CHEMICAL EQUILIBRIUM

Table of Contents

 Theory .................................................................................................................................. 2

 Solved Examples .................................................................................................................. 7

 Exercise - 1 : Basic Objective Questions ............................................................................. 13

 Exercise - 2 : Previous Year JEE MAINS Questions ............................................................ 21

 Exercise - 3 : Advanced Objective Questions ..................................................................... 24

 Exercise - 4 : Previous Year JEE Advanced Questions ...................................................... 36

 Answer Key .......................................................................................................................... 39

 2 CHEMICAL EQUILIBRIUM

THEORY

1. INTRODUCTION 2.3 Concept of Chemical Equilibrium

Equilibrium represents the state of a process in which the

R
proprties like temperature, pressure, concentration of the
system do not show any change with the passage of time. 1
G P
If the opposing processes involve only physical changes,
3
the equilibrium is called physical equilibrium. If the
opposing processes involve chemical changes, i.e., the
opposing processes are chemical reactions, the equilibrium 2
is called chemical equilibrium.
Progress (R×n Co-ordinate)
2. EQUILIBRIA IN CHEMICAL PROCESSES
 It is the state of minimum Gibb’s energy
2.1 Reversible Reactions
 dG = 0 and G = 0 at this state
A reaction in which not only the reactants react to form the
products under certain conditions but also the products  Rate of forward reaction = Rate of backward reaction
react to form reactants under the same conditions is called
a reversible reaction. In other words a reaction which takes  This equilibrium is dynamic and stable in nature
place not only in the forward direction but also in the
backward direction under the same conditions is called a Dynamic Nature of Chemical Equilibrium
reversible reaction.
In the Haber’s process, starting with definite amounts of
A reversible reaction between A and B to form C and D is N2 and H2 and carrying out the reaction at a particular
represented as : temperature, when equilibrium is attained, the
concentrations of N2, H2 and NH3 become constant. If the
 C + D experiment is repeated by taking deuterium (D2) in place of
A + B 
H2 but with the same amounts and exactly similar conditions
2.2 Irreversible Reactions as before, equilibrium is attained containing D2 and ND3 in
place of H2 and NH3 but in the same amounts. Now, if the
If a reaction cannot take place in the reverse direction, i.e., two reaction mixtures are mixed, then after some time, it is
the products formed do not react to give back the reactants found that the concentrations of ammonia and hydrogen
under the same conditions, it is called an irreversible are same except that now all forms of ammonia (i.e., NH3,
reaction. NH2D, NHD2, ND3) and all forms of hydrogen (i.e., H2, HD,
D2) are present. This shows that at equilibrium, the reaction
A + B 
 C+D is still going on, i.e., equilibrium is dynamic in nature.
 3 CHEMICAL EQUILIBRIUM

t 0
Units of rate : conc/time or mol/Ls

3.2 Overall rate of a reaction

aA + bB cC + dD
Overall Rate =
– (1/a) A/t = – (1/b) B/t = + (1/c) C/t = + (1/d) D/t
Overall rate :
Rate of forward reaction – Rate of backward reaction
“At equilibrium the overall rate of a reversible reaction
becomes zero”.

4. EQUILIBRIUM CONSTANT (K)

2.4 Characteristics of Chemical Equilibrium

4.1 Law of Mass Action
(i) At equilibrium, the concentration of each of the reactants
and the products becomes constant. The rate of a reaction is proportional to the product of the
active masses of the reactants, each raised to the power
(ii) At equilibrium, the rate of forward reaction becomes equal equal to its stoichiometric coefficient as represented by
to the rate of backward reaction and hence the equilibrium the balanced chemical equation.
is dynamic in nature.

(iii) A chemical equlibrium can be established only if none of aA + bB + cC + ...... 

 Products
the products is allowed to escape out or separate out as a
Rate of reaction  [A]a [B]b [C]c .....
solid.
Law of Chemical Equilibrium is a result obtained by applying
e.g. if CO2 gas escapes out in case of decomposition of
the Law of Mass Action to a reversible reaction in
CaCO3, the reaction will no longer remain reversible.
equilibrium.
Similarly, the reaction is irreversible if one of the products
separates out as solid,  C + D
A + B 

AgNO3 + KCl 
 AgCl  + KNO3 Rate of the forward reaction  [A] [B] = kf [A] [B]

(iv) Chemical equilibrium can be attained from either direction, Rate of the backward reaction  [C] [D] = kb [C] [D]
i.e., from the direction of the reactants as well as from the
At equilibrium,
direction of the products.
Rate of forward reaction = Rate of backward reaction
3. RATE OF A REACTION
[C][D] k f
k f [A] [B]  k b [C] [D] or  K
[A][B] k b
Average Rate = Change in concentration/Time taken
= c/t
At constant temperature, as kf and kb are constant, therefore,
c = Final Concentration – Initial concentration
kf
3.1 Instantaneous rate k b = K is also constant at constant temperature and is
called ‘Equilibrium constant’.
Lim c/t = dc/dt
 4 CHEMICAL EQUILIBRIUM

The product of the molar concentrations of the products,

each raised to the power equal to its stoichiometric 4.4 Reaction Quotient (Q)
coefficient divided by the product of the molar
concentrations of the reactants, each raised to the power aA + bB cC + dD
equal to its stoichiometric coefficient is constant at constant
Q = [C]c [D]d/ [A]a [B]b
temperature and is called Equilibrium constant.
Q > Kc : Reaction will tend towards backward direction
4.2 Characteristics of Equilibrium Constant Q > Kc : Reaction will tend towards forward direction
Q > Kc : Reaction will be at equilibrium
(i) The value of the equilibrium constant for a particular
reaction is always constant depending only upon the
temperature of the reaction and is independent of the Note :
concentrations of the reactants with which we start or the
Q is a variable which always approaches Keq which is a
direction from which the equilibrium is approached.
constant.
(ii) If the reaction is reversed, the value of the equilibrium
constant in inversed.

(iii) If the equation (having equilibrium constant K) is divided 4.5 Calculating Equilibrium Concentrations
by 2, the equilibrium constant for the new equation is the
Suppose we are given the following data :
square root of K (i.e., K ).
1. The balanced reaction and value of Kc
(iv) If the equation (having equilibrium constant K) is multiplied 2. The initial concentration of the reactants, or the initial moles
by 2, the equilibrium constant for the new equation is the
3. Volume of the container
square of K (i.e., K2)
And we need to find the final equilibrium concentration of
(v) If the equation (having equilibrium constant K) is written the reactants and products. Then we can follow the
in two steps (having equilibrium constant K1 and K2) then following steps :
K1 × K2 = K.
Step-1
(vi) The value of the equilibrium constant is not affected by the Write down the balanced chemical equation for the reaction
addition of a catalyst to the reaction.
Step-2
This is because the catalyst increases the speed of the
Under every reactant and product, write down the initial
forward reaction and the backward reaction to the same
moles/concentration
extent.
Step-3
4.3 Extent of Reaction Subtract the amount reacting and add the amount produced
in terms of a variable x and note down the equilibrium
High value of Kc (Kc > 103)  At equilibrium reaction is concentration in terms of x. If we are dealing in moles then
forward dominant we will need to divide the moles by volume to obtain
Low value of Kc (Kc < 10–3)  At equilibrium reaction is concentrations.
backward dominant Step-4
3 –3
Moderate value of Kc (between 10 and 10 )  At Substitute the equilibrium concentration in the expression
equilibrium neither direction dominates of Kc and equate it to the value of Kc.
Step-5
Very Kc Very
small large
10
–3
1 10
3 Solve the above equation and calculate the value of x and
Reaction proceeds
hardly at all.
Appreciable concentrations
of both reactants and products
Reaction proceeds in case of multiple solutions select the value which is
nearly to completion.
are present at equilibrium
sensible from reaction point of view. Then back substitute
5 CHEMICAL EQUILIBRIUM

the value of x in the equilibrium concentration expression

and obtain the actual value of the same. POINTS TO REMEBER
Whether the reaction is exothermic or endothermic on
4.6 Equilibrium constant Kp increasing the temperature, it will tend towards
endothermic direction.
aA + bB  cC + dD
Kp = (PCc × PDd)/ (PAa × PBb) 5. HOMOGENOUS EQUILIBRIA
where PC, PD, PA, PB are partial pressures of A, B, C and D
respectively. Reactions in which all reactants and products are in the
same phase Homogenous Reactions can further be divided
Kp = Kc (RT)n into three sub-categoreis :
R = 0.0821 L atm/mol–K 5.1 Those reactions where gaseous moles increase
(n = +ve)
4.7 Relationship of Keq and G PCl5 (g) PCl3 (g) + Cl2 (g)
5.2 Those reactions where gaseous moles remain the same
For any reaction :
(n = 0)
G = Gº + RT InQ Where Q is the reaction quotient.
H2 (g) + I2 (g)  2HI (g)
At equilibrium G = 0 5.3 Those reactions where gaseous moles decrease
Gº = –RT lnKeq = – 2.303RT log10Keq (n = – ve)

where Keq is generally taken as Kp. It depends on the 2NO2 (g)  N2O4 (g)
definition of standard values to define Gº.
If the standard active masses are taken as 1 M each then
6. DEGREE OF DISSOCIATION, 
we will take Keq = KC and if they are taken as 1 atm each
It is defined as the fraction of molecules dissociating. For
then we will take Keq = Kp.
example, if 100 molecules are present and only 40 dissociate
then the degree of dissociation is 0.4 or 40%.
4.8 Dependence of Keq on temperature

7. HETEROGENEOUS EQUILIBRIA
Van’t Hoff Equation :
ln (K2/K1) = (H/R) (1/T1–1/T2) or Category of reactions where various phases/states exist in
log10 (K2/K1) = (H/2.303R) (1/T1–1/T2) the same reaction.
Exothermic Reactions In presence of gases the activity of solids and excess liquids
is constant. Therefore we can assume the active masses of
H = negative solids and excess liquids as constant.
On increasing the temperature the equilibrium constant will
CaCO3(s)  CaO(s) + CO2(g)
decrease i.e. The reaction will become more backward
dominant. Kc = [CO2]
Endothermic Reaction Kp = PCO
2

H = possitive
On increasing the temperature the equilibrium constant will 8. LE CHATELIER’S PRINCIPLE
increase. The reaction will become more forward dominant.
If a distrubance is introduced in an equilibrium mixture it
will behave so as to undo the distrubance and re-establish
equilibrium.
6 CHEMICAL EQUILIBRIUM

8.5 Effect of a Catalyst

8.1 Effect of Change of Concentration

If in a reaction in equilibrium, the concentration of any A catalyst increases the rate of the chemical reaction by
reactant is increased, the equilibrium shifts in the forward making available a new low energy pathway for the
direction. On the other hand, if the concentration of any conversion of reactants to products. It increases the rate
product is increased, the equilibrium shifts in the backward of forward and reverse reactions that pass through the same
direction. The reverse happens if the concentrations are transition state and does not affect equilibrium. Catalyst
decreased. lowers the activation energy for the forward and reverse
reactions by exactly the same amount. Catalyst does not
8.2 Effect of change of temperature affect the equilibrium composition of a reaction mixture. It
does not appear in the balanced chemical equation or in
Exothermic reactions are favoured by low temperature the equilibrium constant expression.
whereas endothermic reations are favoured by high
temperature. eg contact process,

8.3 Effect of change of pressure 2SO2 (g)  O2 (g)  2SO3 (g); K c  1.7 1026

Low pressure favours those reactions which are Practically the oxidation of SO2 to SO3 is very slow. Thus,
accompanied by increase in total number of moles and high platinum or divanadium penta-oxide (V2 O5) is used as
pressure favours those reactions which take place with
catalyst to increase the rate of the reaction.
decrease in total number of moles. However, pressure has
no effect on an equilibrium reaction which proceeds with 8.6 Effect of adding an inert gas to a reaction mixture
no change in total number of moles. in equilibrium.

8.4 Effect of change in volume

(a) If the reaction takes place at constant volume addition of
The effect of decrease of volume is equivalent to the effect an inert gas will not change the molar concentrations of the
of increase of pressure. reactants and products. Hence, the state of equilibrium will
remain unaffected.
hence the effect of decrease in volume will be to shift the
equilibrium in the direction in which the number of moles (b) If the reaction takes place at constant pressure, addition of
decreases. inert gas must accompany in increase in the total volume to
keep pressure constant. Thus, reaction shifts towards larger
number of moles.
 7 CHEMICAL EQUILIBRIUM

SOLVED EXAMPLES

Example - 1 Example - 3

The following reaction has attained equilibrium One mole of H2O and one mole of CO are taken in a 10
litre vessel and heated at 725 K. At equilibrium 40% of
CO(g)  2H 2 (g) CH 3 OH(g), H o  92.0kJ mol1 water (by mass) reacts with CO according to the
equation:
What will happen if (i) volume of the reaction vessel is
suddenly reduced to half? (ii) the partial pressure of H 2 O(g)  CO(g) H 2 O(g)  CO 2 (g)
hydrogen is suddenly doubled? (iii) an inert gas is added
to the system? Calculate the equilibrium constant for the reaction.

Kc 
CH 3OH  , K  PCH OH 3
1  0.40
Sol.
 CO H 2 
2 p
PCO  p 2H Sol. At equilibrium  H 2 O   mol L1 = 0.06 mol L–1,
2 10
[CO]= 0.06 mol L–1.
(i) When volume of the vessel is reduced to half, the
concentration of each reactant or product becomes double.
0.4
Qc 
2 CH3OH 1
 Kc
H2   mol L1  0.04 mol L1 ,
Thus, 2[CO]  (2[H2 ])2 4
As Q c  K c , equilibrium 10

will shift in the forward direction, producing more of [CO2] = 0.04 mol L–1,
CH 3 OH to make Q c  K c .

