΔUθ
(iv) = 0
Ans: Since H  U  n g RT and U  -X kJ mol-1 ,
H  (-X)  n g RT
 H  U
Therefore, alternative (iii) is correct.

5. 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 respectively.
Enthalpy of formation of CH 4 (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: According to the question,
(i) CH4 (g)  2O2 (g)  CO2 (g)  2H 2O(l); cH  890.3kJ mol 1
(ii) C(s)  2O2 (g)  CO2 (g); cH  393.5kJ mol1
(iii) 2H2 (g)  O2 (g)  2H 2O(l); cH  285.8kJ mol 1
Thus, the desired equation is the one that represents the formation of CH 4 (g) that is
as follows:
C(s)  2H2 (g)  CH4 (g); f HCH4  cHc  2cHH2  cHCO2
Substituting the values in the above formula :
Enthalpy of formation CH 4 (g) = (393.5)  2  (285.8)  (890.3)  74.8kJmol 1
Therefore, alternative (i) is correct.

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

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 (iii) not possible at any temperature
(iv) possible at any temperature
Ans: 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)
That results in G  negative
Therefore, the reaction is spontaneous at any temperature.
Hence, alternative (iv) is correct.

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?
Ans: 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.

8. The reaction of cyanamide, NH 2CN  s  with dioxygen was carried out in a

bomb calorimeter and ΔU was found to be -742.7 KJ mol 1 at 298 K.
Calculate the enthalpy change for the reaction at 298 K.
3
NH4CN(g) + O2(g)  N2(g) +CO2(g) +H2O(l)
2
Ans: Enthalpy change for a reaction  H  is given by the expression,
H  U  n g RT
Where,
U = change in internal energy

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n g = change in number of moles
For the given reaction,
n g  n g (products) -  n (reactants)
g

n g  (2  1.5) moles
n g  0.5 moles
And, U = -742.7 kJ mol1
T = 298 K
R = 8.314 103 kJ mol1K 1
Substituting the values in the expression of H
H   742.7 kJ mol 1    0.5 mol   298 K  8.314  103 kJmol1K 1
H = -742.7 + 1.2
H   741.5kJ mol1

9. Calculate the number of kJ of heat necessary to raise the temperature of 60

g of aluminium from 35C to 55°C . Molar heat capacity of Al is
24J mol -1K -1 .
Ans: From the expression of heat (q),
q  m. c. T
Where,
c = molar heat capacity
m = mass of substance
T = change in temperature
Given,
m = 60 g
c = 24J mol-1K 1
T   55  35 C
T   328  308 K  20K
Substituting the values in the expression of heat:
 60 
q   mol   24Jmol1K 1   20K 
 27 
q = 1066.7 J
q = 1.07 kJ

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10. Calculate the enthalpy change on freezing of 1.0 mol of water at 10.0°C to
ice at -10.0°C , Δfus H = 6.03 KJ mol -1 at 0°C .
Cp H2O  l   = 75.3 J mol -1 K -1 ;
Cp H2O  s   = 36.8 J mol -1 K -1 .
Ans: 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 10.0C to
1mol of water at 0C .
(b) Energy change involved in the transformation of 1 mol of water at 0C 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  Hfreezing  Cp H2O  s  T
H   75.3 Jmol1K 1   0  10  K   6.03  103 Jmol 1    36.8 Jmol 1K 1   10  0  K
H   753 J mol1  6030 J mol1  368 J mol1
H   7151 J mol1
H   7.151 kJ mol1
Hence, the enthalpy change involved in the transformation is  7.151 kJ mol1

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 CO 2 from carbon
and dioxygen gas.
Ans: Formation of CO 2 from carbon and dioxygen gas can be represented as
C(s)  O2(g)  CO2(g) ; H  393.5kJ mol1 (1mole=44g)
Heat released in the formation of 44 g of CO 2 = 393.5 kJmol1
Heat released in the formation of 35.2 g of
(35.2g)
CO2  (393.5kJ)   314.8kJ
(44g)
So, heat released upon formation of 35.2 g of CO 2 from carbon and dioxygen gas
is 314.8 kJ.

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12. Enthalpies of formation of CO (g), CO 2 (g) , N 2O(g) and N 2O 4 (g) are -110 ,
-393, 81 kJ and 9.7 kJ mol -1 respectively. Find the value of Δr H for the
reaction:
N2O4(g) +3CO(g)  N2O(g) +3CO2(g)
Ans:  r H for a reaction is defined as the difference between  f H value of
products and  f H value of reactants.
rH =  H (product) -  H (reactant)
f f

For the given reaction,

N2O4(g)  3CO(g)  N2O(g)  3CO2(g)
r H  f H(NO2 )  3f H(CO2 )  f H(N2O)  3f H(CO)
Substituting the values of  f H for CO (g), CO2 (g) , N 2O(g) and N 2O4 (g) from the
question, we get:
 r H  81kJmol1  3(393)kJmol1  9.7kJmol1  3(110)kJmol1
 r H  777.7kJ mol1
Hence, the value of  r H for the reaction is 777.7kJ mol1

13. Given
N2(g) +3H2(g)  2NH3(g) ;Δr Hθ =-92.4kJmol -1
What is the standard enthalpy of formation of NH 3 gas?
Ans: 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 NH 3 (g) is as follows:
1 3
N2(g)  H2(g)  2NH3(g)
2 2
Therefore, standard enthalpy of formation of NH 3 (g)
= 1
2  r H
= 1
2  92.4 kJ mol 
1

