Sri Chaitanya IIT Academy., India.

Chemical Equilibrium

Sri Chaitanya IIT Academy., India.

A.P, TELANGNA, KARNATAKA, TAMILNADU, MAHARASHTRA, DELHI, RANCHI
A right Choice for the Real Aspirant
ICON Central Office, Madhapur- Hyderabad
Topic: Chemical Equilibrium
SINGLIE OPTION QUESTIONS
Equilibrium Concentrations
01. The equilibrium SO 2  g Cl 2  SO 2 g   Cl 2 g  is attained at 25°C in a closed container and
an inert gas, helium is introduced. Which of the following statements is/are correct?
1) Concentrations of SO2, Cl2 and SO2Cl2 change
2) More chlorine is formed.
3) Concentration of SO2 is reduced
4) All are incorrect
KEY: D
SOL: At constant volume, there is not effect on addition of inert gas to a reaction in
equilibrium. At constant pressure, for the reaction in equilibrium. At constant pressure,
for the reaction for which n  0 , There is no effect on addition of inert gas to a reaction
in equilibrium. At constant pressure, for the reactions for which n  0 , the equilibrium
shifts in the direction of more no. of moles.
Factors Affecting the Equilibrium
02. For the reaction,
CO g   H 2 O g   CO 2 g   H 2  g 
At a given temperature, the equilibrium amount of CO 2 g  can be increased by
1) Adding a suitable catalyst
2) Adding on inert gas
3) Decreasing the volume of the container
4) Increasing the amount of CO g 
KEY: D
SOL CO g   H 2O g   CO 2 g   H 2 g 
At constant volume, there is no effect on addition of inert gas to a reaction in equilibrium.
At constant pressure, for the reactions for which n g  0 , there is no affect on addition of
inert gas to a reaction in equilibrium. The presence of the catalyst just helps to achieve
the equilibrium at a different pace. It does not affect the amount of reaction (or) a product
at equilibrium. Only if the reactant concentration is increased the equilibrium shifts
forward and the product concentration is increased
Units of equilibrium constant
Sri ChaitanyaIIT Academy, India jee main Questions
03. Units of equilibrium constant is
1 n n
A. 
mol 
B. 
mol  n
  C.  atm  D.All of these
 L   L 
1) A, B 2) B, C 3) C, D 4) A, D
SOL Conceptual
Key B
04. Assertion A: For N 2 (g)  3H 2 (g)  2NH3 (g) the equilibrium constant is K then for
1 3
N 2 (g)  H 2 (g)  NH3 the equilibrium constant will be k
2 2
Reason R: If concentration are changed to half the equilibrium constant will be halved
1. If both (A) and (R) are correct and (R) is the correct explanation of A
2. If both (A) and (R) are correct and (R) is the incorrect explanation of A
3. If A is correct but R is incorrect 3. If A is incorrect but R is correct
Key 3
Sol If an equation is multiple by n, The K becomes K n and if it is divided by n. The k
becomes m K
Thus the reaction is correct but the reason is incorrect
05. Assertion A: The active mass of pure solid and pure liquid is taken unity
Reason R: The active mass of pure solid and liquid depends on density and molecular
mass. The density and molecular mass of pure liquid and solid are constant
1. If both (A) and (R) are correct and (R) is the correct explanation of A
2.If both (A) and (R) are correct and (R) is the incorrect explanation of A
3. If A is correct but R is incorrect 3. If A is incorrect but R is correct
Key 1
Sol Active mass the term active mass mean the concentration of the reactants as products
expressed in moles per litre (molar concentration) active mass is usually expressed by
enclosing the symbol of the reactants in square bracket [ ]. The active mass of solids and
pure liquids is a constant quantities (unity) and solvent (excess) is considered as one
because there is no change in activities with the change in quantities or volume of vessel
changed in activity with the change in quantity or volume of vessel as density of pure
solid and liquid is constant and molecular mass in also constant. But this is not applicable
to the aqueous solution (or) gaseous solid because their amount in a given volume vessel
Relation between k p and k c
06. For the reaction, CaCO3 s   CaO s   CO 2 g  which is correct representation?

