C H E M I S T R Y

CHEMICAL EQUILIBRIUM
TYPES OF EQUILIBRIUM CONSTANTS AND
REACTION QUOTIENT

What you already know

• What is an equilibrium • Rates and concentration plots

• Physical equilibrium • Law of mass action
• Rate of reaction • Equilibrium constant
• Collision frequency • Types of equilibrium

What you will learn

• Kp, Kc, and Kx • Reaction quotient

• Homogeneous equilibria • Predicting the extent of reaction
• Heterogeneous equilibria • Degree of dissociation

Molar concentration

The equilibrium N2(g) + O2(g) ⇌ 2NO(g) is established in a

reaction vessel of 2.5 L capacity. The amounts of N2 and O2
taken at the start were 2 and 4 moles, respectively, and half
a mole of nitrogen was used up at equilibrium. What is the
molar concentration of nitric oxide?
At time t = 0 At equilibrium
(a) 0.2 (b) 0.4 (c) 0.6 (d) 0.1

N2(g) O2(g) NO(g)

Solution

Consider the equilibrium, N2(g) + O2(g) ⇌ 2NO(g)

N2(g) O2(g) NO(g)

No. of moles initially 2 mol 4 mol 0 mol

No. of moles at equilibrium 2 − 0.5 = 1.5 mol 4 − 0.5 = 3.5 mol 2 × 0.5 = 1 mol

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Number of moles
Molar concentration of nitric oxide =
Volume of the gas
1
=
2.5
= 0.4
(Volume of the container is taken as the volume of the gas)
Hence, option (b) is the correct answer.

Based on equilibrium constant

If 0.5 moles of H2 reacts with 0.5 moles of I2 in a 10 litre

container at 444 °C and at the same temperature, the value
of equilibrium constant Kc is 49. What will be the ratio of
[HI] and [I2]?
At time t = 0 At equilibrium

H2(g) I2(g) HI(g)

Solution

The equilibrium reaction is, H2(g) + I2(g) ⇌ 2HI(g)

H2(g) I2(g) HI(g)

No. of moles initially 0.5 0.5 0

No. of moles at equilibrium 0.5 − X 0.5 − X 2X

2
HI
Equilibrium constant, K c =  
H2   I2 

Given, Kc = 49
At equilibrium, [H2] = [I2]
2
HI
Therefore, 49 =  2
I2 
HI
49 =  
I2 
HI
=7
I2 
Hence, the ratio of [HI] and [I2] at equilibrium = 7

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Based on equilibrium constant

For the reaction equilibrium, N2O4(g) ⇌ 2NO2(g), the concentrations

of N2O4 and NO2 at equilibrium are 4.8 × 10−2 and 1.2 × 10−2 mol L−1,
N2O4(g)
respectively. What will be the value of Kc for the reaction?
(a) 3.3 × 102 mol L−1 (b) 3.0 × 10−1 mol L−1 NO2(g)
(c) 3.0 × 10−3 mol L−1 (d) 3.0 × 103 mol L−1

Solution

For the reaction, N2O4(g) ⇌ 2NO2(g), the equilibrium constant is calculated as,
2
NO2 
Kc =
N2 O 4 
Given, [N2O4] = 4.8 × 10−2 mol L−1
[NO2] = 1.2 × 10−2 mol L−1
2
1.2 × 10−2 
Kc = −2
mol L−1
4.8 × 10
Kc = 3.0 × 10−3 mol L−1
Hence, option (c) is the correct answer.

BOARDS MAIN ADVANCED

Kp, Kc, and K x

Consider the general equilibrium reaction, aA(g) + bB(g) ⇌ cC(g) + dD(g)

The equilibrium constants in terms of pressure, concentration, and mole fraction are as follows:

(pC )eq (pD )eq ( x C )eq ( xD )eq

c d c d c d
C eq D eq
Kp = Kc = Kx =
(p A )eq (pB )eq ( x A )eq ( xB )eq
a b a b a b
 A eq Beq

Where, pA, pB, pC, and pD are the partial pressures of components of A, B, C, and D, respectively.
xA, xB, xC, and xD are the mole fractions of components A, B, C, and D, respectively.