K
 H 2  CO2   0.04  0.04  0.444
PCH3 OH 1
(ii) QP  2
 (2 p H 2 )  K p .  H 2 OCO 0.06  0.06
p CO 4

Again Qp < Kp, equilibrium will shift in the forward direction Example - 4
to make Qp= Kp.
At 700 K, equilibrium constant for the reaction
(iii) As volume remains constant, molar concentration will not H 2 (g)  I2 (g) 2HI(g)is 54.8. If 0.5 mol L–1 of HI
change. Hence there is no effect on the state of equilibrium.
(g) is present at equilibrium at 700K, what are the
Example - 2 concentrations of H2(g) and I2(g) assuming that we
initially started with HI (g) and allowed it to reach
A sample of HI (g) is placed in a flask at a pressure of
equilibrium at 700 K.
0.2 atm. At equilibrium, the partial pressure of HI (g) is
0.04 atm. What is Kp for the given equilibrium?
1
Sol. 2HI(g) H 2 (g)  I 2 (g) Sol. 2HI(g) H 2 (g)  I2 (g), K 
54.8
Initial pressure 0.2 atm 0 0
At equilibrium [HI]= 0.5 mol L–1,
0.16 0.16
At eqm. 0.04 atm atm atm
2 2 x x 1
 H2   [I2 ]  x mol L1  K  (0.5)2 
54.8
= 0.08 atm
(Decrease in the pressure of HI = 0.2–0.04=0.16 atm.) This gives x  0.068. i.e., [H2]= [I2] = 0.068 mol L–1

p H 2  p I2 0.08atm  0.08atm
 Kp  2
  4.0.
p HI (0.04atm)2
 8 CHEMICAL EQUILIBRIUM

(ii) CH3COOH  C2H5OH CH3COOC2 H5  H2O

Example - 5
What is the equilibrium concentration of each of Initial 1.00 mol 0.180 mol
substances in the equilibrium when the initial
concentration of ICI was 0.78 M? At eqm.1–0.171 0.180–0.171 0.171 mol 0.171 mol
2I Cl(g) I 2 (g)+Cl 2 (g),K c =0.14 = 0.829 mol = 0.009 mol

Sol. Suppose at equilibrium,  I2  = Cl2  =xmolL-1 . Then Molar

2ICl I 2 (g) + Cl 2 (g) concs 8.29/V 0.009/V 0.171/V 0.171/V

Initial conc. 0.78M 0 0

Kc 
 CH3COOC2 H5  H 2 O   0.171/ V  0.171/ V   3.92
CH3COOHC2 H5OH   0.829 / V  0.009 / V 
At eqm. 0.78-2x x x
(iii) CH3COOH  C2H5OH CH3COOC2 H5  H2O
 I  Cl2 
Kc = 2  0.14 
x x
2
 ICl  (0.78  2 x) 2 Initial 1.000 mol 0.500 mol

After time t 1–0.214 0.500–0.214 0.214 mol 0.214 mol

x
or x2  0.14(0.78  2x)2 or  0.14  0.374
0.78  2x = 0.786 mol = 0.286 mol

or x  0.292  0.748 x or 1.748 x  0.292 or x  0.167

 0.214 / V  (0.214 / V)  0.204
Hence, at equilibrium, Reaction quotient (Qc) =
(0.786 / V)(0.286 / V)

 I2  =  Cl2  =0.167M, ICI =0.78-2×0.167M=0.446M

As Q c  K c , equilibrium has not been attained

Example - 6
Example - 7
Ethyl acetate is formed by the reaction between ethanol A sample of pure PCl5 was introduced into an evacuated
and acetic acid and the equilibrium represented as: vessel at 473 K. After equilibrium was attained,
CH 3 COOH(l )  C2 H 5 OH(l ) CH3COOC 2 H 5 (l )  H 2 O(l ) concentration of PCl5 was found to be 0.5×10–1 mol L–1.
If value of Kc is 8.3 × 10–3, what are the concentrations
(i) Write the concentration ratio (reaction quotient), of PCl3 and Cl2 at equilibrium?
Qc for this reaction (Note: water is not in excess
and is not a solvent in this reaction) Sol. PCl5 (g) PCl3 (g)  Cl2(g)
(ii) At 293 K, if one starts with 1.00 mol of acetic acid
and 0.18 mol of ethanol, there is 0.171 mol of ethyl At eqm 0.5× 10–1 mol L–1 x mol L–1 x mol L–1 (suppose)
acetate in the final equilibrium mixture. Calculate
the equilibrium constant. x2
 Kc   8.3  103 (Given)
(iii) Starting with 0.5 mol of ethanol and 1.0 mol of 0.5  101
acetic acid and maintaining it at 293 K, 0.214 mol
of ethyl acetate is found after some time. Has or x 2  (8.3  10 3 )(0.5  101 )  4.15  104 or
equilibrium been reached?

CH3COOC2 H5  H 2 O x  4.15 104  2.04 102 M  0.02M

Sol. (i) Q c  CH COOH C H OH
 3  2 5 
Hence,  PCl3 eq   Cl 2 eq  0.02M
 9 CHEMICAL EQUILIBRIUM

Example - 8 Example - 10
Equilibrium constant, K c for the reaction, Dihydrogen gasusedinHaber’sprocess isproduced by reacting
N 2 (g)  3H 2 (g) 2NH 3 (g) at 500 K is 0.061. At a methane fromnatural gas with high temperature steam. The
first stage of two stage reaction involves the formation of CO
particular time, the analysis shows that composition of
and H2. In second stage, CO formed in first state is reacted
the reaction mixture is 3.0 mol L–1 N2, 2.0 mol L–1 H2
with more steam in water gas shift reaction,
and 0.5 mol L–1 NH3. Is the reaction at equilibrium? If
not, in which direction does the reaction tend to proceed CO(g)  H2 O(g) CO2 (g)  H2 (g) . If a reaction
to reach equilibrium? vessel at 400ºC is charged with an equimolar mixture
of CO and steam such that pCO  pH2O = 4.0 bar, what

Qc 
 NH3 2   0.52  0.0104 will be the partial pressure of H2 at equilibrium? Kp =
Sol.
 N 2  H 2 3  3.0  2.0 3 0.1 at 400ºC.

As Q c  K c , reaction is not in equilibrium Sol. Suppose the partial pressure of H2 at equilibrium= p bar

CO(g)  H 2 O(g) CO2(g) + H2 (g)

As Q c  K c , reaction will proceed in the forward direction.
Initial pressure 4.0 bar 4.0 bar
Example - 9
At eqm (4–p) (4–p) p p
The equilibrium constant for the reaction
H 2 (g)  Br2 (g) 2HBr(g) at 1024 K is 1.6 ×105. Find p2 p
Kp  2
 0.1(given)   0.1  0.316
the equilibrium pressure of all gases if 10.0 bar of HBr (4  p) 4p
is introduced into a sealed container at 1024 K.
p = 1.264–0.316p or 1.316p=1.264 or p=0.96 bar. Hence,

1 (pH2 )eq = 0.96 bar

Sol. 2HBr(g) H2 (g)  Br2 (g). K 
(1.6 105 )
Example - 11
Initial 10 bar Predict which of the following reaction will have
appreciable concentration of reactants and products:
At eqm. 10–p p/2 p/2
(a) Cl 2 (g) 2Cl(g), K c  5  10 39
2
(p / 2)(p / 2) 1 p 1
Kp  2
 
(10  p) 1.6  10 4(10  p) 1.6  105
5 2
(b) Cl2 (g)  2NO(g) 2NOCl(g),Kc  3.7 108

Taking square root of both sides, we get (c) Cl2 (g)  2NO2 (g) 2NO2 Cl(g), K c  1.8

p 1
 2
2(10  p) 4  102 or 4  10 p  2(10  p) or Sol. For reaction (c), as Kc is neither high nor very low, reactants
and products will be present in comparable amounts.

20 Example - 12
402p  20 or p   4.98  10 2 bar
402 The value of Kc for reaction, 3O2(g) 2O3 (g), is
–50
2.0 × 10 at 25ºC. If the equilibrium concentration of O2
Hence, at equilibrium p H2  p Br2 in air at 25ºC is 1.6 × 10–2, what is the concentration of O3?

2 2
= p/2 = 2.5×10–2 bar, p HBr  10  p  10 bar O 
K c  3 3  2.0  1050 
 O3 
Sol.  O2 
3
1.6 102 
 10 CHEMICAL EQUILIBRIUM

or [O3]2 = (2.0 × 10–50) (1.6×10–2)3 = 8.192×10–56 or Example - 15

–28
[O3]= 2.86×10 M Prove that the pressure necessary to obtain 50%
dissociation of PCl5 at 500 K is numerically equal to
Example - 13
three times the value of the equilibrium constant, Kp.
The reaction, CO(g)+3H2(g) CH4(g) + H2O (g), is at
equilibrium at 1300 K in a 1 L flask. It also contains Sol. PCl5 PCl3  Cl2
0.30 mol of CO, 0.10 mol of H2 and 0.02 mol of H2O and
an unknown amount of CH4 in the flask. Determine the Initial moles 1 0 0
concentration of CH4 in the mixture. The equilibrium Moles at eqm. 1–0.5=0.5 0.5 0.5 Total=1.5 moles
constant, Kc, for the reaction at the given temperature
is 3.90. If P is the total required pressure, then

0.5 P 0.5 P
Kc 
 CH 4  H 2 O p PCl5   P  ,PPCl3  P 
Sol. 3 1.5 3 1.5 3
CO H 2 
0.5 P
p Cl2  P 
 3.90 
 CH 4   0.02  1.5 3
3 (molar conc= No. of moles
 0.30  0.10 
p PCl3  pCl2 (P / 3)(p / 3) P
because volume of flask = 1L)  Kp    or P  3K p.
p PCl5 (p / 3) 3
or [CH4]= 0.0585 M=5.85×10–2 M

Example - 14 Example - 16

At emperature T, a compound AB2(g) dissociates What is the effect of reducing the volume on the system
according to the reaction described below?

2AB 2 2AB(g) + B 2 (g) 2C(s)  O 2 (g) 2CO(g)

with a degree of dissociation, x, which is small compared Sol. On reducing the volume, the pressure will increase. By Le
with unity. Deduce the expression for x in terms of the Chatelier’s principle, equilibrium will shift to the side
equilibrium constant Kp and the total pressure, P. accompanied by decrease of pressure, i.e., decrease in the
number of gaseous moles, i.e., backward direction.
Sol. 2AB2 2AB(g)  B2 (g)
Initial 1 mole 0 0 Example - 17

At equilibrium 1 – x 2x x The degree of dissociation is 0.4 at 400 K and 1.0 atm

for the gaseous reaction
Total number of moles at equilibrium = 1–x+2x+x=1+2x
PCl5 PCl3 + Cl2.
1 x 2x x
p AB2   P, p AB   P, p B2  P
1 2 x 1  2x 1  2x Assuming ideal behaviour of all the gases, calculate
the density of the equilibrium mixture at 400 K and 1.0
p 2AB  p B2 2
 2x  P   x  P  1  x 
2
atmosphere. (Atomic mass of P = 31.0 and Cl = 35.5)
 Kp      P
p 2AB2  1  2x   1  2x  1  2x 
Sol. PCl5 PCl3 + Cl2
3
4x P Initial 1 mole 0 0
or K p 
1  x 1  2x 
At eqm. 0.6 0.4 0.4 moles
Neglection x in comparison to unity,
Average molecular mass of mixture
1/ 3
3  Kp 
K p  4x P or x   
 4P 
 11 CHEMICAL EQUILIBRIUM

Step 2. To calculate extra CO2 to be added

0.6(31  5  35.5)  0.4(31  3 35.5)  0.4(2  35.5)

0.6  0.4  0.4 Suppose extra CO2 to be added = x mole. Then writing the
reverse reaction, we have
125.1  55  42.6
  148.92 CO2 + H2 CO + H2O
1.4
initial moles after
For ideal gases,
addition 0.2 + x 0.6 0.4 0.3
w w
PV  nRT  RT or PM  RT  d RT Moles (Molar
M V
Conc.)at new (0.2+x –0.2) (0.6–0.2) 0.6 (0.3+0.2)
PM 1 148.92 equilibrium =x = 0.4 = 0.5
d   = 4.5374 g L–1
RT 0.08205  400
(V=1L) (given)
Example - 18
1 0.6  0.5
At 540 K, 0.10 mol of PCl5 are heated in a 8.0 L flask. Kc '    1 or x  0.75 moles
Kc x  0.4
The pressure of the equilibrium mixture is found to be
1.0 atm. Calculate Kp and Kc for the reaction.
Example - 20

Sol. PCl5 PCl3  Cl2 The degree of dissociation of N2O4 into NO2 at one
atmospheric pressure and 313 K is 0–310. Calculate
Initial 0.1 mol
Kp of the dissociation reaction at this temperature. What
At eqm. 0.1 – x x x will be the degree of dissociation at 10 atmospheric
Total no. of moles at eqm. = 0.1 + x pressure at the same temparture?

PV 1 8 Sol.
PV  nRT, i.e., n    0.18
RT 0.0821 540
For the dissociation
 0.1  x  0.18 or x  0.08
reaction N 2 O 4 (g) 2NO2 (g)
(0.08 / 8)(0.08 / 8)
 Kc   0.04 Initial moles 1 0
(0.02 / 8)
Moles at eqm. 1–0.310=0.69 2×0.310=0.62 ( 0.310,Given)
K p  K c (RT) n  0.04(0.0821 540)1  1.77
Total = 0.69+0.62=1.31 moles
Example - 19 At one atmospheric
An equilibrium mixture,
0.69 0.62
pressure, p N 2 O4   1 atm, p NO2  1atm
CO(g)  H 2 O(g) CO 2 (g)  H 2 (g), present in a 1.31 1.31
vessel of one litre capacity at 1000 K was found to
contain 0.4 mole of CO, 0.3 mole of H2O, 0.2 mole of p 2NO2 (0.62 /1.31atm) 2
CO2 and 0.6 mole of H2. If it is desired to increase the Kp    0.425atm
p N 2 O4 (0.69 /1.31atm)
concentration of Co to 0.6 mole by adding CO2 into the
vessel, how many moles of it must be added into At 10 atmoshperic pressure, suppose degree of dissociation =  .
equilibrium mixture at constant temperature in order Then
to get this change.
N2 O4 2NO2
Sol. Step 1. To calculate Kc of the reaction.
Initial moles 1 0

Kc 
 CO(g) H 2 (g)  0.2  0.6  1 Moles at eqm 1  2 , Total = 1+ 
 CO(g) H2 O(g) 0.4  0.3
 12 CHEMICAL EQUILIBRIUM

1  2 Example - 23
p N 2 O4   10atm, p NO2   10atm
1  1 
0.1 mole of N2O4 (g) was sealed in a tube under
atmospheric condition at 25ºC. Calculate the number
[20 /(1   )]2 40 2 40 2 of moles of NO2(g) present if the equilibrium N2O4(g) is
Kp   
[10(1   ) /(1  )] 1   (1   ) 1   2 reached after some time (Kp = 0.14).