A. k p   PCO2  B. k p  k c  RT  C. k c 
 CO2  D. k c   CaO CO2 
1
1)A, B, C 2) B, C, D 3) A, C, D 4) A, B, D
KEY: A

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SOL As we known, CaCO3 s   CaO s   CO 2 g 

n
k p  k c  RT 
here

n  1  0  so, k p  k c  RT  & k p  pCO2 
1
Also, k c   CO 2     CO 2 
1
07. Assertion: Kp can be equal to or less than or even greater than the value of Kc
Reason: K P nd K C  RT n
1. If both (A) and (R) are correct and (R) is the correct explanation of A
2.If both (A) and (R) are correct and (R) is the incorrect explanation of A
3. If A is correct but R is incorrect 3. If A is incorrect but R is correct
Key a
h
Sol K p  K c  RT1 
n = moles of gaseous product mole of gaseous reactants
08. For the reaction,
1 1
N 2  O 2  2NO, k1;   N 2    O 2  NO, k 2 ;
2 2
1 1
2NO  N 2  O 2 , k 3 ; NO    N 2    O 2 , k 4
2 2
Correct relation(s) between k1, k2, k3 and k4 is/are
A. k1  k 3  1 B. k1  k 4  1 C. k 3  k 2  1 D.None
1)A, B, C 2) B, C, D 3) A, C, D 4) A, B, D
KEY: A
SOL N 2  O 2  2NO

k1 
 NO 
2

 N 2 O2 
1 1
N 2  O 2  NO
2 2

k2 
 NO
 N 2 1/2 O2 1/2
2NO  N 2  O2

k3 
 N 2 O2 
 NO2
1 1
NO  N2  O2
2 2

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k4 
 N 2   O2 
1/2 1/2

 NO
A) k1  k 3 
 NO 
2
 N O 
 2 22  1 B) k1  k 4 
 NO 

 N 2  O2 
1/2 1/2
1
 N 2 O2   NO  2  2
N
1/2
O
1/2
 NO 

C) k3  k 2 
 N 2  O2 
1/2 1/2

 NO 1
 NO  N2 1/2 O2 1/2
Predicting the direction fo the reaction:
09. Assertion A: for PCl5 (g)  PCl3 (g)  Cl2 (g) If more Cl2 is added the equilibrium will
shift in backward direction hence, equilibrium constant will decreases
Reason R: Addition of inert gas to the equilibrium mixture at constant volume does not
alter the equilibrium
1. If both (A) and (R) are correct and (R) is the correct explanation of A
2.If both (A) and (R) are correct and (R) is the incorrect explanation of A
3. If A is correct but R is incorrect 3. If A is incorrect but R is correct
Key 4
Sol For PCl5 (g)  PCl3 (g)  Cl2 (g) if more Cl2 is added the equilibrium will shift in
backward direction. But the value of the equilibrium constant will remain same. Addition
of inert gas to the equilibrium mixture at constant volume does not alter the equilibrium
2
10. Assertion A: The QC for the reaction: 2SO2(g)  O2  2SO3(g) is QC 
 SO3 
SO3 2 O2 
Reason R: When QC  K C the reaction is not at equilibrium and it will be fast in
backward reaction
1. If both (A) and (R) are correct and (R) is the correct explanation of A
2.If both (A) and (R) are correct and (R) is the incorrect explanation of A
3. If A is correct but R is incorrect 3. If A is incorrect but R is correct
Key 3
2
Sol The QC for the reaction 2SO2(g)  O2  2SO3(g) is QC 
 SO3 
when QC  K C .
SO3 2 O2 
The reaction is not at equilibrium and it will proceed in forward direction. This is because
the product concentration is less than equilibrium concentration and the reactants
concentration is more than equilibrium concentration

