Equilibrium

Equilibrium is the state at which the concentration of reactant and

products do not change with time .
Concentration of reactants and products become constant.

In a reversible reaction

R1+ R2 ⇌ P1 + P2

Reactants products

At Equilibrium:
Rate of forward reaction (rf) = rate of backward reaction (rb)
Equilibrium
At equilibrium:
Concentration (mole/L) of reactant and product remains
constant with respect to time.
 Types of equilibrium on the basis of process

Physical Equilibrium Chemical Equilibrium

Equilibrium in physical process Equilibrium in chemical process
is called physical equilibrium is called chemical equilibrium

For example phase change like For example

H2(g) + Cl2(g) ⇌ 2HCl(g)
H2O(I) ⇌ H2O(g);

Solvation like
H2O
NaCl(s) NaCl(aq)
excess
Characteristics of Chemical equilibrium

● It is dynamic in nature- at this stage, reaction

take place in both the direction with same speed
so., there is no net change

● At equilibrium the reaction proceeds both the

side , equally.

● Equilibrium can be obtained from either side of

the reaction.
Characteristics of Chemical equilibrium

● At equilibrium , both reactants and products are

present and their concentration do not change with
respect to time.

● A catalyst can alter the rate of approach of equilibrium

but does not change the state of equilibrium

● At equilibrium, free energy change ΔG = 0.

● Change in pressure , temperature or concentration

favours one of the reactions and thus shift the
equilibrium point in one direction .
 Equilibrium constant (Kc)

For a general reaction

aA + bB ⇌ cC + dD,
Forward reaction rate rf = kf[A]a [B]b,
Backward reaction rate rb = kb [C]c [D]d,
At equilibrium r f = rb
kf [A]aeq [B]beq = kb [C]ceq
[D]deq
The concentration of reactants & products at equilibrium are related by
 Kp (Equilibrium constant in terms of partial pressure)

It is defined for the equilibrium reaction which contains at least one

gaseous component.

aA(g) + bB(g) ⇌ cC(g) + dD(g)

Where various pressure are the partial pressures of various gases

substances.
 Relation between Kp & Kc

aA(g) + bB(g) ⇌ cC(g) + dD(g)

KP = KC(RT)Δng

Δng =
sum of the number of
moles of gaseous products - sum of the number of moles
of gaseous reactants
In which one of the following equilibria, Kp ≠ Kc ?

A 2C(s) + O2(g) ⇌ 2CO(g)

B 2HI(g) ⇌ H2(g) + I2(g)

C NO2(g) + SO2(g) ⇌ NO(g) + SO3(g)

D 2NO(g) ⇌ N2(g) + O2(g)

In which one of the following equilibria, Kp ≠ Kc ?

A 2C(s) + O2(g) ⇌ 2CO(g)

B 2HI(g) ⇌ H2(g) + I2(g)

C NO2(g) + SO2(g) ⇌ NO(g) + SO3(g)

D 2NO(g) ⇌ N2(g) + O2(g)

Q- The ratio Kp / KC for the reaction, CO(g) + ½ O2(g) ⇌ CO2(g) is :

A 1 / √(RT)

(RT)½
B

C RT

D 1
Q- The ratio Kp / KC for the reaction, CO(g) + ½ O2(g) ⇌ CO2(g) is :

A 1 / √(RT)

(RT)½
B

C RT

D 1
Solution:
Q- The equilibrium constant at 298 K for a reaction,
A + B ⇌ C + D is 100. If the initial concentrations of all the four species were 1 M each,
then equilibrium concentration of D (in mol L -1 ) will be :
JEE Main 2021

A 0.818

B 1.818

C 1.182

D 0.182
Q- The equilibrium constant at 298 K for a reaction,
A + B ⇌ C + D is 100. If the initial concentrations of all the four species were 1 M each,
then equilibrium concentration of D (in mol L -1 ) will be :

A 0.818

B 1.818

C 1.182

D 0.182
Solution:
Properties of Equilibrium constant

● Equilibrium constant does not depend upon

concentration of various reactants, presence of
catalyst, direction from which equilibrium is
reached
● The equilibrium constant does not give any idea
about time taken to attain equilibrium.
Properties of Equilibrium constant

Equation constant
A(g) ⇌ B(g)
K1
B(g) ⇌
C(g) K2
On adding A(g) ⇌ C(g)
K = K 1 . K2
 Properties of Equilibrium constant

A(g) + B(g) ⇌
C(g) +D(g) K=K1
On reversing C(g) + D(g) ⇌ A(g) + B(g)
K = 1/K1
 Properties of Equilibrium constant

e.g D2(g) ⇌

2A(g) K=K1

½ D2 ⇌ A

K = (K1)1/2
At 298 K, the equilibrium constant is 2 × 1015 for the reaction:

Cu(s) + 2Ag+ (aq) ⇌ Cu2+(aq) + 2Ag(s)

The equilibrium constant for the reaction

JEE Main 2022

is x × 10-8 . The value of x is ________ (Nearest integer)

Solution:
Prediction of extent of reaction
Prediction of direction of reaction

● At each point in the reaction, we can write a ratio of

concentration terms having the same form as the equilibrium
constant expression.
● This ratio is called the reaction quotient denoted by symbol Q. It
helps in predicting the direction of a reaction
Reaction quotient and Its applications

2A(g) + B(g) ⇌ C (g) + D(g)

QC = reaction quotient in terms of concentration

(Here all the conc. are at equilibrium)

Reaction quotient and Its applications

It helps in predicting the direction of a reaction.

❏ If Q > KC reaction will proceed in backward

direction until equilibrium is reached.
❏ If Q <KC reaction will proceed in forward
direction until equilibrium is established.
❏ If Q = KC reaction is at equilibrium.
In which of the following case - the extent of reaction towards the
product side is maximum?

A Kc=103

Kc=102
B

C Kc=10-2

D Kc=10-3
In which of the following case - the extent of reaction towards the
product side is maximum?

A Kc=103

Kc=102
B

C Kc=10-2

D Kc=10-3
Q- When two reactants, A and B are mixed to give products, C and D, the reaction
quotient, (Q ) at the initial stages of the reaction :

A Is zero

decreases with time

B

C is independent of time

D increases with time

Q- When two reactants, A and B are mixed to give products, C and D, the reaction
quotient, (Q ) at the initial stages of the reaction :

A Is zero

decreases with time

B

C is independent of time

D increases with time

Solution:
Degree of dissociation
Degree of dissociation
Degree of dissociation
Q- At a certain temperature, only 50% HI is dissociated into H2 and I2 at equilibrium.
The equilibrium constant is :

A 1.0

3.0
B

C 0.5

D 0.25
Q- At a certain temperature, only 50% HI is dissociated into H2 and I2 at equilibrium.
The equilibrium constant is :

A 1.0

3.0
B

C 0.5

D 0.25
Solution:
The gas A2 in the left flask allowed to react with gas B2 present in right
flask as
A2(g) + B2(g) ⇌ 2AB(g) ; Kc = 4 at 27°C.
What is the concentration of AB when equilibrium is established?
Solution:
Q- In reaction A + 2B ⇌ 2C + D , initial concentration of B was 1.5 times of [A], but at
equilibrium the concentrations of A and B became equal. The equilibrium constant
for the reaction is :

A 8

4
B

C 12

D 6
Q- In reaction A + 2B ⇌ 2C + D , initial concentration of B was 1.5 times of [A], but at
equilibrium the concentrations of A and B became equal. The equilibrium constant
for the reaction is :

A 8

4
B

C 12

D 6
Solution:
Thermodynamics of Equilibrium

ΔG = ΔGo + 2.303RT log10Q

ΔG = Gibb’s energy
ΔGo = standard Gibb’s energy
Q = reaction quotient
 Thermodynamics of Equilibrium

Spontaneous Reaction in forward

Keq > 1 ΔG⊖ < 0
reaction direction

Keq < 1 ΔG⊖ > 0 Non spontaneous Reaction in backward

reaction direction

Keq = 1 ΔG⊖ = 0 Not shift reaction in

Equilibrium
any direction
Thermodynamics of Equilibrium
Thermodynamics of Equilibrium
Thermodynamics of Equilibrium

● Vant Hoff equation

Q- The standard Gibbs energy change at 300 K for the reaction,
2A ⇌ B + C is 2494.2 J. At a given time, the composition of the reaction mixture is [A]
= ½ , [B] = 2 and [C] = ½ . The reaction proceeds in the : [ R = 8.314 J K mol -1, e =
2.718]

A forward direction because Q > KC

B reverse direction because Q > KC

C forward direction because Q < KC

D reverse direction because Q < KC

Q- The standard Gibbs energy change at 300 K for the reaction,
2A ⇌ B + C is 2494.2 J. At a given time, the composition of the reaction mixture is [A]
= ½ , [B] = 2 and [C] = ½ . The reaction proceeds in the : [ R = 8.314 J K mol -1, e =
2.718]

A forward direction because Q > KC

B reverse direction because Q > KC

C forward direction because Q < KC

D reverse direction because Q < KC

Solution:
 Le-chatelier’s principle

If a change is applied to the system at equilibrium, then

equilibrium will be shifted in that direction in which it can
minimise the effect of change applied and the equilibrium is
established again under new conditions.
 Le-chatelier’s principle

● Effect of concentration :

N2(g) + 3H2(g) ⇌ 2NH3(g)

[reactant]↑ Forward shift

[Product]↑ Backward shift

 Le-chatelier’s principle

Effect of volume :

● If volume is increased, pressure decreases hence reaction will shift in

the direction in which pressure increases that is in the direction in

which number of moles of gases increases and vice versa.