Sol. N 2 O 4 (g) 2NO2(g)

40 2
  0.425
1  2 Initial amount 0.1 mole 0
At equilibrium (0.1–x) 2x, Total=0.1+x moles
Neglecting 2 in comparison to 1, 40 2 = 0.425
0.1  x 2x
or  = 0.103 = 10.3 % As P=1 atm, p N 2O 4  , p NO2  atm
0.1  x 0.1  x

Example - 21
p 2NO2 (2x /(0.1  x)) 2
When α - D glucose is dissolved in water, it undergoes Kp  
p N2 O4 (0.1  x) /(0.1  x)
mutarotation to form an equilibrium mixture of
α - D glucose and β - D glucose containing 63.6% of 4x 2 4x 2
the latter. Calculate Kc for the mutarotation.  
(0.1  x)(0.1  x) 0.01  x 2

Sol. α-D glucose  - D glucose

4x 2
  0.14 or 4.14 x2 = 0.0014 or x=0.018
At equilibrium 36.4% 63.6% 0.01  x 2

 No. of moles of NO2 at equilibrium = 2x=2×0.018= 0.036

63.6 mole
Kc   1.747
36.4

Example - 22

At 77ºC and one atmoshpheric pressure, N2O4 is 70%

dissociated into NO2. What will be the volume occupied
by the mixture under these conditions if we start with
10g of N2O4?

Sol. Molar mass of N 2 O 4  28  64  92g mol 1

N2 O4 2NO2

10
Initial moles 0
92

10 70 10
After dissociation   2×0.076
92 100 92

= 0.109–0.076=0.033 = 0.152
 13 CHEMICAL EQUILIBRIUM

EXERCISE - 1 : BASIC OBJECTIVE QUESTIONS

Equilibrium : Definition 1 1
(a) (b)
4 2
1. In chemical reaction A B, the system will be known
(c) 1 (d) 4
in equilibrium when
7. On a given condition, the equilibrium concentration of HI,
(a) A completely changes to B
H2 and I2 are 0.80, 0.10 and 0.10 mole/litre. The equilibrium
(b) 50% of A changes to B
constant for the reaction H2 + I2 2HI will be
(c) The rate of change of A to B and B to A on both the
sides are same (a) 64 (b) 12
(c) 8 (d) 0.8
(d) Only 10% of A changes to B
2. According to law of mass action rate of a chemical reaction 8. For the system A(g) + 2B(g) C(g),the equilibrium
is proportional to concentrations are (A) 0.06 mole/litre (B) 0.12 mole/litre
(C) 0.216 mole/litre. The Keq for the reaction is
(a) Concentration of reactants
(b) Molar concentration of reactants (a) 250 (b) 416
–3
(c) 4 × 10 (d) 125
(c) Concentration of products
(d) Molar concentration of products 9. For the reaction A + 2B C, the expression for
equilibrium constant is
3. The active mass of 64 gm of HI in a two litre flask would be
(a) 2 (b) 1 [A ] [ B] 2 [A] [B]
(a) (b)
(c) 5 (d) 0.25 [C ] [C]
4. The rate constant for forward and backward reactions of
[C ] [C ]
hydrolysis of ester are 1.1 × 10–2 and 1.5 × 10–3 per minute (c) 2 (d) 2 [B] [A ]
[A ] [ B]
respectively. Equilibrium constant for the reaction is
CH3COOC2H5 + H2O CH3COOH + C2H5OH 10. For which of the following reactions does the equilibrium
constant depend on the units of concentration
(a) 4.33 (b) 5.33
(c) 6.33 (d) 7.33 1 1
(a) NO(g) N 2 (g)  O2 (g)
Equilibrium Constant : Expression 2 2

5. For the system 3A + 2B C, the expression for (b) Zn (s)  Cu 2 (aq) Cu (s)  Zn 2 (aq)
equilibrium constant is (c) C2H5OH (l) + CH3COOH CH3COOC2H5(l) + H2O (l)
[C] (Reaction carried in an inert solvent)
[3A][2B]
(a) (b) [3A][2B]
C (d) COCl2(g) CO(g) + Cl2(g)

[A]3[B]2 [C] 11. Unit of equilibrium constant for the reversible reaction
(c) (d) [A]3[B]2 H2 + I 2 2HI is
[C]

6. 4 moles of A are mixed with 4 moles of B. At equilibrium for (a) mol–1 litre (b) mol–2 litre
the reaction A + B C + D, 2 moles of C and D are (c) mol litre–1 (d) None of these
formed. The equilibrium constant for the reaction will be
 14 CHEMICAL EQUILIBRIUM

12. In a reaction A + B C + D, the concentrations of A, B, 19. An equilibrium mixture of the reaction

C and D (in moles/litre) are 0.5, 0.8, 0.4 and 1.0 respectively. 2H2S(g) 2H2 (g) + S2(g)
The equilibrium constant is
had 0.5 mole H2S, 0.10 mole H2 and 0.4 mole S2 in one litre
(a) 0.1 (b) 1.0 vessel. The value of equilibrium constant (K) in mole litre-1
(c) 10 (d)  is
13. The suitable expression for the equilibrium constant of (a) 0.004 (b) 0.008
the reaction 2NO (g) + Cl2(g) 2NOCl (g) is (c) 0.016 (d) 0.160
20. For the equilibrium N2 + 3H2 2NH3, Kc at 1000K is
2 –3
[2 NOCl] [ NOCl] 2.37 × 10 If at equilibrium [N2] = 2M, [H2] = 3M, the
(a) K c  [2 NO] [Cl ] (b) K c 
2 [ NO]2 [Cl 2 ] concentration of NH3 is
(a) 0.00358 M (b) 0.0358 M
[ NOCl]2 [ NOCl]2
(c) K c  (d) K c  (c) 0.358 M (d) 3.58 M
[ NO] [Cl 2 ]2 [ NO]2 [Cl 2 ]2
21. Two moles of NH3 when put into a previously evacuated

14. A+ B C + D. If finally the concentration of A and B vessel (one litre), partially dissociate into N2 and H2. If at
are both equal but at equilibrium concentration of D will equilibrium one mole of NH3 is present, the equilibrium
be twice of that of A then what will be the equilibrium constant is
constant of reaction. (a) 3/4 mol2 litre–2 (b) 27/64 mol2 litre–2
(a) 4 / 9 (b) 9 / 4 (c) 27/32 mol2 litre–2 (d) 27/16 mol2 litre–2
(c) 1 / 9 (d) 4 22. In Haber process 30 litres of dihydrogen and 30 litres of
dinitrogen were taken for reaction which yielded only 50%
15. For the reaction 2SO2 + O2 2SO3, the units of Kc are of the expected product. What will be the composition of
gaseous mixture under the aforesaid condition in the end
(a) litre/mole (b) mol/litre
–1 2 (a) 20 litres ammonia, 25 litres nitrogen, 15 litres hydrogen
(c) (mol litre ) (d) (litre mole–1)2
(b) 20 litres ammonia, 20 litres nitrogen, 20 litres hydrogen
16. The equilibrium concentration of X, Y and YX2 are 4, 2 (c) 10 litres ammonia, 25 litres nitrogen, 15 litres hydrogen
and 2 moles respectively for the equilibrium
(d) 20 litres ammonia, 10 litres nitrogen, 30 litres hydrogen
2X + Y YX2. The value of Kc is
23. For the reaction equilibrium N2O4 2NO2(g), the
(a) 0.625 (b) 0.0625 concentrations of N2O4 and NO2 at equilibrium are
(c) 6.25 (d) 0.00625 4.8 × 10–2 and 1.2 × 10–2 mol litre–1 respectively. The value

17. In a 500 ml capacity vessel CO and Cl2 are mixed to form of Kc for the reaction is

COCl2. At equilibrium, it contains 0.2 moles of COCl2 and (a) 3.3 × 102 mole litre–1 (b) 3 × 101 mol litre–1

0.1 mole of each of CO and CO2. The equilibrium constant (c) 3 × 10–3 mol litre–1 (d) 3 × 103 mol litre–1
Kc for the reaction CO + Cl2 COCl2 is 24. The equilibrium constant for the reaction
N2(g) + O2(g) 2NO (g) at temperature T is 4 × 10–4.
(a) 5 (b) 10
(c) 15 (d) 20 The value of Kc for the reaction

18. 4.5 moles each of hydrogen and iodine heated in a sealed 1 1

NO (g) N 2 (g )  O 2 (g) at the same temperature
ten litre vessel. At equilibrium, 3 moles of HI were found. 2 2
The equilibrium constant for H2(g) + I2(g) 2 HI(g) is is

(a) 1 (b) 10 (a) 4 × 10–4 (b) 50

(c) 5 (d) 0.33 (c) 2.5 × 10 2
(d) 0.02
 15 CHEMICAL EQUILIBRIUM

25. In the reaction, H2 + I2 2HI. In a 2 litre flask 0.4 moles of Position of Equilibrium : Extent of a Reaction
each H2 and I2 are taken. At equilibrium 0.5 moles of HI are 30. In which of the following, the reaction proceeds towards
formed. What will be the value of equilibrium constant, Kc completion

(a) 20.2 (b) 25.4 (a) K = 103 (b) K = 10–2

(c) 0.284 (d) 11.1 (c) K = 10 (d) K = 1

26. 2 mol of N2 is mixed with 6 mol of H2 in a closed vessel of 31. A 1 M solution of glucose reaches dissociation equilibrium
according to equation given below 6HCHO C6H12O6
one litre capacity. If 50% of N2 is converted into NH3
What is the concentration of HCHO at equilibrium if
at equilibrium, the value of K c for the reaction
equilibrium constant is 6 × 1022
N2(g) + 3H2(g) 2NH3(g) is
(a) 1.6 × 10–8 M (b) 3.2 × 10–6 M
(a) 4/27 (b) 27/4
(c) 3.2 × 10–4 M (d) 1.6 × 10–4 M
(c) 1/27 (d) 24
Equilibrium Constant : Effect of Stoichiometry Kp and Kc Relationship

27. Equilibrium constants K1 and K 2 for the following 32. In which of the following reaction, the value of K p will be

equilibria equal to K c

(a) H2 + I2 2HI (b) PCl5 PCl3 + Cl2

1
NO(g) + O NO2(g)
2 2 (c) 2NH3 N2 + 3H2 (d) 2SO2 + O2 2SO3
and 2NO2(g) 2NO(g) + O2(g) are related as 33. For N2 + 3H2 2NH3 + heat

1 (a) Kp = Kc (RT) (b) Kc = Kp (RT)

(a) K 2  K (b) K 2  K12 (c) Kp = Kc (RT) –2
(d) Kp = Kc (RT)–1
1
34. In which of the following equilibria, the value of Kp is less
K1 1
(c) K 2  (d) K 2  than Kc
2 K12
(a) H2 + I2 2HI
28. Two gaseous equilibria
(b) N2 + 3H2 2 NH3
1 1 (c) N2 + O2 2NO
SO 2 (g)  O 2 (g) SO 2 (g)  O 2 (g) SO3(g)
2 2 (d) CO + H2O CO2 + H2
and
35. For the reaction H2(g) + I2(g) 2HI(g) at 721K the
2SO3(g) 2SO2(g) + O2(g) have equilibrium constants
value of equilibrium constant (Kc) is 50. When the
K1 and K2 respectively at 298 K. Which of the following
equilibrium concentration of both is 0.5M, the value of Kp
relationships between K1 and K2 is correct
under the same conditions will be
(a) K1 = K2 (b) K2 = K12
(a) 0.002 (b) 0.2
(c) K2 = 1/K12 (d) K2 = 1/K1
(c) 50.0 (d) 50 / RT
29. At a given temperature, the equilibrium constant for
36. The reaction between N2 and H2 to form ammonia has
reaction PCl5(g) PCl3(g) + Cl2(g) is 2.4 × 10–3. At the
same temperature, the equilibrium constant for reaction Kc = 6 × 10–2 at the temperature 500°C. The numerical
PCl3(g) + Cl2(g) PCl5(g) is value of Kp for this reaction is

(a) 2.4 × 10–3 (b) – 2.4 × 10–3 (a) 1.5 × 10–5 (b) 1.5 × 105
(c) 4.2 × 102 (d) 4.8 × 10–2 (c) 1.5 × 10–6 (d) 1.5 × 106
 16 CHEMICAL EQUILIBRIUM

37. For the reversible reaction, 42. 40% of a mixture of 0.2 mol of N2 and 0.6 mol of H2 reacts to
N2(g) + 3H2(g) 2NH3(g) give NH3 according to the equation :

at 500°C, the value of Kp is 1.44 × 10–5 when partial pressure N 2 (g)  3H 2 (g)  2NH 3 (g)
is measured in atmospheres. The corresponding value of
at constant temperature and pressure. Then the ratio of
Kc with concentration in mole litre-1, is the final volume to the initial volume of gases are
(a) 1.44 × 10–5/(0.082 × 500)–2 (a) 4 : 5 (b) 5 : 4
–5 –2 (c) 7 : 10 (d) 8 : 5
(b) 1.44 × 10 /(8.314 × 773)

(c) 1.44 × 10–5/(0.082 × 773)2 43. XY2 dissociates as :

–5 –2
(d) 1.44 × 10 /(0.082 × 773) XY2 (g)  XY(g)  Y(g)
Equilibrium : Analysis
Initial pressure of XY2 is 600 mm Hg. The total pressure at
38. A mixture of 0.3 mole of H2 and 0.3 mole of I2 is allowed to equilibrium is 800 mm Hg. Assuming volume of system to
react in a 10 litre evacuated flask at 500ºC. The reaction is remain constant, the value of Kp is
H2 + I 2 2HI, the K is found to be 64. The amount of
(a) 50 (b) 100
unreacted I2 at equilibrium is
(c) 200 (d) 400
(a) 0.15 mole (b) 0.06 mole
44. 15 mol of H2 and 5.2 moles of I2 are mixed and allowed to
(c) 0.03 mole (d) 0.2 mole
attain equilibrium at 500ºC. At equilibrium, the
39. 0.6 mole of NH3 in a reaction vessel of 2dm3 capacity was concentration of HI is found to be 10 mol. The equilibrium
brought to equilibrium. The vessel was then found to constant for the formation of HI is.
contain 0.15 mole of H2 formed by the reaction (a) 50 (b) 25
2NH3(g) N2(g) + 3H2(g) (c) 200 (d) 15