Homogeneous equilibria

In a homogeneous system, all the reactants and the products are in the same phase.
For example, in the gaseous reaction, N2(g) + 3H2(g) ⇌ 2NH3(g), the reactants and the products are
in the same homogeneous gas phase.

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N2(g) H2(g) NH3 N2(g) H2(g) NH3(g)

At time t = 0 At equilibrium
Fig. 1: Homogeneous equilibrium
Equilibrium constants in gaseous systems

11 11
(1) N2(g) + 3H2(g) ⇌ 2NH3(g) (2) HH22((gg)) ++ I2I2((gg))⇌HI
(2)
(2) HI((gg))
22 22
[NH3 ]eq
2

Kc = [HI] eq
[N2 ]eq [H2 ]eq
3 Kc = 1 1
[H2 ]eq2 [I2 ] eq2
(p )
2

Kp =
NH3 eq (pHI )eq
(p ) (p ) Kp =
3
1 1

(pH2 ) 2 (pI2 ) 2
N2 eq H2 eq
eq eq

( xNH3 )
2

Kx = eq
( xHI )eq
(x ) (x ) Kx =
3
1 1

(x ) (x )
N2 eq H2 eq 2 2
H2 I2
eq eq

Note

The equilibrium reaction should be balanced before finding the equilibrium constants.

Heterogeneous equilibria

The equilibrium in a system having more than one phase is known as heterogeneous equilibrium.
For example, the equilibrium between water vapor and the liquid water in a closed container is an
example of heterogeneous equilibrium, i.e., H2O(l) ⇌ H2O(g).

Fig. 2: Heterogeneous equilibrium

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Consider the general heterogeneous equilibrium reaction, where one of the species is in the solid
state.
aA(s) + bB(g) ⇌ cC(g) + dD(g)
The collisions of the reactants lead to the formation of the products. Considering only the forward
reaction, the collision frequency of B with A increases with the increase in the concentration of B.
However, the other reactant, i.e., A, has no effect on the rate of the forward reaction because the
number of particles undergoing collisions will not change if we increase the concentration of A as
it is solid. Therefore, at equilibrium,
Rate of the forward reaction = Rate of the backward reaction
kf [B]b = kb [C]c [D]d … (Active mass of A is neglected as it is solid)

[C ] [D]
c d
Kf
=
[B]
b
Kb

c d
C  D 
K eq =   b 
B 

Where, Keq = Equilibrium constant

The active masses of solids and liquids in a reaction at equilibrium are taken as 1 for
convenience.

Examples:
(1) CaCO3(s) ⇌ CaO(s) + CO2(g) (2) 2KClO3(s) ⇌ 2KCl(s) + 3O2(g)

Kc = [CO2 ]eq Kc = [O2 ]eq

3

Kp = (pCO2 ) Kp = (pO2 )
3
eq eq

K x = ( x CO2 ) K x = ( x O2 )
3
eq eq

BOARDS MAIN ADVANCED

Reaction Quotient

The reaction quotient in terms of concentration may be defined as the ratio of the product of the molar
concentrations of the products to that of the product of the molar concentrations of the reactants,
with each concentration term raised to a power equal to the stoichiometric coefficient in the balanced
chemical equation. However, the concentrations in Qc are not necessarily the equilibrium values.
The expression of reaction quotient (Q) is written in a similar way as the equilibrium constant
expression.
Consider the general equilibrium reaction, aA(g) + bB(g) ⇌ cC(g) + dD(g)

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The reaction quotients in terms of concentration and partial pressure are as follows:

[ C ] [D] (p ) (p )
c d c d

Qc = Qp = C a D b
[ A ]a [B]b ( p A ) ( pB )
Consider the general reaction,
A(g) + B(g) ⇌ C(g)

t=0 2 mol 2 mol 0

t = 10 min 1.5 mol 1.5 mol 0.5 mol

t = teq 0.5 mol 0.5 mol 1.5 mol

At time t = teq, we define, Kp, Kc, and Kx, while at any point in time, Qc, Qp, and Qx are defined.
From the given data,
1.5
Kc = =6
0.5 × 0.5
0
Qc = = 0 at time t = 0 min
2×2
0.5
Qc = = 0.22 at time t = 10 min
1.5 × 1.5
(Provided that the reaction is occurring in a 1 L container, so that the concentration of the components
n
is equal to the number of given moles, since C = .)
V