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11. Assertion A: The reaction N 2 (g)  3H 2 (g)  2NH3 (g) will shift in forward direction by
increase in pressure
Reason R: On increasing the pressure the equilibrium will shift in forward direction
1. If both (A) and (R) are correct and (R) is the correct explanation of A
2.If both (A) and (R) are correct and (R) is the incorrect explanation of A
3. If A is correct but R is incorrect 3. If A is incorrect but R is correct
Key 1
Sol The reaction N 2 (g)  3H 2 (g)  2NH3 (g) will shift in forward direction by increase in
pressure. On increasing the pressure, the equilibrium will shift in forward direction both
assertion and reason are correct and reason is the correct explanation for assertion
Factor Affecting equilibrium position:
12. Assertion A: the equilibrium of  PCl5(g)  PCl3(g)  Cl2(g)  not affected by changing
the volume of container
Reason R: On increasing the pressure, the equilibrium will shift in forward direction
1. If both (A) and (R) are correct and (R) is the correct explanation of A
2.If both (A) and (R) are correct and (R) is the incorrect explanation of A
3. If A is correct but R is incorrect 3. If A is incorrect but R is correct
Key 1
Sol The position of the equilibrium  PCl5(g)  PCl3(g)  Cl2(g)  is affected bychanging the
volume of container. However the value of the equilibrium constant is not affected by

changing the volume of container K C 

 PCl3 Cl2  equilibrium constant, K does not
C
 PCl5 
depend on the volume of vessel. It is dependent of concentration (or partial pressure of
reactants and products) It depends on the temperature assertion is incorrect but reason is
correct
Gibbs free Energy
13. Assertion A: At equilibrium G 0
Reason R: The Gibbs free energy of reactants and products decreases and become equal
at equilibrium
1. If both (A) and (R) are correct and (R) is the correct explanation of A
2.If both (A) and (R) are correct and (R) is the incorrect explanation of A
3. If A is correct but R is incorrect 3. If A is incorrect but R is correct
Key 1
Sol At equilibrium G  0
The Gibbs free energy of reactant and products decrease and become equal at equilibrium
Both assertion and reason are correct and reason is the correct explanation for assertion
G G   RT loge K c
Substitute G  0 for equilibrium concentration

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O  G  RT log e K c  G   Rt log e K C
Calculation of G and K
14. Assertion A: At equilibrium G  0
Reason R: G   RT log c K c at equilibrium
1. If both (A) and (R) are correct and (R) is the correct explanation of A
2. If both (A) and (R) are correct and (R) is the incorrect explanation of A
3. If A is correct but R is incorrect 3. If A is incorrect but R is correct
Key 1
Sol G  H  S
At equation G 0
H  TS
Also at equation H TS
G  0
Applications of Equilibrium constant
15. For the reaction,
PCl5 g   PCl3 g   Cl 2 g 
the forward reaction at constant temperature is favoured by:
A.Introducing an inert gas at constant volume.
B. Introducing chlorine gas at constant volume.
C. Introducing an inert gas at constant pressure
D. Increasing the volume of the container
1) A, B 2) B, C 3) C, D 4) A, D
KEY: B
SOL For the reaction PCl5 g   PCl3 g   Cl2 g 
The forward reaction at constant temperature is favoured by introducing inert gas at
constant pressure, introducing chlorine gas, removing chlorine gas and removing PCl3
gas
Applications of Lechatlier principle
16. Which of the following will favour the formation of NH3 by Haber’s process?
A.Increase of temperature B.Increase of pressure
C.Addition of catalyst D.Addition of promoter
1)A, B, C 2) B, C, D 3) A, C, D 4) A, B, D
KEY: B
SOL The given reaction is
N 2 g   3H 2 g   2NH 3 g  ; H  0
(I) The forward reaction is accompanied decrease in no. of moles so, if pressure is
increased then by Le chatlier’s principle at equilibrium shift in direction of formation of
NH3.
(II) Finely divide iron is used in this reaction to achieve the reaction equilibrium rapidly.
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(III) Molybdenum is used as a promoter to increase the efficiency of the catalyst
Factors affecting equilibrium (reaction) position
17. Which of the following will not affect the value of equilibrium, constant of a reaction?
A.Change in the concentration of the reactants.
B.Change in the temperature
C.Change in the pressure
D.Addition of catalyst.
1)A, B, C 2) B, C, D 3) A, C, D 4) A, B, D
KEY: C
SOL: The following will not affect the value of equilibrium constant of a reaction.
(a) Change in the concentration of the reactants.
(b) change in pressure (D) addition of catalyst.
The addition of catalyst affects the rate of forward reaction and the rate of reverse
reaction but the value of the equilibrium constant is unaffected. However, the value of the
equilibrium constant is affected by (B) the change in temperature. When the reaction is
endothermic reaction, the increase in temperature increases the value of the equilibrium
and when reaction is exothermic it decreases the value.
ONE OR MORE THAN ONE QUESTIONS
Equilibrium Concentrations
18. For the gas phase reaction, C2 H 4  H 2  C2 H 6 Carried out in a vessel, the equilibrium
concentration of C2H4 out in a vessel, the equilibrium concentration of C2H4 can be
increased by
1) Increasing the temperature 2) Decreasing the pressure
3) Removing some H2 4) Adding some C2H6
KEY KEY: ABCD
SOLTUION: Applying Le-chatelier’s principle, when the temperature is increased, the equilibrium
shifts in the direction of less no. of moles. The removal of reactant and a addition of a
product shift the equilibrium in the backward reaction
Topic: predicting the direction of reaction
19. When NaNO3 is heated in a closed vessel oxygen is liberated and NaNO2 is left behind.
At equilibrium
1) Addition of NaNO2 favours reverse reaction.
2) Addition of NaNO3 favours forward reaction.
3) Increase in temperature favours forward reaction.
4) Increasing pressure favours reverse reaction.
KEY: CD
SOLTUION 2NaNO3  g   2NaNO 2 g   O 2 g 
H  positive, endothermic
Addition of solids does not affect the equilibrium.