Which of the following statements is true 45. For the equilibrium AB (g)  A(g) + B(g). Kp is equal to
(a) 0.15 mole of the original NH3 had dissociated at four times the total pressure. Calculate the number moles
of A formed if one mol of AB is taken initially.
equilibrium
(b) 0.55 mole of ammonia is left in the vessel (a) 0.45 (b) 0.30
(c) 0.60 (d) 0.90
(c) At equilibrium the vessel contained 0.45 mole of N2

(d) The concentration of NH3 at equilibrium is 0.25 mole 46. I 2  I   I3

per dm3 This reaction is set-up in aqueous medium. We start with
–
40. 5 moles of SO2 and 5 moles of O2 are allowed to react to 1 mol of I2 and 0.5 mol of I in 1L flask. After equilibrium is
form SO3 in a closed vessel. At the equilibrium stage 60% reached, excess of AgNO3 gave 0.25 mol of yellow
of SO2 is used up. The total number of moles of SO2, O2 precipitate. Equilibrium constant is
and SO3 in the vessel now is (a) 1.33 (b) 2.66
(a) 10.0 (b) 8.5 (c) 2.00 (d) 3.00
(c) 10.5 (d) 3.9
47. One mole of N2O4(g) at 100 K is kept in a closed container
41. The equilibrium P4 (s) + 6 Cl2 (g)  4 PCl3(g) is attained

at 1.0 atm pressure. It is heated to 400 K, where 30% by
mass of N2O4(g) decomposes of NO2(g). The resultant
by mixing equal moles of P4 and Cl2 in an evacuated vessel.
pressure will be
Then at equilibrium
(a) 4.2 (b) 5.2
(a) [Cl2] > [PCl3] (b) [Cl2] > [P4]
(c) 3.2 (d) 6.2
(c) [P4] > [Cl2] (d) [PCl3] > [P4]
 17 CHEMICAL EQUILIBRIUM

Equilibrium Constant and G pressure in the flask rises to 0.84 atm. The equilibrium
48. Gº(HI;g)   1.7 kJ. What is the equilibrium constant constant for NH4HS decomposition at this temperature is

at 25ºC for 2HI(g) H2(g) + I2(g) (a) 0.30 (b) 0.18

(c) 0.17 (d) 0.11
(a) 24.0 (b) 3.9 55. Calculate the partial pressure of carbon monoxide from
(c) 2.0 (d) 0.5 the following
49. Calculate Gº for conversion of oxygen to ozone CaCO3 (s) CaO(s) + CO2 ; Kp = 8 × 10–2
3/2 O2(g)  O3(g) at 298 K, if Kp for this conversion is CO2(g) + C (s)  2CO (g) ; Kp = 2
2.47 × 10–29
(a) 0.2 (b) 0.4
(a) 163 kJ mol–1 (b) 2.4 × 102 kJ mol–1 (c) 1.6 (d) 4
(c) 1.63 kJ mol–1 (d) 2.38 × 106 kJ mol–1 56. Change in volume of the system does not alter the number
of moles in which of the following equilibrium
Homogeneneous and Heterogeneous Equilibria,
Degree of Dissociation (a) N2(g)+ O2(g) 2NO (g)

50. Pure ammonia is placed in a vessel at temperature where (b) PCl5 (g) PCl3 (g) + Cl2(g)
its dissociation (  ) is appreciable. At equilibrium (c) N2(g) + 3H2(g) 2NH3(g)
(a) Kp does not change significantly with pressure (d) SO2Cl2(g) SO2(g) + Cl2(g)
(b)  does not change with pressure 57. The equilibrium constant (K p ) for the reaction
(c) Concentration of NH3 does not change with pressure PCl5(g)  PCl3(g) + Cl2(g) is 16. If the volume of the
container is reduced to one half its original volume, the
(d) Concentration of H2 is less than that of N2
value of Kp for the reaction at the same temperature will be
51. At a certain temp. 2HI H2 + I2 Only 50% HI is (a) 32 (b) 64
dissociated at equilibrium. The equilibrium constant is (c) 16 (d) 4
(a) 0.25 (b) 1.0 58. Consider the following equilibrium in a closed container :
(c) 3.0 (d) 0.50 N2O4 (g)  2 NO2(g)
52. 3.2 moles of hydrogen iodide were heated in a sealed bulb At a fixed temperature, the volume of the reaction container
at 444°C till the equilibrium state was reached. Its degree is halved. For this change, which of the following
of dissociation at this temperature was found to be 22%. statements, holds true regarding the equilibrium constant
The number of moles of hydrogen iodide present at (Kp) and degree of dissociation () ?
equilibrium are (a) neither Kp nor  changes
(a) 2.496 (b) 1.87 (b) both Vp and  change
(c) 2 (d) 4
(c) Kp changes but  does not change
53. CaCO3 (s)  CaO(s)  CO2 (g) in closed container at (d) Kp does not change but  changes
equilibrium. What would be the effect of addition of CaCO3 59. Calculate the partial pressure of carbon monoxide from
on the equilibrium concentration of CO2. the following data :

(a) Increases (b) Decreases 

CaCO3 (s)   CaO (s)  CO 2 , Kp = 8 × 10–2
(c) Data is not sufficient (d) Remains unaffected
CO2(g) + C (s) 
 2 CO (g), Kp = 2
54. An amount of solid NH4HS is placed in a flask already
containing ammonia gas at a certain temperature and 0.50 (a) 0.2 (b) 0.4
atm. pressure. Ammonium hydrogen sulphide decomposes (c) 1.6 (d) 4
to yield NH3 and H2 S gases in the flask. When the
60. A small amount of NH4HS is placed in a flask already
decomposition reaction reaches equilibrium, the total
containing ammonia gas at a certain temperature and
0.50 atm pressure. Ammonium hydrogen sulphide
 18 CHEMICAL EQUILIBRIUM

decomposes to yield NH3 and H2S gases in the flask. When the observed molecular weight of N2O4 is 80 g mol–1 at 350
the decomposition reaction reaches equilibrium, the total K. The percentage of dissociation of N2O4 (g) at 350 K is
pressure in the flask rises to 0.84 atm. The equilibrium
constant for NH4HS decomposition at this temperature is (a) 10% (b) 15%

(a) 0.30 (b) 0.18 (c) 20% (d) 18%

(c) 0.17 (d) 0.11 Le Chatelier’s Principle

61. The vapour density of completely dissociated NH4Cl is 65. What is the effect of halving the pressure by doubling the
(a) double than that of NH4Cl volume on the following system at 500°C

(b) half than that of NH4Cl H2(g) + I2(g) 2HI(g)

(c) same as that of NH4Cl (a) Shift to product side
(d) determined by the amount of solid NH4Cl taken
(b) Shift to product formation
62. The following two equilibria exist simultaneously in a
closed vessel : (c) Liquifaction of HI

 PCl3(g) + Cl2 (g)

PCl5(g)  (d) No effect

66. In equilibrium CH3COOH + H2O CH3COO– + H+

 CO (g) + Cl2 (g)
COCl2 (g) 

If some CO is added into the vessel, then after the The equilibrium constant may change when
equilibrium is attained again, concentration of
(a) CH3COO– are added (b) CH3COOH is added
(a) PCl5 will increase (b) PCl5 wil decrease
(c) Catalyst is added (d) Mixture is heated
(c) PCl5 will remain unaffected
67. Which of the following statements regarding a chemical
(d) Cl2 will increase
equilibrium is wrong
63. The equilibrium constant (Kp) for the decomposition of
(a) An equilibrium can be shifted by altering the
gaseous H2O
temperature or pressure
1 (b) An equilibrium is dynamic
H2O (g)  H2 (g) + O (g)
2 2
(c) The same state of equilibrium is reached whether one
is related to degree of dissociation () at a total pressure starts with the reactants or the products
p, given by
(d) The forward reaction is favoured by the addition of a
3 1/ 2
p catalyst
(a) K p 
(1  ) (2   )1/ 2
68. In the reaction, A2(g) + 4 B2(g) 2AB4(g)

 3 p3 / 2 H  0 the formation of AB4 is will be favoured at

(b) K p 
(1   ) (2  )1/ 2
(a) Low temperature, high pressure
(b) High temperature, low pressure
3 / 2 p2
(c) K p 
(1   ) (2  )1/ 2 (c) Low temperature, low pressure
(d) High temperature, high pressure
 3 / 2 p1/ 2
(d) K p  69. The formation of SO 3 takes place according to
(1   ) (2  )1/ 2
the following reaction,
64. At the equilibrium of the reaction, 2SO2 + O2 2SO3 ; H = – 45.2 kcal
N2O4 (g)  2 NO2 (g),
 19 CHEMICAL EQUILIBRIUM

The formation of SO3 is favoured by (c) At low temperature and high pressure

(a) Increasing in temperature (d) At low temperature and low pressure

(b) Removal of oxygen 76. Following gaseous reaction is undergoing in a vessel

C2H4 + H2 C2H6; H = – 32.7 Kcal
(c) Increase of volume
(d) Increasing of pressure Which will increase the equilibrium concentration of C2H6

70. N2 + O2 2NO - Q cals (a) Increase of temperature

In the above reaction which is the essential condition for (b) By reducing temperature
the higher production of NO
(c) By removing some hydrogen
(a) High temperature (b) High pressure
(c) Low temperature (d) Low pressure (d) By adding some C2H6
71. Which of the following reactions proceed at low pressure 77. The effect of increasing the pressure on the equilibrium
(a) N2 + 3H2 2NH3 (b) H2 + I2 2HI 2A + 3B 3A + 2B is

(c) PCl5 PCl3 + Cl2 (d) N2 + O2 2NO (a) Forward reaction is favoured

72. In the following reversible reaction (b) Backward reaction is favoured

2SO2 + O2 2SO3 + Q Cal (c) No effect

(d) None of the above
Most suitable condition for the higher production of SO3
is 78. The exothermic formation of ClF3 is represented by the
(a) High temperature and high pressure equation
(b) High temperature and low pressure Cl2(g) + 3F2(g) 2ClF3(g); H = – 329 kJ
(c) Low temperature and high pressure
Which of the following will increase the quantity of ClF3
(d) Low temperature and low pressure
in an equilibrium mixture of Cl2, F2 and ClF3
73. The reaction A + B C + D +heat has reached
equilibrium. The reaction may be made to proceed (a) Increasing the temperature
forward by
(b) Removing Cl2
(a) Adding more C
(c) Increasing the volume of the container
(b) Adding more D
(c) Decreasing the temperature (d) Adding F2
(d) Increasing the temperature 79. In which of the following system, doubling the volume of
74. According to Le-chatelier principle, if heat is given to solid- the container cause a shift to the right
liquid system, then (a) H2(g) + Cl2(g) 2HCl(g)
(a) Quantity of solid will reduce
(b) 2CO(g) + O2(g) 2CO2(g)
(b) Quantity of liquid will reduce
(c) Increase in temperature (c) N2(g) + 3H2(g) 2NH3(g)

(d) Decrease in temperature (d) PCl5(g) PCl3(g) + Cl2(g)

75. In the reaction A(g) + 2B(g) C(g) + Q kJ, greater 80. Which of the following information can be obtained on
product will be obtained or the forward reaction is favoured the basis of Le-chatelier’s principle
by (a) Entropy change in a reaction
(a) At high temperature and high pressure (b) Dissociation constant of a weak acid
(b) At high temperature and low pressure (c) Equilibrium constant of a chemical reaction
 20 CHEMICAL EQUILIBRIUM

(d) Shift in equilibrium position on changing value of a 84. The yield of product in the reaction
constant
A2(g)+ 2B(g) C(g) + Q.kJ. would be high at
81. The equilibrium SO2Cl2 (g) SO2(g) + Cl2(g) is attained
(a) High temperature and high pressure
at 25°C in a closed container and an inert gas helium is
introduced which of the following statement is correct (b) High temperature and low pressure

(a) More chlorine is formed (c) Low temperature and high pressure
(d) Low temperature and low pressure
(b) Concentration of SO2 is reduced

(c) More SO2Cl2 is formed

(d) Concentration of SO2Cl2(SO2) and Cl2 does not change

82. H2(g) + I2(g) 2HI(g) H = + q cal, then formation of HI

(a) Is favoured by lowering the temperature
(b) Is favoured by increasing the pressure
(c) Is unaffected by change in pressure
(d) Is unaffected by change in temperature
83. The formation of nitric oxide by contact process
N2 + O2 2NO. H = 43.200 kcal is favoured by
(a) Low temperature and low pressure
(b) Low temperature and high pressure
(c) High temperature and high pressure
(d) High temperature and excess reactants concentration
 21 CHEMICAL EQUILIBRIUM

EXERCISE - 2 : PREVIOUS YEAR JEE MAINS QUESTION

1. In which of the following equilibrium change in the volume 6. What is the equilibrium expression for the reaction
of the system does not alter the number of moles (2002) (2004)

(a) N2(g) + O2 (g) 2NO (g) P4 (s) + 5O2 (g) P4O10 (s) ?