Based on reaction quotient

Write the expression for Qc and Qp for the reaction,

1
NOBr ( g)  NO ( g) + Br2 ( g)
2

Solution

( pNO ) ( pBr ) 2
1
[NO][Br2 ] 2
Qp = 2
Qc =
( pNOBr ) [NOBr ]

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Application of reaction quotient

The equilibrium constant helps in predicting the direction in which a given reaction will proceed
at any stage. For this purpose, we calculate the reaction quotient Q.
Consider a general reaction, aA(g) + bB(g) ⇌ cC(g) + dD(g)
c d
C  D 
Then, Q c =   a  b ... (1)
 A  B

Qc
Case 1: Qc > Kc Kc
Qc Kc
Qc will be greater than Kc when the concentration of the
products is more than what can be present at equilibrium for
the given amount of the reactants according to equation (1). ⇒
In order to achieve equilibrium, the reaction should go in the
backward direction so that the concentration of the products
can be decreased as shown in Fig. 3 i.e., if Qc > Kc, the reaction
will proceed in the direction of the reactants (reverse reaction). Equilibrium R P
Fig. 3: Qc > Kc

Case 2: Qc < Kc Kc Qc Kc
Qc will be smaller than Kc when the concentration of the Qc
products is smaller than what can be present at equilibrium
for the given amount of the reactants according to equation (1). ⇒
In order to achieve equilibrium, the reaction should go in the
forward direction so that the concentration of the products can
be increased as shown in Fig. 4. i.e., if Qc < Kc, the reaction will R P Equilibrium
proceed in the direction of the products (forward reaction). Fig. 4: Qc < Kc
Case 3: Qc = Kc
If Qc = Kc, the reaction mixture is already at equilibrium so that there will be no shift in the reaction.

Difference between Keq and Q

Keq (Equilibrium constant) Q (Reaction quotient)

The concentrations represented in the ratio The concentrations represented in the ratio
are at equilibrium. may or may not be at equilibrium.

Rate of forward reaction = Rate of backward Rate of forward reaction may or may not be
reaction equal to rate of backward reaction.

Table 1: Comparison between equilibrium constant and reaction quotient

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Reaction direction

2
NH3 
The reaction quotient Q for N2(g) + 3H2(g) ⇌ 2NH3(g) is given as, Q c = 3
N2  H2 
When will the reaction proceed in the backward direction?
(a) Qc = Kc (b) Qc < Kc (c) Qc > Kc (d) Qc = 0

Solution

The concentration of the product should be more than that present at equilibrium for the given
amount of the reactants for the reaction to proceed in the backward direction. So, Qc > Kc.
Hence, option (c) is the correct answer.

Reaction direction

For the reaction

1
NOBr ( g)  NO ( g) + Br2 ( g), Kp = 0.15 atm1/2 at 90 °C. If NOBr, NO, and Br2 are mixed at this
2
temperature having partial pressures 0.1 atm, 0.08 atm, and 0.04 atm, respectively, check whether
Br2 is consumed or formed.

Solution

( pNO ) ( pBr ) 2
Qp = 2

( pNOBr )
p
pNOBr == 0.1
0.1 atm
atm
pNOBr = 0.1 atm
NO =
NOBr
p
p = 0.08 atm
0.08 atm
NO = 0.08 atm
pNO
p
pBr2 =
= 0.04 atm
0.04 atm
pBr2 = 0.04 atm
Br2

1
( 0.08 )( 0.04 ) 2
Qp =
( 0.1)
= 0.16 atm1/2

Kp = 0.15 atm1/2
The value of Qp is greater than Kp. Therefore, the concentration of the products is more than that
can be present at equilibrium for the given amount of the reactants. In order to achieve equilibrium,
the reaction should go in the backward direction so that the concentration of products can be
decreased. Hence, Br2 will be consumed.