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Endothermic reaction is favoured by, increase in temperature. Increased pressure shifts
the equilibrium in the direction of less gaseous moles.
Factors Affecting the Equilibrium position
20. For the reaction, PCl5  g   PCl3 g   Cl 2 g 
Theforward reaction at constant temperature is favoured by
1) Introducing an inert gas at constant volume
2) Introducing chlorine gas at constant volume.
3) Introducing an inert gas at constant pressure
4) Introducing PCl5 at constant volume.
KEY: CDE
SOLUTION: At constant volume, there is no effect on addition of inert gas to a reaction in
equilibrium. At constant pressure for the reactions for which n  0 . There is no effect on
addition of inert gas to a reaction in equilibrium. At constant pressure, for the reactions,
for the reactions, for which n  0 . The equilibrium shifts in the direction of more no. of
moles. Addition of the reactant favours forward reaction. Increase the volume means,
decrease the pressure. Which shifts the reaction in the direction of more no. of gaseous
moles.
Predicting the direction of reaction
21. The equilibrium 2Cu1  Cu   Cu11 .
In aqueous medium, at 25°C shifts towards the left in the presence of
1) NO3 2) Cl 3) SCN  4) CN 
KEY: BCD
SOL: Cl and CN ions both make precipitate with Cu1 and hence drive the reaction to the
left.
Cupric thicynate Cu(SCN)2, black powder, insoluble in water readily turning into cuprous
thicynate Cu(SCN) a whitish yellow powder, hence it also drives the equilibrium to the left.

Equilibrium constant
22. The thermal dissociation equilibrium of CaCO 3 s  is studied under different conditions.
CaCO3 s   CaO s   CO 2 g  . For this equilibrium, the correct statement(s) is (are).
1) H is dependent on T
2) K is independent on the initial amount of CaCO3.
3) K is dependent on the pressure of CO2 at a given T.
4) H is independent of the catalyst, if any
KEY: ABD
SOL: (a) H  C p rn  T . Hence enthalpy depends on temperature.
(b) CaCO3  g   CaO s   CO 2 g  k p  PCO2