(b) PCl5 (g) PCl3 (g) + Cl2 (g) [P4 O10 ] 1

(a) K c  5 (b) K c 
(c) N2 (g) + 3H2 (g) 2NH3 (g) [ P4 ] [O 2 ] [O 2 ]5

(d) SO2Cl2 SO2 (g) + Cl2 (g) [P4 O10 ]

(c) Kc = [O2]5 (d) K c  5 [P ] [O ]
2. For the reaction (2002) 4 2

1 7. For the reaction (2004)

CO (g) + O (g) CO2 (g), Kp/Kc is
2 2 CO(g) + Cl2 (g) COCl2 (g),
(a) RT (b) (RT)–1
Kp
(c) (RT)–1/2 (d) (RT)1/2 the
Kc
is equal to
3. In which of the following reactions, increase in the pressure
at constant temperature does not affect the moles at 1
equilibrium (2002) (a) (b) 1.0
RT
(a) 2NH3(g) N2(g) + 3H2(g)
(c) RT (d) RT
(b) C(g) + 1/2O2(g) CO(g)
8. The equilibrium constant for the reaction
(c) H2(g) + 1/2O2(g) H2O(g)
N2(g) + O2(g) 2NO(g)
(d) H2(g) + I2(g) 2HI(g)
at temperature T is 4 × 10–4. The value of Kc for the reaction
4. For the reaction equilibrium
N2O4 (g) 2NO2 (g) 1 1
NO2(g) N2(g) + O2(g)
2 2
the concentrations of N2O4 and NO2 at equilibrium are
4.8 × 10–2 and 1.2 × 10–2 mol L–1 respectively. The value of at the same temperature is (2004)
Kc for the reaction is (2003) (a) 2.5 × 102 (b) 0.02
3 –1 2 –1
(a) 3 × 10 mol L (b) 3.3 × 10 mol L (c) 4 × 10–4 (d) 50
–1 –1 –3 –1
(c) 3 × 10 mol L (d) 3 × 10 mol L 9. A small amount of NH4HS is placed in a flask already
5. The conditions favourable for the reaction containing ammonia gas at a certain temperature and 0.50
atm pressure. Ammonium hydrogen sulphide decomposes
2SO2(g) + O2(g) 2SO3(g); Hº = – 198 kJ to yield NH3 and H2S gases in the flask. When the
are (2003) decomposition reaction reaches equilibrium, the total
pressure in the flask rises to 0.84 atm. The equilibrium
(a) Low temperature, high pressure
constant for NH4HS decomposition at this temperature is
(b) Any value of T and P (2005)
(c) Low temperature and low pressure (a) 0.30 (b) 0.18
(d) High temperature and high pressure
(c) 0.17 (d) 0.11
 22 CHEMICAL EQUILIBRIUM

10. For the reaction 15. A vessel at 1000 K contains CO2 with a pressure of 0.5 atm.
2NO2(g) 2NO (g) + O2(g) Some of the CO2 is converted into CO on the addition of
–6 graphite. If the total pressure at equilibrium is 0.8 atm, the
(Kc = 1.8 × 10 at 184ºC)
value of Kp is (2011)
(R = 0.0831 kJ/(mol.K)
(a) 1.8 atm (b) 3 atm
When Kp and Kc are compared at 184ºC it is found that
(c) 0.3 atm (d) 0.18 atm
(2005) 1
(a) Whether Kp is greater than, less than or equal of Kc 16. For the reaction SO2(g)  O2(g)  SO3(g) , if
2
depends upon the total gas pressure Kp = KC(RT)x where the symbols have usual meaning then
(b) Kp = Kc
the value of x is :
(c) Kp is greater than Kc
(d) Kp is greater than Kc (assuming ideality) (2014)
11. Phosphourus pentachloride dissociates as follows, in a
closed reaction vessel,
1 1
PCl5 (g) PCl3(g) + Cl2(g) (2006) (a)  (b)
2 2
If total pressure at equilibrium of the reaction mixture is P
(c) 1 (d) –1
and degree of dissociation of PCl5 is x, the partial pressure
of PCl3 will be 17. The standard Gibbs energy change at 300 K for the
 x   2x  reaction 2A  B + C is 2494.2 J. At a given time, the
(a)  P (b)  P
 x 1 1 x  1
composition of the reaction mixture is [A] = , [B] = 2
1 2
 x   x 
(c)  P (d)  P and [C]= . The reaction proceeds in the : (2015)
 x 1  1 x  2
12. The equilibrium constant for the reaction [R = 8.314 J/K/mol, e = 2.718]

1 (a) forward direction because Q < KC

SO3(g) SO2(g) + O (g)
2 2 (b) reverse direction because Q < KC
is KC = 4.9 × 10–2. The value of KC for the reaction
2SO2 + O2(g) 2SO3(g) will be (2006) (c) forward direction because Q > KC
(a) 416 (b) 2.40 × 10–3 (d) reverse direction because Q > KC
(c) 9.8 × 10–2 (d) 4.9 × 10–2
18. The equilibrium constant at 298 K for reaction
13. The equilibrium constants K p and K p for the reactions
1 2
A + B  C + D is 100. If the initial concentration of all the
X 2Y and Z P + Q, respectively are in the ratio
of 1 : 9. If the degree of dissociation of X and Z be equal four species were 1M each, then equilibrium concentration
then the ratio of total pressure at these equilibria is of D (in mol L–1) will be: (2016)
(2008)
(a) 1 : 36 (b) 1 : 1 (a) 0.818 (b) 1.818
(c) 1 : 3 (d) 1 : 9
14. For the following three reactions 1, 2 and 3 equilibrium (c) 1.182 (d) 0.182
constants are given 19. An aqueous solution contains 0.10 M H2S and 0.20 M
(1) CO(g) + H2O(g) CO2(g) + H2(g); K1
HCl. If the equilibrium constants for the formation of
(2) CH4(g) + H2O(g) CO(g) + 3H2(g); K2
HS– from H2S is 1.0 × 10–7 and that of S2– from HS– ions is
(3) CH4(g) + 2H2O(g) CO2(g) + 4H2(g); K3
Which of the following relations is correct ? (2008) 1.2 × 10–13 then the concentration of S2– ions in aqueous
(a) K 1 K 2  K 3 (b) K 2 K 3  K1 solution is: (2018)
(a) 5 × 10–19 (b) 5 × 10–8
(c) K3 = K1K2 (d) K3 . K 32 K12
(c) 3 × 10–20 (d) 6 × 10–21
 23 CHEMICAL EQUILIBRIUM

JEE MAINS ONLINE QUESTION 6. A solid XY kept in an evacuated sealed container

undergoes decomposition to form a mixture of gases X
1. At a certain temperature, only 50% HI is dissociated into and Y at temperature T. The equilibrium pressure is 10 bar
H2 and I2 at equilibrium. The equilibrium constant is: in this vessel. Kp for this reaction is :
Online 2014 SET (1) Online 2016 SET (2)
(a) 1.0 (b) 3.0 (a) 5 (b) 10
(c) 0.5 (d) 0.25 (c) 25 (d) 100
2. What happens when an inert gas is added to an equilibrium 7. The following reaction occurs in the Blast Furnace where
keeping volume unchanged? Online 2014 SET (3) iron ore is reduced to iron metal :
(a) More reactant will form Fe2O3 (s)  3CO(g)  2Fe(l)  3 CO2 (g)
(b) More product will form
Using the Le Chatelier’s principle, predict which one of
(c) Equilibrium will remain unchanged the following will not disturb the equilibrium ?
(d) Less product will form Online 2017 SET (2)
3. For the decomposition of the compound represented as (a) Removal of CO (b) Removal of CO2

NH2 COONH4  s   2NH3  g   CO2  g  (c) Addition of CO2 (d) Addition of Fe2O3
8. In which of the following reactions, an increase in the
The Kp = 2.9 × 10–5 atm3.
volume of the container will favour the formation of
If the reaction is started with 1 mol of the compound, the products ? Online 2018 SET (1)
total pressure at equilibrium would be :
(a) 2NO2  g   2NO  g  + O2  g 
Online 2014 SET (4)
(a) 5.82 × 10–2 atm (b) 7.66 × 10–2 atm (b) H2  g  + I2  g   2HI  g 
(c) 38.8 × 10–2 atm (d) 1.94 × 10–2 atm
(c) 4NH3  g  + 5O2  g   4NO  g  + 6H2 O  l 
4. 
The increase of pressure on ice  water system at
(d) 3O2  g   2O3  g 
constant temperature will lead to :
Online 2015 SET (1) 9. At a certain temperature in a 5L vessel, 2 moles of carbon
monoxide and 3 moles of chlorine were allowed to reach
(a) a decrease in the entropy of the system equilibrium according to the reaction,
(b)an increase in the Gibbs energy of the system

CO + Cl2  COCl2
(c)no effects on the equilibrium
(d)a shift of the equilibrium in the forward direction At equilibrium, if one mole of CO is present then
equilibrium constant (Kc) for the reaction is :
5. 
For the equilibrium, A(g)  B(g), H is 40 kJ/mol. Online 2018 SET (2)
If the ratio of the activation energies of the forward (Ef) (a) 2 (b) 2.5
2 (c) 3 (d) 4
and reverse (Eb) reactions is then :
3
10. The gas phase reaction 2NO 2(g)  N 2 O 4(g) is an
Online 2015 SET (1) exothermic reaction. The decomposition of N2O4, in
(a) Ef = 80 kJ/mol; Eb = 120 kJ/mol equilibrium mixture of NO2(g) and N2O4(g), can be
increased by : Online 2018 SET (3)
(b) Ef = 60 kJ/mol; Eb = 100 kJ/mol
(a) lowering the temperature.
(c) Ef = 30 kJ/mol; Eb = 70 kJ/mol
(b) increasing the pressure.
(d) Ef = 70 kJ/mol; Eb = 30 kJ/mol (c) addition of an inert gas at constant volume.
(d) addition of an inert gas at constant pressure.
 24 CHEMICAL EQUILIBRIUM

EXERCISE - 3 : ADVANCED OBJECTIVE QUESTIONS

1. All questions marked “S” are single choice questions
2. All questions marked “M” are multiple choice questions
3. All questions marked “C” are comprehension based questions
4. All questions marked “A” are assertion–reason type questions
(A) If both assertion and reason are correct and reason is the correct explanation of assertion.
(B) If both assertion and reason are true but reason is not the correct explanation of assertion.
(C) If assertion is true but reason is false.
(D) If reason is true but assertion is false.
5. All questions marked “X” are matrix–match type questions
6. All questions marked “I” are integer type questions

Equilibrium : Definition and Expression 4. (S) For a reversible reaction : A + B C

1. (A) Assertion : For a reaction at equilibrium, the free energy

 dx 
  = 2.0 × 103 L mol–1 s–1 [A] [B] – 1.0 × 102 s–1 [C]
for the reaction is minimum.  dt 
Reason : The free energy for both reactants and
where x is the amount of ‘A’ dissociated. The value of
products decreases and become equal. equilibrium constant (Keq) is :
(a) A (b) B (a) 10 (b) 0.05
(c) C (d) D (c) 20 (d) Can’t be calculated

2. (A) Assertion : Chemical equilibrium represents a state of a 5. (A) Assertion : The reaction quotient, Q has the same form
as the equilibrium constant Keq and is evaluated using
reversible reaction in which measurable properties of
any given concentrations of the species involved in the
the system (pressure, concentration, colour etc.) reaction, and not necessarily equilibrium concentrations.
become constant under the given set of conditions.
Reason : If the numerical value of Q is not the same as
Reason : The chemical equilibrium is an apparent state the value of equilibrium constant, a reaction will proceed.
of rest in which two opposing reactions are proceeding
(a) A (b) B
at the same rate.
(c) C (d) D
(a) A (b) B
6. (A) Assertion : The active mass of pure solids and pure
(c) C (d) D liquids is taken unity.

3. (S) Which of the following statements about the reaction Reason : The active mass of pure solids and liquids
quotient, Q are correct ? depends on density and molecular mass. The density
and molecular mass of pure liquids and solids are
(a) the reaction quotient, Q and the equilibrium constant
constant.
always have the same numerical value

(b) Q may be lesser than, equal to or greater than Keq (a) A (b) B

(c) Q (numerical value) varies as reaction proceeds (c) C (d) D

(d) Q = 1 at equilibrium
 25 CHEMICAL EQUILIBRIUM

7. (A) Assertion : If some PCl 5 (g) containing labelled 11. (S) Equilibrium constant Kc for the following reaction at
phosphorus p31 is added to a system with following 800K is, 4.
equilibrium, after sometime the system was found to
1 3
contain radioactive PCl3. NH3 (g)  N 2 (g)  H 2 (g)
2 2
PCl5(g) PCl3(g) + Cl2(g)
The value of kp for the following reaction will be :
Reason : Chemical equilibrium is dynamic in nature.
N 2 (g)  3H 2 (g)  2NH 3 (g)
(a) A (b) B
(c) C (d) D 2
 800R 
(a)   (b) 16 × (800R)2
8. (A) Assertion : As a reversible system approaches  4 
equilibrium, entropy of the system increases.
2
Reason : The state of equilibrium is the most disordered  1 
state of a reversible system. (c)   (d) (800R)1/2 4
 4  800R 
(a) A (b) B
Equilibrium : Analysis
(c) C (d) D
12. (S) N 2O 4 2NO2, Kc = 4. This reversible reaction is
1 1 studied graphically as shown in the given figure. Select
9. (M) N 2 O2  2KO K1 ;   N 2    O2  NO K 2
2 2 the correct statement out of I, II and III.
I : Reaction quotient has maximum value at point A
II : Reaction proceeds left to right at a point when [N2O4]
1 1
2NO  N 2  O 2 K 3 ; NO    N 2    O 2 K 4 = [NO2] = 0.1 M
2 2
III : Kc = Q when point D or F is reached :
Correct relation(s) between K1, K2, K3 and K4 is/are :
A
(a) K2 × K4 = 1 (b) K1  K 4  1 D E
NO2
Concentration

(c) K3  K 2  1 (d) K3  K 2  1
C
N2O4
Kp and KC F G

10. (X) Match the following systems with their K p /K c

relationship B Time

Equilibrium types Kp/Kc (a) I, II (b) II, III

relationship (c) II (d) I, II, III

(a) NO(g)  NO 3 (g)  2NO 2 (g) (p)Kp > Kc 13. (S) I2 + I– I3

This reaction is set-up in aqueous medium. We start

(b) N 2 (g)  3H 2 (g)  2NH 3 (g) (q) Kp= Kc (RT)2
with 1 mol of I2 and 0.5 mol of I– in 1L flask. After
equilibrium is reached, excess of AgNO3 gave 0.25 mol
(c) 2O 3 (g)  3O 2 (g) (r) Kp= Kc
of yellow ppt. Equilibrium constant is : [Given : AgNO3
gives yellow ppt with I–]
1 5
(d) BrF5 (g)  Br2 (g)  F2 (g) (s) Kp< Kc
2 2 (a) 1.33 (b) 2.66
(c) 2.00 (d) 3.00
 26 CHEMICAL EQUILIBRIUM

14. (I) Given the hypothetical reaction : respectively, what is the molarity of HBr ?
–2 –1
2A(s) + nB(g)  3C(g) Kp = 0.0105 (a) 1.8 × 10 M (b) 6.7 × 10 M
0 1
(c) 1.5 × 10 M (d) 3.6 × 10 M
and Kc = 0.45 at 250ºC. What is the value of coefficient
‘n’ ? 21. (S) For the all gas reaction at 1000 K : 2HI  H2 + I2,
15. (S) In the reaction : A + B  2C + D. The initial K = 0.0344. If you were to begin with 8.0 M of HI in a
fixed volume container, what would be the equilibrium
concentration of A and B are 1M each. The value of Kc
8 concentration of H2 ?
is 10 . What is the equilibrium concentration of A ?
–4 4
(a) 1.10 M (b) 0.48 M
(a) 2 × 10 M (b) 2 × 10 M
(c) 5.8 M (d) 2.92 M
(c) 0.005 M (d) 0.0025 M
22. (S) 
In reversible reaction A 
1
 k
 B , the initial
16. (S) Equilibrium constant for two complexes are : k 2