● If volume is increased then, for

Δng > 0 reaction will shift in the forward direction

Δng< 0 reaction will shift in the backward direction

Δng = 0 reaction will not shift.

 Le-chatelier’s principle

Effect of catalyst :

Due to catalyst, the state of equilibrium is not affected i.e. no

shift will occur as catalyst lowers the activation energy of both

the forward & reverse reaction by same amount, thus altering

the forward & reverse rate equally and hence, the equilibrium

will be attained faster i.e time taken to reach the equilibrium is

less.
 Le-chatelier’s principle

Effect of inert gas addition :

(a) At constant volume : Inert gas addition has no effect at

constant volume.

(b) At constant pressure : If inert gas is added then to maintain

the pressure constant, volume is increased. Hence equilibrium will shift
in the direction in which larger no. of moles of gas is formed
(i) Δng > 0, reaction will shift in the forward direction
(ii) Δng < 0, reaction will shift the backward direction
(iii) Δng = 0, no effect
 Le-chatelier’s principle

Effect of temperature

Exothermic reaction : The reaction in which heat is evolved

A(g) + B(g) ⇌ C(g) + D(g) + Heat ΔH = -ve

Reaction will shift in backward direction if T↑

Reaction will shift in forward direction if T↓
Le-chatelier’s principle

Effect of temperature

Endothermic reaction :
A(g) + B(g) ⇌ C(g) +D(g) ∴ ΔH = +ve

T↑ ⇒ forward;
T↓ ⇒ backward
 Le-chatelier’s principle

Effect of pressure :
On increasing pressure, equilibrium will shift in the direction in which
pressure decreases i.e. no. of moles in the reaction decreases and vice
versa.
(i) For Δng = 0 ⟶No. Effects
(ii) For Δng > 0
PCl5(g) ⇌ PCl3(g)+Cl2(g)
P↓ (Forward shift)
P↑ (Backward shift)
 Le-chatelier’s principle

Effect of pressure :
For Δng < 0, eg.
N2(g) + 3H2(g) ⇌ 2NH3(g)
P↑(Forward shift)
P↓ (Backward shift)
Q- The equilibrium SO2Cl2 (g) ⇌ SO2 (g) + Cl2 (g) is attained at 25°C in a closed
container and an inert gas, helium is introduced. Which of the following
statements are correct?

A Concentration of SO2 ,Cl2 and SO2Cl2 change.

B More chlorine is formed

C Concentration of SO2 is reduced

D None of the above

Q- The equilibrium SO2Cl2 (g) ⇌ SO2 (g) + Cl2 (g) is attained at 25°C in a closed
container and an inert gas, helium is introduced. Which of the following
statements are correct?

A Concentration of SO2 ,Cl2 and SO2Cl2 change.

B More chlorine is formed

C Concentration of SO2 is reduced

D None of the above

Solution:

SO2Cl2 (g) ⇌ SO2 (g) + Cl2 (g)

Adding inert gas at constant volume will not affect partial pressure of reactant or
products, hence will not affect equilibrium amount of either reactant or products.
Q- The increase of pressure on ice ⇌ water system at constant temperature will
lead to :

A decrease in the entropy of

A
the system

An increase in the Gibb’s

B
energy of the system

C No effect on the equilibrium

A shift of the equilibrium in the

D
forward reaction
Q- The increase of pressure on ice ⇌ water system at constant temperature will
lead to :

A decrease in the entropy of

A
the system

An increase in the Gibb’s

B
energy of the system

C No effect on the equilibrium

A shift of the equilibrium in the

D
forward reaction
Solution:
Q- Following two equilibrium is simultaneously established in a container
PCl5(g) ⇌ PCl3(g) + Cl2(g) , CO(g) + Cl2(g) ⇌ COCl2(g)
If some Ni(s) is introduced in the container forming Ni(CO)4(g) then at new
equilibrium -

PCl3 concentration will

A
increase

B PCl3 concentration will

decrease

Cl2 concentration will remain

C
same

CO concentration will remain

D
same
Q- Following two equilibrium is simultaneously established in a container
PCl5(g) ⇌ PCl3(g) + Cl2(g) , CO(g) + Cl2(g) ⇌ COCl2(g)
If some Ni(s) is introduced in the container forming Ni(CO)4(g) then at new
equilibrium -

PCl3 concentration will

A
increase

B PCl3 concentration will

decrease

Cl2 concentration will remain

C
same

CO concentration will remain

D
same
Solution:

Ni combines with CO and produced Ni(CO)4 so concentration Cl2 increases and eq. In
1st reaction shifts in backward direction so PCl3 concentration will decrease
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