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(c) k eq depends only on temperature and not on pressure.
(d) Enthalpy of reaction is independent of the catalyst. A catalyst generally lowers
activation energy.
PARAGRAPH QUESTIONS
Paragraph 1: Given: AgCl  2NH 3  Ag(NH 3 ) 2  Cl ; K 0  2.79  10 3
AgCl  2NH 4 OH  Ag(NH 3 ) 2  Cl   2H 2O; K 0  8.46  10 7
23. The solubility of AgCl + 1M NH3 is about
1. 0.053M 2. 2.79  10 3 M 3. 0.53M 4. 0.279 M
Key 1
 Ag(NH )  Cl 
 3 2     s  s 
Sol Å   2.79  103 ;s  2.79  103 M  0.053M
 NH3  2 1M 
24. The solubility of AgCl in 1M NH4OH is about
1. 9.2  102 M 2. 9.2  10 4 M 3. 8.46  10 7 M 4. 0.2 M
Key 1
 Ag(NH )  Cl  
Sol K   3 2    
 s  s   8.46  107 ; s  8.46  107 M  9.2  104 M
 NH 4OH 2 1M 2
25. The equilibrium constant of the reaction NH3  H 2O  NH 4OH is about
1. 3.3  103 2. 3.03  10 4 3. 57.43 4. 1.74  10 2
Key Subtracting the given reactions we get
2.79  103
Sol 2NH3  2H 2O  2NH 4OH K    3298
8.46  107
For NH3  H 2O  NH 4OH K   3298  57.43
Paragraph 2: Given 4NO 2 (g)  O 2(g)  2N 2O5 (g)

 f G  / Kjmol 1 51.3 115.1

26. The standard change in Gibbs function is
1. 166.4 kJ mol 1 2. 166.4 kJ mol1 3. 25.kJ mol1 4. 25.0.kJ mol1
Key 4
Sol  f G   2 f G   N 2O5 .g   4 f G (NO 2 ,g)   2  115.1  4  51.3 kJ mol1  25.0 kJ mol1

27. The value of Kp of the reaction at 298 K is

1. 4.15  105 2. 4.15  10 4 3. 4.15  10 3 4. 4.15  10 2
Key 3
 G   25  103 
Sol K 0p  anti log     anti log     anti log  4.38  4.15  105
 2.303RT   2.303  8.314  298 
 
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28. The value of K C of the reaction at 298K is

1. 6.11 2. 6.1 3. 0.061 4. 0.61
 
Key K e  K p  RT 3vg  4.15  105  0.082  298 3  0.61
Paragraph 3: Given is the following information
2SO3 (g)  2SO 2 (g)  O 2 (g)
 f H  / kJmol 1 -395.7 -296.8
29. The enthalpy change of the reaction is
1. 98.9 kJ mol 1 2. 197.8 kJ mol 1 3. 98.9 kJ mol 1 4. 197.8 kJ mol 1
Key 2
Sol  f H  2 f H  SO 2 .g   2 f H  SO3 ,g    2  296.8   2  395.7   kJ mol1  197.8kJ mol 1
30. On increasing temperature the reaction is
1. shifted to the right side 2. Shifted to the left side
3. no affected 4. Affected but cannot be predicted
Key 1
Sol Since the reaction is endothermic increasing temperature will cause the reaction to shift
towards right side
31. Decomposition of SO3 is favoured at
1. low temperature and low pressure 2. Low temperature and high pressure
3. high temperature and low pressure 4. High temperature and high pressure
Key 3
Sol Since H    ve and vg  1 , the decomposition of SO3 will be favoured on increasing
temperature and decreasing prssure
NUMERICAL QUESTIONS
Topic: Degree of dissociation and equilibrium constant, Determination of
equilibrium concentration, Calculation of equilibrium constant kc. Calculation of
Equilibrium partial pressure, Calculation of Equilibrium constant kp Calculation of
Equilibrium constants k p and k c . Relation between vapour density and Equilibrium
constant Calculation of k c and k p
Degree of dissociation and equilibrium constant
32. One mole of Cl2 and 3 moles of PCl5 are placed in a 100 L vessel heated to 227°C. The
equilibrium pressure is 2.05 atmosphere. Assuming ideal behavior, Calculate the degree
of dissociation for PCl5 and Kp for the reaction.
PCl5  PCl3  Cl2
key: 0.20
SOL

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PCl5  PCl3  Cl 2
3 0 1
3  x  x x 1
Moles at t = 0
Moles at equilibrium
Total moles present at equilibrium = 4 + x
Given, total pressure at equilibrium = 2.05 atm
Now,
pv  nRT at equilibrium
2.05  100   4  x   0.0821 500
 x  0.9939
Now the degree of dissociation for
Moles dissociated 0.9939
PCl5    0.313  or  33.13%
Total moles 3
 n PCl  n Cl   P  x2  2.05 
 kp   3 2   
   
 n PCl5    n   3  x   4  x 


 0.9939 2  2.05 
  0.20
 3  0.9939   4  0.9939 

Determination of equilibrium concentration

33 The equilibrium constant of the reaction,
A 2 g   B2 g   2AB g 
at 100°C is 50. If a one litre flask containing 1mole of A2 is connected to a two litre flask
containing two moles of B2, how many moles of AB will be formed at 373 k?
KEY 1.86
SOL A 2 g   B2 g   2AB g 
At t = 0 1 2 0
At equilibrium (1-x) (2-x) 2x
Total volume of both containers on joining becomes 3L.