37 concentration of A and B are a and b in moles per litre

A : K4 [Fe(CN)6] 2.6 × 10 (for dissociation)
17
and the equilibrium concentration are (a – x) and (b – x)
B : K3 [Fe(CN)6] 1.9 × 10 (for dissociation) respectively ; express x in terms of k1, k2, a and b.
(a) A and B are equally stable
k1a  k 2 b k1a  k 2 b
(b) A is more stable than A (a) (b)
k1  k 2 k1  k 2
(c) B is more stable than A
(d) the predictable stability k1a  k 2 b k1a  k 2 b
(c) (d)
17. (S)
–
For the reaction, [Ag(CN)2]  Ag + 2CN , the
+ – k1k 2 k1  k 2
–19 +
equilibrium constant Kc at 25ºC is 4 × 10 ; then Ag
Equilibrium Constant and G
concentration in a solution which has 0.1 M KCN and
0.03M AgNO3 is : 23. (S) If for the heterogeneous equilibrium

(a) 7.5 × 10
18
(b) 7.5 × 10
–18
CaCO3(s)  CaO(s) + CO2 (g) ; K = 1 at 1 atm,
19 –19
(c) 7.5 × 10 (d) 7.5 × 10 the temperature is given by :

18. (S) A vessel at 1000 K contains CO2 with a pressure of Sº Hº
0.5 atm. Some of the CO2 is converted to CO on addition (a) T  (b) T 
Hº Sº
of graphite. If the total pressure at equilibrium is 0.8 atm,
the value of K is :
Gº Gº
(c) T  (d) T 
(a) 0.18 atm (b) 1.8 atm R Hº
(c) 3 atm (d) 0.3 atm 24. (X) Match the Column-I with Column-II :
19. (S) The equilibrium reaction : 2AB(aq)  2A(aq) + B2(g) Column-I Column-II
has an equilibrium constant equal to 1.28. If the (Equations) (Type of process)
concentrations of AB and A are 5 mol/L and 4 mol/L
(a) Kp > Q (p) Non spontaneous
respectively, what is [B2] ?
(b) Gº < RT loge Q (q) Equilibrium
(a) 0.50 M (b) 1.60 M
(c) Kp = Q (r) Spontaneous and
(c) 2.00 M (d) 2.84 M
endothermic
20. (S) Consider the reaction NaBr(aq) + H 2 SO 4(aq) 
NaHSO4(aq) + HBr(aq). The equilibrium constant is H
–2 (d) T  (s) Spontaneous
8.3 × 10 . If the equilibrium concentrations of NaBr, S
H2SO4 and NaHSO4 are 6.0 M, 9.0 M and 3.0 M
 27 CHEMICAL EQUILIBRIUM

Passage (For Questions 25 to 27) 26. (C) For exothermic reaction is Sº < 0, then the sketch of log
Effect of temperature on the equilibrium process is K vs 1/T may be
analyzed by using the thermodynamics. From the
thermodynamics relation.
Gº = – 2.303 RT logK ...(i)
Gº : Standard free energy change log k
Gº = Hº – TSº ...(ii)
(a)
Hº : Standard heat of the reaction
From (i) and (ii)
1/T
–2.303 RT log K = Hº – Sº
Sº : Standard entropy change

Hº Sº
 logK    ...(iii)
2.303RT 2.303R log k
If a plot of log K vs 1/T is made then it is a straight line
(b)
Hº Sº
having slope  and Y intercept 
2.303R 2.303R
1/T
If at temperature T1, equilibrium constant be K1 and at
temperature T2, equilibrium constant be K2 then the
above equation reduces to :

Hº Sº
 log K1   2.303RT  2.303R log k
1

(c)
Hº Sº
 log K 2   2.303RT  2.303R
2 1/T
Substracting (iv) from (v) we get.

K2 Hº  1 1 
 log K  2.303R  T  T 
1  1 2 
log k
From the above relation we can conclude that the value
of equilibrium constant increases with increase in (d)
temperature for an endothermic reaction and the same
decreases with the increase in temperature for an 1/T
exothermic reaction. Answer the following three
questions based on the above information.
27. (C) If for a particular reversible reaction : Kc = 57 at 355ºC
25. (C) If standard heat of dissociation of PCl5 is 230 cal, then and Kc = 69 at 450º, then
1 (a) H < 0
slope of the graph of log k vs is
T (b) H > 0
(a) +50 (b) –50 (c) H = 0
(c) 10 (d) None of these (d) Sign of H can’t be determined
 28 CHEMICAL EQUILIBRIUM

28. (M) Variation of equilibrium constant K for the reaction

 d log e K  H
2A(s)  B(g)  C(g)  2D(g) (b)   
 dT P RT
is plotted against absolute temperature T in figure as :
ln K Vs (1/T)
RT
(c) loge K = Constant 
H

H
(d) loge K = Constant 
ln K RT

Homogeneneous and Heterogeneous Equilibria,

Degree of Dissociation
1/T
32. (S) Volume of the flask in which the following equilibria are
ln K vs 1/T separately established are transferred to a flask that is
(a) the forward reaction is exothermic double the size of the earlier flask. In which of the
(b) the forward reaction is endothermic following cases, equilibrium constants are affected ?
(c) the slope of line is proportional to H
(a) N 2  3H 2 2 NH 3 , exothermic
(d) adding ‘A’ favours forward reaction (g ) (g ) (g)

29. (M) Which is/are correct ?

(b) N 2  O 2 2 NO, endothermic
(g ) (g ) (g )
Hº Sº
(a) 2.303 log K   
RT R
(c) PCl5 PCl 3  Cl 2 , endothermic
(b) Gº = – 2.303 RT log K (g) (g ) (g)

Hº Sº (d) none of these

(c) –2.303 log K   
RT 2 R 33. (S) In each of the following, total pressure set-up at
equilibrium is assumed to be equal and is one atm with
1
(d) 2.303 log K  (Hº Sº ) equilibrium constants KP given :
RT
–1 I : CaCO3 (s) CaO (s) + CO2 (g), K1
30. (S) The free energy of formation of NO is 78 kJ mol at the
temperature of an automobile engine (1000 K). What is II : NH4HS (s) NH3 (g) + H2S (g), K2
the equilibrium constant for this reaction at this reaction
at 1000 K ? III : NH2COONH4 (s) 2NH3 (g) + CO2 (g), K3

1 1 In the increasing order :

N 2 (g)  O2 (g)  NO(g)
2 2
–5 –9
(a) K1 = K2 = K3 (b) K1 < K2 < K3
(a) 8.4 × 10 (b) 7.1 × 10
–10 –19
(c) K3 < K2 < K1 (d) None of these
(c) 4.2 × 10 (d) 1.7 × 10
34. (S) During thermal dissociation, the observed vapour
31. (M) The variation of equilibrium constant K with temperature
is represented by : density of N2O4 (g) is 26.0. The extent of dissociation of
N2O4 (g) is :
H T2  1 
(a) log e K 2  log e K1     dT
R T1  T 
(a) 50% (b) 87%
(c) 77% (d) 23%
 29 CHEMICAL EQUILIBRIUM

35. (S) For the reaction N2O4 (g) 2NO2 (g), the value of Kp 38. (I) For the equilibrium AB(g)  A(g) + B(g), at a given
3 4
is 1.7 × 10 at 500 K and 1.78 × 10 at 600 K. Which of the
1 P
following is correct ? temperature rd of AB is dissociated, then will
3 Kp
I. The proportion of NO2 in the equilibrium mixture is
be numerically equal to _____.
increased by decreasing the pressure
39. (I) SO2Cl2 and Cl2 are introduced into a 3L vessel. Partial
II. The standard enthalpy change for the forward
reaction is negative pressure of SO2Cl2 and Cl2 at equilibrium are 1 atm and
2 atm respectively. The value of Kp for the following
III. units of Kp are atm reaction

IV. at 500 K, the degree of dissociation N2O4 decreases SO2Cl2(g)  SO2(g) + Cl2(g) is 10.
by 50% by increasing the pressure by 100%.
The total pressure in atm at equilibrium would be ____.
The correct choice is :
40. (I) What weight of solid ammonium carbamate
(a) I, III (b) I
(NH2COONH4) when vaporised at 200ºC will have a
(c) II, IV (d) III
volume of 8.96 litre at 1 atm ? Assume that solid
36. (S) Consider the equilibrium completely decomposes into CO2 and NH3 at 200ºC and
1 atm.
1
CO2  CO(g)  O2 (g) 41. (A) Assertion : The dissociation of CaCO 3 can be
2
represented as, CaCO3(s)  CaO(s) + CO2(g). Some
The equilibrium constant K is given by (when  <<< 1) : solid CaCO3 is placed in an evacuated vessel enclosed
by a piston and heated so that a portion of it is
3/ 2 3 decomposed. If the piston is moved so that the volume
(a) K  (b) K  of the vessel is doubled, while the temperature is held
2 2
constant, the number of moles of CO2 in the vessel
increases.
 3/ 2 3/ 2
(c) K  (d) K  Reason : The pressure of CO2 in the vessel will remain
2 3
the same.
37. (X) Match the Column-I with Column-II :
Passage : For Questions (42 to 44)
Column-I Column-II
These 3 questions deal with the following chemical
(Reaction) (Effect on equilibrium) reaction:

(A) N2(g) +3H2(g)  2NH3 (q) Forward shift by lowering of

Ni 2 (aq)  6NH3 (aq)  [Ni(NH3 )6 ]2 (aq)
(green solution) (blue solution)
H = –ve temperature

(B) N2(g) + O2(g)  2NO(g) (q) Forward shift by rise in When H+(aq) is added, the colour green is favoured.
Use one or more of the following interpretations to
H = +ve temperature answer the questions.

(c) PCl5(g)  PCl3(g)+Cl2(g) (r) No effect of pressure I. Some unreacted Ni2+ (aq) is present in the solution
at equilibrium.
H = +ve change
II. Some unreacted NH3 (aq) is present in the solution
(d) 2SO2(g)+O2(g)  2SO3(g) (s) Forward shift by rise in
at equilibrium.
H = –ve pressure
 30 CHEMICAL EQUILIBRIUM

III. The colour change indicates new equilibrium 46. (C) The deepening of colour on addition of KSCN supports
conditions with reduced [Ni(NH3)6]2+(aq).
(a) A only (b) A and D only
IV. The colour change indicates new equilibrium
(c) A and B only (d) B and D only
conditions with increased [Ni(NH3)6]2+(aq).
47. (C) The disappearance of colour on addition of Na2HPO4
42. (C) The deepening colour on dissolving more Ni(NO3)2
supports
supports interpretation(s)
(a) I only (b) I and IV only (a) A only (b) A and D only

(c) II and IV only (d) I and II only (c) A and B only (d) C only

43. (C) The deepening colour on addition of more NH3(aq) 48. (M) An industrial fuel, ‘water gas’ which consists of a mixture
supports intepretation(s) of H2 and CO can be made by passing steam over red-
hot carbon. The reaction is
(a) I only (b) I and IV only
(c) I and II only (d) II and IV only C(s) + H2O(g)  CO(g) + H2(g) ; H = + 131 kJ

44. (C) The disappearance of colour on addition of H+ (aq) The yield of CO and H2 at equilibrium would be shifted
supports interpretation(s) to the product side by
(a) I only (b) II and IV only (a) raising the relative pressure of steam
(c) I and II only (d) III only (b) adding hot carbon
Passage : For Questions (45 to 47) (c) raising the temperature
These 3 questions refer to the following experiment.
(d) reducing the volume of the system
Some Fe(NO3)3 solution is added to KSCN solution and
a dark red colour appears. This colour is caused by 49. (S) For the reaction, N2O4(g)  2NO2(g) ; if percentage
FeSCN2+, which is formed by the reaction : dissociation of N2O4 are 25%, 50%, 75% and 100%, then
the sequence of observed vapour densities will be :
Fe (aq) + SCN (aq)  FeCN (aq).
3+ – 2+

(a) d1 > d2 > d3 > d4 (b) d4 > d3 > d2 > d1

Experiments show this colour becomes deeper upon
addition of more Fe(NO3 )3 or KSCN. The colour (c) d1 = d2 = d3 = d4 (d) (d1 = d2) > (d3 = d4)
disappears when Na2HPO4 is added. Use one or more
of the interpretations below. 50. (S) The equilibrium constant for the decomposition of water,

(a) Unreacted Fe 3+ (aq) is present in the original 1

 
equilibrium mixture.  H 2 O(g)  H 2 (g)  4 O 2 (g) 
 
(b) Unreacted SCN– (aq) is present in the original
equilibrium mixture. is given by :

(c) Colour change indicates a new equilibrium ;

 3 p1/ 2
[FeSCN2+ (aq)] has been reduced. (a) K 
(1  )(2  )1/ 2
(d) Colour change indicates a new equilibrium ;
[FeSCN2+ (aq)] has been increased.  3/ 2 p1/ 2
(b) K 
45. (C) The deepening of colour on addition of more Fe(NO3)3 (1  )(2  )1/ 2
supports
(a) A only (b) A and D only 3 p1/ 2 3 p3/ 2
(c) K  (d) K 
(c) A and B only (d) B and D only 2 (1  )(2  )1/ 2
 31 CHEMICAL EQUILIBRIUM

51. (S) The equilibrium constants K p1 and K p2 for the 56. (M) Yield of NH3 in Haber’s process

reactions X  2Y and Z  P  Q ; respectively are N 2(g )  3H 2(g ) 2NH3(g), H = – 22 kcal;

in the ratio of 1 : 9. If the degree of dissociation of X and
can be increased by
Z be equal, then the ratio of total pressures at these
equilibria is : (a) compressing the reaction system
(a) 1 : 9 (b) 1 : 36 (b) raising the temperature
(c) 1 : 1 (d) 1 : 3 (c) decreasing the temperature
52. (S) In the preparation of CaO from CaCO3 using the
(d) using the catalyst to lower down the activation
equilibrium, CaCO3 (s)  CaO(s)  CO 2 (g), energy
(At 1 atm) 57. (M) The volume of the reaction flask is reduced to half of
its initial value, temperature being constant. In which
8500
Kp is expressed as log Kp = 7.282  . of the following cases the position of the equilibrium
T would shift ?
For complete decomposition of CaCO3 the temperature
(a) NH4HS(s) NH3(g) + H2S(s)
is celsius to be used is :
(a) 1167 (b) 894 (b) 2NOCl(g) 2NO(g) + Cl2(g)
(c) 8500 (d) 850
(c) CO(g) + H2O(g) CO2(g) + H2(g)
Le Chatelier’s Principle
(d) I2(g) 2I(g)
53. (A) Assertion : For the reaction
58. (M) KNO3(s) dissociates on heating as :