= 46.2 kJ mol1

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14. Calculate the standard enthalpy of formation of CH 3OH( ) from the
following data:
3
CH3OH(l) + O2(g)  CO2(g) +2H 2O(l) ,Δr Hθ =-726 kJ mol -1
2
C(g) +O2(g)  CO2(g) ;ΔcHθ =-393 kJ mol -1
1
H2(g) + O2(g)  H2O(l) ;Δf Hθ =-286kJ mol -1
2
Ans: The reaction that takes place during the formation of CH3OH( ) can be
written as:
1
C(s)  2H2O(g)  O2 (g)  CH3OH( ) (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)
 f H   CH3OH( )    c H   2 f H [H 2O(l)]   r H 
= (-393 kJ mol1 ) + 2(-286 kJ mol1 ) - (-726 kJ mol1 )
= (-393 - 572 + 726) kJ mol1
Therefore,  f H   CH3OH( )   239 kJmol1

15. Calculate the enthalpy change for the process

CCl 4  g   C  g  + 4Cl  g 
and calculate bond enthalpy of C-Cl in CCl 4  g  .
Δvap Hθ (CCl 4 )=30.5 kJmol -1
Δf Hθ (CCl 4 )=-135.5 kJmol -1
Δa Hθ (C)=715.0 kJmol -1 where, Δa H θ is enthalpy of atomization
Δa Hθ (Cl 2 )=242 kJmol -1
Ans: The chemical equations implying to the given values of enthalpies are:
(i) CC4(l)  CCl4(g) vap H  30.5kJmol1
(ii) C(s)  C(g) a H  715.0 kJ mol1

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 (iii) Cl2(g)  2Cl(g) a H  242 kJ mol1
(iv) C(g)  4Cl(g)  CCl4(g) f H  135.5 kJ mol1
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  a H (C)  2a H (Cl2 )   vap H  f H
=  715.0 kJ mol1   2  242 kJ mol1    30.5 kJ mol1    135.5 kJ mol1  Therefore,
H  1304 kJ mol1
Bond enthalpy of C-Cl bond in CCl4 (g)
1304
 kJmol1
4
 326 kJ mol1

16. For an isolated system, ΔU=0 , what will be ΔS ?

Ans: S will be positive i.e., greater than zero.
Since for an isolated system, U  0 , hence S will be positive and the reaction
will be spontaneous.

17. For the reaction at 298 K,

2A+B  C
ΔH= 400 kJ mol -1 and ΔS= 0.2 kJ K -1 mol -1 At what temperature will the
reaction become spontaneous considering ΔH and ΔS to be constant over
the temperature range?
Ans: 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)

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 400 kJ mol1

0.2 kJ K 1 mol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.

18. For the reaction,

2Cl(g)  Cl 2 (g)
What are the signs of ∆H and ∆S ?
Ans: H and S are negative.
The given reaction represents the formation of chlorine molecules from chlorine
atoms. Here, bond formation is occurring. 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.

19. For the reaction

2A  g  + B  g   2D  g 
ΔUθ = -10.5 kJ and ΔSθ = -44.1 JK -1 .
Calculate ΔG θ for the reaction, and predict whether their action may
occur spontaneously.
Ans: For the given reaction,
2A  g   B  g   2D  g 
n g  2  (3) = -1 mole
Substituting the value of U  in the expression of H :
H  U  n g RT
 (10.5 kJ)  (1) 8.314  10 3 kJ K 1 mol 1  (298 K)
=-10.5 kJ - 2.48kJ
H  12.98kJ
Substituting the values of H and S in the expression of G  :
G  H  TS

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= -12.98 kJ - (298 K) (-44.1 J K 1 )
= -12.98 kJ + 13.14 kJ
G  = + 0.16 kJ
Since G  for the reaction is positive, the reaction will not occur spontaneously.

20. The equilibrium constant for a reaction is 10. What will be the value of
ΔG θ ? R = 8.314 JK -1 mol -1 , T = 300 K.
Ans: From the expression,
G    2.303 RTlogKeq
G  for the reaction,
= (2.303) (8.314 JK 1 mol1 ) (300 K) log10
= -5744.14 Jmol1
= -5.744 k Jmol1

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

1 1
NO(g)+ O2 (g)  NO2 (g):Δr Hθ =90kJmol -1
2 2
1
NO(g) + O2(g)  O2(g) :Δr Hθ =-74 kJ mol -1
2
Ans: The positive value of  r H indicates that heat is absorbed during the
formation of NO(g). This means that NO(g) has higher energy than the reactants (
N 2 and O 2 ). Hence, NO(g) is unstable. The negative value of  r H indicates that
heat is evolved during the formation of NO 2 (g) from NO(g) and O 2 (g). The
product, NO 2 (g) is stabilized with minimum energy.
Hence, unstable NO(g) changes to unstable NO 2 (g) .

22. Calculate the entropy change in surroundings when 1.00 mol of H 2O(l) is
formed under standard conditions. Δf H θ = -286 kJ mol -1 .
Ans: It is given that 286 kJ mol-1 of heat is evolved on the formation of 1 mol of
H 2O(l) . Thus, an equal amount of heat will be absorbed by the surroundings.
q surr = +286 kJ kJ mol-1

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 q surr
Entropy change  Ssurr  for the surroundings =
7
286kJ mol1

298K
Therefore,  Ssurr  = 959.73J mol1K 1 .

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