 At equilibrium,  A 2  
1 x
,  B2  
 2  x  , AB  2x
 
3 3 3

 kc 
 AB2  4x 2

4x 2
 50
 A 2  B2  9 1  x   2  x  2  3x  x 2
 3   3 

 4x 2  100  150x  50x 2  or  46x 2  150x  100  0

(or) x = 0.93 and 2.326 which is not valid since x  2
 moles of AB  2x  2  0.93  1.86

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Sri ChaitanyaIIT Academy, India jee main Questions
Calculation of equilibrium constant kc
34. At a certain temperature, equilibrium constant (kc) is 16 for the reaction.
SO 2 g   NO 2 g   SO3 g   NO  g 
If we take one mol of each of all the four gases in a one litre containr, what would be the
equilibrium concentration of NO and NO2?
KEY 0.4 mol/L and 1.6 mol/L
SOL “ SO 2 g   NO 2 g   SO3 g   NO g 
At t = 0 1 1 1 1
At equilibrium (1-x) (1-x) (1+x) (1+x)
Let the total volume of the mixture is V litre
 1  x  1  x 
 v   v   1  x 2 
 kc   
1  x  1  x   1  x 2 
 v   v   


1 x
2
 16
1  x 2
 Given , k c  16 
1  x   4 or x  3  0.6
  
1 x 5
Volume  1L
SO 2    NO 2   1  x  1  0.6  0.4 mol / L
and SO3    NO   1  x  1  0.6  1.6 mol / L

Calculation of Equilibrium constant kp

35. N2O4 is 25% dissociated at 37°C and one atmosphere pressure. Calculate
(i) kp and
(ii) The percentage dissociation at 0.1 atmosphere and 37°C.
KEY 0.267 &  0.65  or  65%
SOL: N 2O 4  2NO 2
Before dissociation 1 0
After dissociation 1-a 2a
Total moles after dissociation   n   1    2
 1   
Where  is the degree of dissociation
n
 kp 
 nNO2   p 
2
 
 nN2O4    n 

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Sri ChaitanyaIIT Academy, India jee main Questions


 2   P  (or) k  4 2p
2 1

1    1    p
1  2
4  0.25   1
2
k p     25%, given  0.25 
1   0.25 
2

4 2 p
Again at 0.1 atm k p 
1  2
0.25
  0.267
0.9375
Calculation of Equilibrium partial pressure
36. The equilibrium constant kp of the reaction.
2SO 2 g   O 2 g   2SO3 g 
is900 atm at 800 k. A mixture containing SO3 and O2 having initial pressure of 1 and 2
atm respectively is heated at constant volume to equilibrium. Calculate the partial
pressure of each gas at 800 k.
KEY Key: 2.0118 atm
Consider the reaction,
SOL : 2SO3  2SO 2  O 2
Initial pressure 1 0 2
 x
At equilibrium 1  x  x  2  2 
1 1
k1   atm
k p 900

 p SO  p O 
2
1 1
2 2
k1 
 p SO 1 2
3

 x
x 2 2  
1 2
  
900 1 x 2
 
 Since k p of this reaction is small and thus x < 1
x
2 2
2
1 x 2  2
 
900 1  x 2

2x 2

1  x 2

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Sri ChaitanyaIIT Academy, India jee main Questions