A  g   B g   C  g   D g 
at the given temperature, there will be no effect by 1
KNO3(s) KNO2(s) + O 2( g )
addition of inert gas either at constant pressure or at 2
constant volume.
At equilibrium in a closed container
Reason : For the reaction where n = 0, there is no
effect of inert gas either at constant volume or at (a) addition of NaNO3(s) favours forward reaction
constant pressure because Kp becomes purely a number.
(b) addition of KNO2(s) favours reverse reaction
(a) A (b) B
(c) C (d) D (c) increasing temperature favours forward reaction
54. (A) Assertion : Addition of an inert gas at constant pressure (d) decreasing pressure favours forward reaction
equilibrium will support the dissociation of PCl5 at the
59. (M) The dissociation of phosgene, which occurs according
same temperature.
to the reaction :
Reason : The addition of an inert gas will tend to increase
the total pressure. COCl2(g) CO(g) + Cl2(g)
(a) A (b) B
is an endothermic process. Which of the following factors
(c) C (d) D
55. (A) Assertion : The addition of an inert gas under constant will increase the degree of dissociation of COCl2 ?
volume condition cause the total pressure of the system
(a) Adding Cl2 to the system
to increase. This would thus lower the degree of
(b) Adding helium to the system at constant pressure
dissociation of PCl5.
Reason : Addition of inert gas at equilibrium increase (c) Decreasing the temperature of the system
the kinetic energy of molecules. (d) Reducing the total pressure
(a) A (b) B
(c) C (d) D
 32 CHEMICAL EQUILIBRIUM

60. (M) The dissociation of ammonium carbamate may be 64. (S) To the system H2 (g) + I2 (g) 2HI (g)
represented by the equation
in equilibrium, some N2 gas was added at constant
NH4CO2NH2(s) 2NH3(g) + CO2(g) volume. Then,

H° for the forward reaction is negative. The equilibrium (a) Kp will remain constant and Kc will change
will shift from right to left if there is
(b) Kc will remain constant and Kp will change
(a) a decrease in pressure
(c) Both Kp and Kc will remain constant
(b) an increase in temperature
(d) Both Kp and Kc will change
(c) an increase in the concentration of ammonia
65. (S) In a 1.0 L aqueous solution when the reaction
(d) an increase in the concentration of carbon dioxide
2 Ag (aq )  Cu (s ) Cu (2aq

)  2 Ag ( s )
61. (M) Which of the following factors will increase solubility
of a well known weak base, NH3(g), in H2O ? reaches equilibrium, [Cu2+] = x M and [Ag+] = y M.

NH3(g) + H2O(aq) NH4OH(aq) If the volume of solution is doubled by adding water,

then at equilibrium :
(a) increase in pressure (b) addition of water
2 x y
(c) addition of an acid to water (a) [Cu ]  M, [Ag  ]  M
2 2
(d) addition of a base to water
2 x y
(b) [Cu ]  M, [Ag  ]  M
62. (M) For the following endothermic equilibrium established 2 2
by dissociation of NH4HS to its components,
2 x y
(c) [Cu ]  M, [Ag  ]  M
NH4HS(s) NH3(g) + H2S(g) 2 2

partial pressure of NH3 will increase 2 x y

(d) [Cu ]  M, [Ag  ]  M
2 2
(a) if NH3 is added after equilibrium is established
66. (S) For the reaction PCl5 (g) PCl3 (g) + Cl2 (g)
(b) if H2S is added after equilibrium is established
Which of the following sketch may represent above
(c) temperature is increased equilibrium ? Assume equilibrium can be achieved from
either side and by taking any one or more components
(d) volume of the flask is decreased
initially. (Given KC for the reaction < 2) ?
63. (M) Volume of the flask in which the following equilibria are
separately established are transferred to a flask that is 6 Cl2
double the size of the earlier flask. In which of the following
4 PCl3
cases, equilibrium concentrations are affected ? (a) Concentration
Mol/litre 2 PCl5
(a) N 2  3H 2 2 NH 3
(g ) (g ) (g ) 0
Total

(b) N 2  O 2 2 NO
(g ) (g ) (g) 6
4
(b) Concentration 3 PCl5
(c) PCl 5 PCl 3  Cl 2 Mol/litre PCl3
(g) (g ) (g ) 2
Cl2

(d) 2 NOBr N2  O2 Total

(g) (g ) (g )
 33 CHEMICAL EQUILIBRIUM

(c) A2(g)  2A(g) ; Kp = 2. At (r) n(A) > n(A2) at

6 PCl5
equilibrium the total pressure equilibrium
4 PCl3
(c) Concentration is 2.0 atm.
Mol/litre 2 Cl2
(d) 2A(g)  A2(g)Kp = 2. A (s) n(A) < n(A2) at
0
Total mixture, initially containing equilibrium

6 PCl5 both A and A2 at 1.0 atm

4 Cl2 partial pressure is prepared.

(d) Concentration
Mol/litre 2 PCl3 69. (X) Match the Column–I with Column–II
Column–I Column–II
0
Total
(A) N2(g) + 3H2(g)  2NH3(g) (p) Forward shift by
67. (S) For the following reaction through stages I, II and III
increase in pressure
I II III
A
 B  C  D
(B) N2(g) + O2(g)  2NO(g) (p) No effect of
quantity of the product formed (x) varies with
temperature (T) as given. Select correct statement : pressure change

(C) CaCO3(s)  CaO(s)+CO2(g) (r) No effect of inert

B gas addition at
A I II D constant volume
III
(D) NH2COONH4(s)  2NH3(g)
X C
+ CO2(g)

T (s) Addition of inert gas

will favour backward
(a) Stages I and III are endothermic but II is exothermic direction (Not at
(b) Stages I and III are exothermic but II is endothermic constant volume)

(c) Stages II and III are exothermic but I is endothermic Passage : For Questions (70 to 72)
(d) Stage I is exothermic but stages II and III are Le-Chatelier’s principle : If a system at equilbrium is
endothermic subjected to a change of any one of the factors such as
68. (X) Match the conditions on the left column with states on concentration, pressure or temperature, the system
the right column. adjusts itself in such a way as to “Nullify” the effect of
that change.
Equilibrium types Kp/Kc
Change of Pressure :
relationship
If a system in equilibrium consists of gases, then the
(a) A2(g)  2A(g); Kc = 1. (p) System is at
concentrations of all components can be altered by
Mixture of 1.0 mole of each equilibrium changing the pressure. When the pressure on the
is prepared in a 1.0 L flask. system is increased, the volume decreases
proportionately. The total number of moles per unit
(b) A(g) + 2B(g)  AB2(g) (q) Goes to right volume will now be more and the equilibrium will shift in
Kc= 2. A mixture of 2.0 moles that direction in which there is decrease in number of
moles i.e, towards the direction in which there is decrease
of each A, B and AB2
in volume.
is prepared in a 1.0 L flask.
 34 CHEMICAL EQUILIBRIUM

Effect of Pressure on Melting Point :

1 1
There are two types of solids : 72. (C) For the reaction : N 2 (g)  O2 (g)  NO(g)
2 2
(a) Solids whose volume decreases on melting e.g., ice, If pressure is increased by reducing the volume of the
diamond, carborundum, magnesium nitride and quartz. container, then
Solid (higher volume)  liquid (lower volume) (a) total pressure at equilibrium will change
The process of melting is facilitated at higher pressure, (b) concentration of all the components at equilibrium
thus the melting point is lowered. will change

(b) Solids whose volume increase on melting e.g. Fe, (c) concentration of all the components at equilibrium
Cu, Ag, Au, etc. will remain same
(d) equilibrium will shift in the forward direction
Solid (lower volume)  liquid (higher volume)
73. (M) For the reaction : PCl5(g)  PCl3(g) + Cl2(g),
In this case, the process of melting becomes difficult at
high pressure ; thus melting point becomes high. The forward reaction at constant temperature is
favoured by
(c) Solubility of substances : When solid substances
are dissolved in water, either heat is evolved (exothermic) (a) introducing an inert gas at constant volume
or heat is absorbed (endothermic) : (b) introducing chlorine gas at constant volume
KCl + aq  KCl(aq) + heat (c) introducing an inert gas at constant pressure
(d) increasing the volume of the container
In such cases, solubility increases with increase in
temperature. Consider the case of KOH; when this is 74. (M) Which of the following factors will favour the backward
dissolved, heat is evolved; reaction ?

KOH + aq  KOH(aq) – heat Cl2(g) + 3F2(g)  2ClF3(g) ; H = –ve

In such cases, solubility decrease with increse in (a) Addition of inert gas at constant pressure
temperature. (b) Addition of Cl2 gas
(d) Solubility of gases in liquids : When a gas dissolves (c) Increase in the temperature of reaction
in liquid, there is decrease in volume. Thus, increase of (d) Increasing the volume of the container
pressure will favour the dissolution of gas in liquid.
Answer the following three questions based on the 75. (M) For the gas phase reaction,
–1
above information. C2H4(g) + H2(g)  C2H6(g) ; Hº = –136.8 kJ mol
70. (C) When a gas “X” is dissolved in water, the heat is evolved. carried out in a vessel, the equilibrium concentration of
Then solubility of ‘X’ will increase at C2H4 can be increased by :
(a) low pressure, high temperature (a) increase in temperature(b) decrease in pressure
(b) low pressure, low temperature (c) removing some H2 (d) adding some C2H6
(c) high pressure, high temperature
Physical Equilibria
(d) high pressure, low temperature
76. (S) Densities of diamond and graphite are 3.5 and 2.3 g/mL
71. (C) Au(s)  Au(l) respectively. Increase of pressure on the equilibrium
Above equilibrium is favoured at C (diamond)  C (graphite)
(a) high pressure low temperature (a) favours backward reaction
(b) high pressure high temperature (b) favours forward reaction
(c) low pressure, high temperature (c) has no effect

(d) low pressure, low temperature (d) increase the reaction rate
 35 CHEMICAL EQUILIBRIUM
77. (S) Some quantity of water is contained in a container as If initially only NO and NO2 are present in a 3 : 5 mole
shown in figure below. As neon is added to this system ratio and the total pressure at equilibrium is 5.5 atm with
at constant pressure, the amount of liquid water in the the pressure of NO2 is 0.5 atm, calculate K p (in 10–1).
vessel : 1

82. (I) Two solids A and C dissociate into gas products as

follows.
A(s)  B(g) + D(g); K p = 400
1

C(s)  E(g) + D(g); K p = 900

2
Vapour
At 25ºC, the pressure over excess solid A only is 40
atm, and that over solid C only is 60 atm. Find the
Water pressure over the solid mixture.
83. (S) On heating a mixture of SO2Cl2 and CO, two equilibria
are simultaneously established :
(a) increases (b) decrease SO 2 Cl 2 (g)  SO 2 (g)  Cl 2 (g)
(c) remains same (d) change unpredictably
CO(g)  Cl2 (g)  COCl2 (g)
78. (S) Solubility of a substance which dissolves with a decrease
in volume and absorption of heat will be favoured by On adding more SO2 at equilibrium what will happen ?
(a) high p and high T (b) low p and low T (a) Amount of CO will decrese
(c) high p and Low T (d) low p and high T (b) Amount of SO2Cl2 and COCl2 will increase
79. (S) A solution is transferred to a 1 L flask, some pure ice is (c) Amount of CO will remain unaffected
added and a stopper is inserted to close the flask. After (d) Amount of SO2Cl2 and CO will increase
the system has reached constant temperature, there are 84. (S) Two solid compounds X(s) and Y(s) undergo
still a few cubes of ice left in the flask, but no other dissociation as follows :
solid. Which of the following statements is false relative
to this system at equilibrium ? X(s)  A(g)  2B(g) ; K p1  9  10 3 bar 3
(a) The system is a heterogeneous one.
Y(s)  2B(g)  C(g) ; K p2  4.5  103 bar 3
(b) There are four phases present in the system, not
including the container and stopper. The total pressure of gaseous mixture at equilibrium will
be :
(c) The vapour pressure is constant.
(a) 4.5 bar (b) 0.45 bar
(d) The temperature of the system is below 0ºC.
(c) 0.6 bar (d) 1.2 bar
80. (S) When a liquid in equilibrium with its vapour is heated
85. (S) Given the following reactions and associated equilibrium
(a) the rate of the reaction, vapour  liquid, is constants, select the correct expression for the third
increased equilibrium constant in terms of the first two.
(b) the same equilibrium mixture is re-established (A) 2CO(g)  O 2 (g)  2CO2 (g)K c
1

(c) a new equilibrium mixture with a higher vapour

pressure is established 1
(B) H 2 (g)  O 2 (g)  H 2 O(g)K c2
(d) a new equilibrium mixture is established in which the 2
rate of evaporation is greater than the rate of
condensation (C) CO(g)  H 2 O(g)  CO2 (g)  H 2 (g)K c3

Simultaneous Equilibria 1/ 2
K c1 K c1
81. (I) Two equilibria are simultaneously existing in a vessel (a) K c3  K (b) K c3 
c2 K c2
at 25ºC
NO(g) + NO2(g)  N2O3(g); K p (say) 1/ 2
1  
(c) K c3  K c1  K c2