1 2x

30 1  x 
x  0.0236
 At equilibrium
P1SO3  1  x  1  0.0236  0.9764 atm
P1SO 2  x  0.0236 atm
x
P1O 2  2     2.0118 atm
2
Calculation of Equilibrium constants k p and k c .
37. For the reaction,
CO g   2H 2 g   CH 3OH  g 
Hydrogen gas is introduced into a five litre flask at 327°C, containing 0.2 mol of CO(g)
and a catalyst, until the pressure is 4.92 atm. At point, 0.1 mol of CH3OH(g) is formed.
Calculate the equilibrium constants kp and kc.
KEY 1.0327 atm-2
SOL Let the number of moles of hydrogen introduced be n moles.
Total moles of CO and hydrogen = 0.2 + n
Applying PVl = nRT
P = 4.92 atm, V = 5, R = 0.082
T = (273 + 327) = 600 k
4.92  5  0.082  600   0.2  n 
4.92  5
 0.2  n 
0.082  600
 n  0.3mol
CO g   2H 2 g   CH 3OH g 
At equilibrium 0.2 – x 0.3-2x x
or 0.2–0.1 0.3–0.2 0.1
or 0.1 0.1 0.1
0.1 0.1 0.1
  CO   ; H 2   ;  CH3OH    Active masses 
5 5 5
Applying the law of mass action.
0.1
kc 
 CH3OH   5  2500 mol2 L2
COH 2  0.1   0.1 
2 2
 
5  5 
We known that k p  k c  RT n , n  2
2
k p  2500  0.082  600 

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Sri ChaitanyaIIT Academy, India jee main Questions
2500
kp   1.0327 atm 2
 49.2  2

Calculation of Equilibrium constant k p

38. At temperature T, a compound AB2(g) dissociates according to the reaction
2AB2  g   2AB g   B2 g 
with a degree of dissociation x which is small compared with unity. Deduce the
expression for x in terms of the equilibrium constant kp and the total pressure, p.
1/3
x3  2k 
KEY k p  p  or  x   p 
2  p 
2AB2  g   2AB g   B2 g 
Initial mole 1 0 0
x
Mole at equilibrium 1–x x
2
x x
Total moles at equilibrium  1  x  x   1
2 2
2x

2

PAB2 
1  x  P  2 1  x  P
x 2x
2
2
x 2x
PAB  P P
x 2  x
2
2
x/2 x
PB2  P P
x 2  x
2
2
2
 2x   x 
 p  p
 kp 
 PAB   PB2 
2

2x  2 x 
 PAB2 
2 2
 2 1  x  
 p
  2  x  
x 3p

 2  x 1  x 2
1/3
x3  2k p 
kp  p  or  x   
2  p 
Relation between vapour density and Equilibrium constant
39. The degree of dissociation is 0.4 at 400 k and 1.0 atm for the gaseous reaction
PCl5  PCl3  Cl2

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Sri ChaitanyaIIT Academy, India jee main Questions
Assuming ideal behavior of all the gases, calculate the density of equilibrium mixture at
400 k and 1.0 atmosphere (relative atomic mass of p is 31.0 and Cl is 35.5)
Key: 45.9762
SOL: PCl5  g   PCl3 g   Cl 2 g 
At t = 0 1 0 0
At equilibrium (1- 0.4) 0.4 0.4
Total moles at equilibrium  1  0.4  0.4  0.4
= 1.4
PV  nRT
1 V  1.4  0.0821 400
1.4  0.0821  400
V
1
 45.976L
Calculation of k c and k p
40. When 3.06g of solid NH4HS is introduced into a two litre evacuated flask at 27°C, 30%
of the solid decomposes into gaseous ammonia and hydrogen sulphide.
(i) Calculate kc and kp for the reaction at 27°C.
(ii) What would happen to the equilibrium when more solid NH4HS is introduced into the
flask?
Key: 0.048 atm2
SOL: (i) Weight of NH4HS = 3.06 g
3.06 3.06
 Mole of NH 4 HS    0.06
mol.wt 51
NH 4 HS s   H 2S g   NH 3 g 
At T = 0 0.06 mole 0 0
At equilibrium  0.06  0.018  mole 0.018 mole 0.018 mole
(on 30% decomposition)
At equilibrium
0.018
 H 2S   0.009 mol / L
2
0.018
 NH3    0.009 mol / L  volume of flask is 2L 
2
k c   H 2S NH 3   0.009  0.009  81  10 6  mol / L 
2

As we known that k p  k c   RT n

n for above reaction  2
( n  number of gaseous mole of right side number of gaseous mole of left side = 2 – 0
= 2)
T  27C  273  300 K

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Sri ChaitanyaIIT Academy, India jee main Questions
R  0.0821 L  atom / k1mol
k p  81  106   0.0821  300   0.048 atm 2
2

MATCHIGN TYPE QUESTIONS

Equilibrium constant KC
2
41. For the reaction: N 2(g)  3H 2(g)  2NH 3(g) equilibrium constant KC 
 NH3 
Some
 N2  H2 3
reactions are written below in column I and their equilibrium constants in terms of KC are
written in column II Match the following reaction with the corresponding equilibrium
constant
Column I Column II
i. 2N 2(g)  6H 2(g)  4NH 3(g) a. 2K C
ii. 2NH 3(g)  N 2(g)  3H 2(g) b. K1/2
C
1 3 1
iii. N 2(g)  H 2(g)  NH3(g) c.
2 2 KC
2
d. K C
key i-d, ii – c, iii - b
sol
For N 2 (g)  3H 2(g)  2NH3 (g)
2
KC 
 NH3 
 N 2  H 2 3
2N 2(g)  6H 2(g)  4NH3(g) ; K1C  K C
2

1
2NH3(g)  N 2(g)  3H 2(g) ; K1C 
KC
1 3
N 2(g)  H 2(g)  NH 3(g) ; K1C  K1/2
C
2 2
Reaction between KP and KC

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Sri ChaitanyaIIT Academy, India jee main Questions
42. Match the following
List I List II
Kp
A. 2NH3  N 2  3H 2 I.   RT  
KC
Kp 1
B. PCl5  PCl3  Cl2 II.   RT 
KC
Kp 2
C. 3Fe (s)  4H 2O (g)  Fe3O 4(g)  4H 2(g) III.   RT 
KC
Kp 2
D. 2SO 2  O 2  2SO3 IV.   RT 
KC
Kp 1
V.   RT 
KC
Key A – III, B – V, C – I , D - II
Kp
Sol A. n  2, so   RT  2
KC
Kp 1
B. n  1, so   RT 
KC
Kp 0
C.n  0 ,so   RT  for gaseous reagents
Kc
Kp 1
D. n  1,    RT 
Kc
Predicting the direction of the reaction
43. Match the following
Column I Column II
A. K c  103 P. Reactions proceeds nearly
B. K c  103 Q Appreciable concentration of reactants and products
C.10 3  K C  103 R. The product of concentration of products is equal to the products
of conc.
reactants
D. K C  1 S. Unpredictable
T. Reaction goes to completion
Key A – T, B – P, C – Q, D - R
Sol A: High K C reaction goes to completion ion the forward reactions
B: K C is very slow, the reaction proceeds very slowly in forward direction (I)
C; K C is in a range such that forward and backward reaction proceed appricially and
hence reactans and products are present (II)

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Sri ChaitanyaIIT Academy, India jee main Questions
D: The numerater is the products of the concentration of products and denominator is the
product of the concentration of reactants,. At K C  1 these are equal to each other
Factors effecting equilibrium position
44. Match the following
Column I Column II
A. PCl5 (g)  PCl5(g)  Cl2 P. Increase of pressure shifts the equilibrium
forward
B. 2SO 2(g)  O 2(g)  2SO3(g) Q. Decrease of temperature shifts the
equilibrium
forward
C. CO (g)  H 2O (g)  CO 2(g)  2H 2(g) R. Addition of inert gas at constant pressure
shifts
the equilibrium forward
D. 4NH 3(g)  SO 2(g)  4NO (g)  6H 2O(g) S. Addition of catalyst has no effect on the
equilibrium
key A- RS, B- QS, C-R, D-QS

45. Match the following

Column I Column II
A. N 2(g)  O 2(g)  2NO (g) P. K C  K P
B. PCl5(g)  PCl3(g)  Cl 2(g) Q units of K p are atm 1
C. N 2(g)  3H 2(g)  2NH3(g) R. with increase in temperature equilibrium
constant
increases
D. O (g)  H 2O (g)  CO (g)  H 2(g) S. equilibrium is unaffected by pressure
Key A-RS, B-PR, C-QR, D- PR

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