2NO2(g)  N2O4(g); K p = 8 atm–1 1/ 2 1/ 2

2
 
(d) K c3  K c1  
 K c2
 36 CHEMICAL EQUILIBRIUM

EXERCISE - 4 : PREVIOUS YEAR JEE ADVANCED QUESTION

1. The oxidation of SO2 by O2 to SO3 is an exothermic 6. For the reversible reaction, N2(g) + 3H2(g) 2NH3(g)
reaction. The yield of SO3 will be maximum if (1981) at 500ºC, the value of Kp is 1.44 × 10–5 when partial pressure
(a) temperature is increased and pressure is kept constant is measured in atmospheres. The corresponding value of
Kc, with concentration in mole litre–1 is (2000)
(b) temperature is reduced and pressure is increased
(c) both temperature and pressure are increased 1.44  10 5 1.44 10 5
(a) 2 (b)
(d) both temperature and pressure are reduced (0.082  500) (8.314  773)  2
2. For the reaction :
H2(g) + I2(g) 2HI (g) 1.44  10 5 1.44 10 5
(c) 2 (d)
(0.082  773) (0.082  773)  2
The equilibrium constant Kp changes with (1981)
(a) total pressure (b) catalyst 7. When two reactants, A and B are mixed to give products C
(c) the amounts of H2 and I2 present and D, the reaction quotient Q, at the initial stages of the
reaction (2000)
(d) temperature
(a) is zero (b) decreases with time
3. Pure ammonia is placed in a vessel at a temperature where
its dissociation constant () is appreciable. At equilibrium (c) is independent of time (d) increases with time
N2 + 3H2 NH3 (1984) 8. At constant temperature, the equilibrium constant (Kp) for
the decomposition reaction N2O4 2NO2 is expressed
(a) Kp does not change significantly with pressure
by Kp = (4x2P) (1 – x2), where P = presssure, x = extent of
(b)  does not change with pressure decomposition. Which one of the following statements is
(c) concentration of NH3 does not change with pressure true ? (2001)
(d) concentration of hydrogen is less than that of nitrogen (a) Kp increases with increase of P
4. For the reaction ; (b) Kp increases with increase of x
CO (g) + H2O(g) CO2 (g) + H2 (g),
(c) Kp increases with decrease of x
at a given temperature, the equilibrium amount of CO2(g)
(d) Kp remains constant with change in P and x
can be increased by (1998)
(a) adding a suitable catalyst 9. Consider the following equilibrium in a closed container

(b) adding an inert gas N2O4 (g) 2 2NO2(g)

(c) decreasing the volume of the container At a fixed temperature, the volume of the reaction container
(d) increasing the amount of CO(g) is halved. For this change, which of the following
statements hold true regarding the equilibrium constant
5. For the chemical reaction
(Kp) and degree of dissociation () ? (2008)
3X (g) + Y (g) X3Y (g)
(a) Neither Kp nor  changes
the amount of X3Y at equilibrium is affected by (1999)
(b) Both Kp and  changes
(a) temperature and pressure
(b) temperature only (c) Kp changes but  does not change

(c) pressure only (d) Kp does not change but  changes

(d) temperature, pressure and catalyst
 37 CHEMICAL EQUILIBRIUM

10. N2 + 3H3 2NH3 Objective Questions (One or more than one correct
Which is correct statement if N2 is added at equilibrium
option)
13. For the gas phase reaction
condition ? (2006)
C2H4 + H2 C2H6 (H = – 32.7 kcal)
(a) The equilibrium will shift to forward direction because
carried out in a vessel, the equilibrium concentration of
according to IInd law of thermodynamics the entropy C2H4 can be increased by (1984)
must increase in the direction of spontaneous reaction (a) Increasing the temperature
(b) decreasing the pressure
(b) The condition for equilibrium is G N 2  3G H 2  2G NH3 (c) removing some H2
where G is Gibbs free energy per mole of the gaseous (d) adding some C2H6
species measured at that partial pressure. The 14. When NaNO3 is heated in a closed vessel, oxygen is
liberated and NaNO2 is left behind. At equilibrium (1986)
condition of equilibrium is unaffected by the use of
(a) addition of NaNO2 favours reverse reaction
catalyst, which increases the rate of both the forward
(b) addition of NaNO3 favours forward reaction
and backward directions to the same extent
(c) increasing temperature favours forward reaction
(c) The catalyst will increase the rate of forward reaction (d) increasing pressure favours reverse reaction
by  15. The equilibrium SO2Cl2(g) SO2 (g) + Cl2(g) is
(d) Catalyst will not alter the rate of either of the reaction. attained at 25ºC in a closed container and an inert gas,
Paragraph helium is introduced. Which of the following statements
Thermal decomposition of gaseous X2 to gaseous X are correct ? (1989)
at 298 K takes place according to the following (a) Concentration of SO2, Cl2 and SO2Cl2 change
(b) More chlorine is formed
equation :
(c) Concentration of SO2 is reduced
X2 (g)  2X(g) (d) All the above are incorrect
The standard reaction Gibbs energy, rG°, of this 16. For the reaction, PCl5 (g) PCl3(g) + Cl2(g)
reaction is positive. At the start of the reaction, there The forward reaction at constant temperature is favoured
by (1991)
is one mole of X2 and no X. As the reaction proceeds,
(a) introducing chlorine gas at constant volume
the number of moles of X formed is given by . Thus, (b) introducing an inert gas at constant pressure
 equilibrium is the number of moles of X formed at (c) increasing the volume of the container
equilibrium. The reaction is carried out at a constant (d) introducing PCl5 at constant volume
total pressure of 2 bar. Consider the gases to behave 17. For a reaction, A  P, the plots of [A] and [P] with time
ideally. (Given : R = 0.083 L bar K–1 mol–1) (2016) at temperatures T1 and T2 are given below. (2018)
11. The equilibrium constant Kp for this reaction at 298 K,
in terms of equilibrium, is
2 2
8equilibrium 8equilibrium
(a) 2   (b) 2
equilibrium 4  equilibrium

2 2
4equilibrium 4equilibrium
(c) (d) 2
2  equilibrium 4  equilibrium

12. The INCORRECT statement among the following, for this If T2 > T1, the correct statement(s) is (are)
reaction, is
(Assume H  and S are independent of temperature
(a) Decrease in the total pressure will result in formation and ratio of lnK at T1 to lnK at T2 is greater than T2/T1.
of more moles of gaseous X Here H, S, G and K are enthalpy, entropy, Gibbs energy
(b) At the start of the reaction, dissociation of gaseous and equilibrium constant, respectively.)
X2 takes place spontaneously (a) H   0, S  0 (b) G   0, H   0
(c) equilibrium = 0.7
(c) G   0, S  0 (d) G   0, S  0
(d) KC < 1
 38 CHEMICAL EQUILIBRIUM

Fill in the Blanks 30. The equilibrium constant Kp of the reaction,

18. For a given reversible reaction at a fixed temperature,
2SO2(g) + O2 (g) 2SO3 (g)
equilibrium constant Kp and Kc are are related by ..............
is 900 atm at 800 K. A mixture containing SO3 and O2 having
(1994)
initial pressure of 1 and 2 atm respectively is heated at
19. A ten-fold increase in pressure on the reaction, N2(g) +
constant volume to equilibrate. Calculate the partial
3H2 (g) 2NH3 (g) at equilibrium, results in ................ pressure of each gas at 800 K. (1989)
in Kp. (1996)
31. For the reaction
20. For a gaseous reaction 2B   A, the equilibrium CO(g) + 2H2 (g) CH3OH(g)
constant Kp is ........... to/than Kc. hydrogen gas is introduced into a five litre flask at 327ºC,
True/False containing 0.2 mole of CO(g) and a catalyst, until the pressure
21. When a liquid and its vapour are at equilibrium and the
pressure is suddenly decreased, cooling occurs. (1984) is 4.92 atm. At this point 0.1 mole of CH3OH(g) is formed.
22. If equilibrium constant for the reaction, A2 + B2 Calculate the equilibrium constant, Kp and Kc. (1990)
32. 0.15 mole of CO taken in a 2.5 L flask is maintained at 750 K
1
2AB, is K, then for the backward reaction AB along with a catalyst so that the following reaction can
2 take place :
1 1 CO (g) + 2H2(g) CH3OH(g)
A 2  B2 , the equilibrium constant is . (1984)
2 K Hydrogen is introduced until the total pressure of the
23. Catalyst makes a reaction more exothermic. (1987) system is 8.5 atm at equilibrium and 0.08 mole of methanol
24. The rate of an exothermic reaction increases with is formed. Calculate (i) Kp and Kc and (ii) the final pressure
increasing temperature. (1993) if the same amount of CO and H2 as before are used, but
Subjective Questions with no catalyst so that the reaction does not take place.
25. One mole of nitrogen is mixed with three moles of (1993)
hydrogen in a four litre container. If 0.25 per cent of nitrogen 33. The progress of reaction,
is converted to ammonia by the following reaction
A nB
N2(g) + 3H2 (g) 2NH3 (g), then with time, is represented in fig. given below. Determine
calculate the equilibrium constant, Kc in concentration
units. What will be the value of Kc for the following
equilibrium ?
1 3
N 2 (g) + H 2 (g) NH3 (g) (1981)
2 2
26. One mole of Cl2 and 3 moles of PCl5 are placed in a 100 litre
vessel heated at 227ºC. The equilibrium pressure is 2.05
atmosphere. Assuming ideal behaviour, calculate the
degree of dissociation for PCl5 and Kp for the reaction
PCl5(g) PCl3 (g) + Cl2 (g) (1984)
27. The equilibrium constant of the reaction (i) the value of n
(ii) the equilibrium constant, K and
A2(g) + B2(g) 2AB (g) at 100ºC is 50. If a one litre
(iii) the initial rate of conversion of A. (1994)
flask containing one mole of A2 is connected to a two litre
34. The degree of dissociation is 0.4 at 400 K and 1.0 atm for
flask containing two moles of B2, how many mole of AB
the gaseous reaction PCl5 PCl3 + Cl2. Assuming
will be formed at 373ºC ? (1985)
ideal behaviour of all the gases, calculate the density of
28. At a certain temperature, equilibrium constant (Kc) is 16
equilibrium mixture at 400 K and 1.0 atm (relative atomic
for the reaction ;
mass of P = 31.0 and Cl = 35.5) (1998)
SO 2 (g) + NO 2 (g) SO3(g) + NO(g) 35. When 3.06 g of solid NH4SH is introduced into a two litre
If we take one mole of each of all the four gases in a one evacuated flask at 27ºC, 30% of the solid decomposes into
litre container, what would be the equilibrium concentration gaseous ammonia and hydrogen sulphide.
of NO and NO2 ? (1987)
(i) Calculate Kc and Kp for the reaction at 27ºC.
29. N2O4 is 25% dissociated at 37ºC and one atmosphere
pressure. Calculate (i) K P and (ii) the percentage (ii) What would happen to the equilibrium when more solid
dissociation at 0.1 atmosphere and 37ºC. (1988) NH4SH is introduced into the flask ? (1999)
 39 CHEMICAL EQUILIBRIUM

ANSWER KEY

EXERCISE - 1 : (Basic Objective Questions)

1. (c) 2. (b) 3. (d) 4. (d) 5. (d) 6. (c) 7. (a) 8. (a) 9. (c) 10. (d)

11. (d) 12. (b) 13. (b) 14. (d) 15. (a) 16. (b) 17. (b) 18. (a) 19. (c) 20. (c)

21. (d) 22. (c) 23. (c) 24. (b) 25. (d) 26. (a) 27. (d) 28. (c) 29. (c) 30. (a)

31. (d) 32. (a) 33. (c) 34. (b) 35. (c) 36. (a) 37. (d) 38. (b) 39. (d) 40. (b)

41. (c) 42. (a) 43. (b) 44. (a) 45. (d) 46. (a) 47. (b) 48. (d) 49. (a) 50. (a)

51. (a) 52. (a) 53. (d) 54. (d) 55. (b) 56. (a) 57. (c) 58. (d) 59. (b) 60. (d)

61. (b) 62. (b) 63. (d) 64. (b) 65. (d) 66. (d) 67. (d) 68. (a) 69. (d) 70. (a)

71. (c) 72. (c) 73. (c) 74. (a) 75. (c) 76. (b) 77. (c) 78. (d) 79. (d) 80. (d)

81. (d) 82. (c) 83. (d) 84. (c)

EXERCISE - 2 : (Previous year JEE Mains Questions)

1. (a) 2. (c) 3. (d) 4. (d) 5. (a) 6. (b) 7. (a) 8. (d) 9. (d) 10. (d)

11. (a) 12. (a) 13. (a) 14. (c) 15. (a) 16. (a) 17. (d) 18. (b) 19. (c)

JEE Mains Online

1. (d) 2. (c) 3. (a) 4. (d) 5. (a) 6. (c) 7. (d) 8. (a) 9. (b) 10. (d)

EXERCISE - 3 : (Advanced Objective Questions)

1. (a) 2. (a) 3. (b,c) 4. (c) 5. (b) 6. (a) 7. (a) 8. (a) 9. (a,c) 11. (c)

12. (a) 13. (a) 14. (0004) 15. (a) 16. (c) 17. (b) 18. (b) 19. (c) 20. (c) 21. (a)

22. (a) 23. (b) 24. (A–s), (B–p), (C–q), (D–r) 25. (b) 26. (b) 27. (b) 28. (a,c,d)

29. (a,b) 30. (a) 31. (a,d) 32. (d) 33. (c) 34. (c) 35. (a) 36. (a)
 40 CHEMICAL EQUILIBRIUM

37. (A–p,q,s), (B-q,r), (C–q), (D–p,s) 38. (0008) 39. (0008) 40. (0006) 41. (b) 42. (c) 43. (b) 44. (d)

45. (d) 46. (b) 47. (d) 48. (a,c) 49. (a) 50. (b) 51. (b) 52. (b) 53. (a) 54. (a)

55. (d) 56. (a,c) 57. (a,b,d) 58. (c,d) 59. (b,d) 60. (b,c,d) 61. (a,b,c) 62. (a,c) 63. (a,c) 64. (c)

65. (c) 66. (d) 67. (a) 69. (A-p,r,s), (B-q,r), (C-r), (D-r) 70. (d) 71. (c) 72. (b)

73. (c,d) 74. (a,c,d) 75. (a,b,c,d) 76. (a) 77. (b) 78. (a) 79. (b) 80. (c) 81. (0004)

82. (0072) 83. (d) 84. (b) 85. (b)

EXERCISE - 4 : (Previous year JEE Advanced Questions)

1. (b) 2. (d) 3. (a) 4. (d) 5. (a) 6. (d) 7. (d) 8. (d) 9. (d) 10. (b)

11. (b) 12. (c) 13. (a,b,c,d) 14. (c,d) 15. (d) 16. (bcd) 17. (a,c) 18. Kp = Kc (RT)n

19. no change 20. smaller 21. (T) 22. (F) 23. (F) 24. (F) 25. 0.468 L2 mol–2, 0.68

175 85
26. 0.33 27. 1.76 29. 0.266 atm; 63% 30. atm , atm 31. Kp = 0.11 atm–2 , Kc = 277.77 M–2
87 87

–5 –2
32. 220 33. (i) n = 2, (ii) 1.2 34. 4.54g/L 35. 8.1 × 10 , 4.84 × 10 , (ii) No effect

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