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BOARDS MAIN ADVANCED

Predicting the Extent of Reaction

It is clearly understandable that,

K ∝ Concentration of products
1
K∝
Concentration of reactants

Equilibrium constant and position of equilibrium

1. Keq is significantly large (Keq > 103)

If Keq is significantly large, the concentration of the products will be significantly higher than the
concentration of the reactants, i.e., [Products] >> [Reactants].
Hence, we can conclude that the position of equilibrium lies far to the right (towards products)
and thus, the reaction has almost gone to completion by the time it attains equilibrium as
shown in Fig. 5.

R P R P R P
At time, t = 0 At time, t = t1 At equilibrium
Concentration

Concentration
Concentration

Time Time Time

Fig. 5: Keq is very large
Consider the reaction, 2H2(g) + O2(g) ⇌ 2H2O(l); Kc = 9.1 × 1080 at 25 °C
Here, Kc is extremely high because of the higher concentration of H2O with respect to the
reactants at equilibrium. So, we can conclude that almost all the H2 and O2 will be converted
into H2O by the time equilibrium is attained.
2. Keq is very small (K < 10−3)
If Keq is very small, the concentration of the products will be extremely lower than the concentration
of the reactants, i.e., [Products] << [Reactants].
Hence, we can conclude that the position of equilibrium lies far to the left (towards reactants)
and the reactants have barely been consumed as shown in Fig. 6.

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R P R P
At time , t = 0 At equilibrium
Concentration

Concentration

Time Time
Fig. 6: Keq is very small
Consider the reaction,
N2(g) + O2(g) ⇌ 2NO(g); Kc = 4.8 × 10−31 at 25 °C
Here, Kc is extremely low because of the low concentration of NO with respect to the reactants
at equilibrium.
Therefore, we can conclude that the reactants will barely be consumed.
3. Keq lies between 10−3 and 103
If Keq lies between 10−3 and 103, there will be substantial amounts of reactants and products.
The position of equilibrium lies between the reactants and the products.

Keq(Kc or Kp)

10−3 1 103
Both Reaction
Reaction
reactants and proceeds
hardly
products are almost to
proceeds
significant completion

Consider the reaction,

N2O4(g) ⇌ 2NO2(g); Kc = 4.64 × 10−3 at 25 °C
Here, Keq lies between 10−3 and 103. Therefore, we can conclude that there is a comparable
concentration of reactants and products, but the concentration of the products may be lower
than that of the reactants.

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Reaction completion

Which of the following reactions will tend to proceed farthest towards completion?
(a) H2(g) + Br2(g) ⇌ 2HBr(g); Kc = 1.4 × 10−21
(b) 2NO(g) ⇌ N2(g) + O2(g); Kc = 2.1 × 1030
(c) 2BrCl(g) ⇌ Br2(g) + Cl2(g); Kc = 0.415

Solution

The one with the highest Kc value is most likely to proceed the farthest towards completion.
i.e., 2NO(g) ⇌ N2(g) + O2(g); Kc = 2.1 × 1030
Hence, option (b) is the correct answer.

BOARDS MAIN ADVANCED

Degree of Dissociation (α)

The fraction of moles of the reactants that undergo dissociation to form products is known as
the degree of dissociation.

Total number of moles of reactant dissociated

α=
Initial moles of reactant

Percentage dissociation = α × 100 %

Consider the dissociation reaction,

PCl5(g) ⇌ PCl3(g) + Cl2(g)
2
Suppose 5 moles of PCl5(g) are taken and 2 moles of PCl5(g) dissociate, then, ⍺ = = 0.4
5
Percentage dissociation = ⍺ × 100
= 0.4 × 100 = 40%

PCl5 PCl3Cl2 PCl5 PCl3Cl2 PCl5 PCl3Cl2

⍺=0 ⍺ = 0.25 ⍺ = 0.5
Fig. 7: Dependence of α and concentration of reactants and products
The reactant concentration decreases and the product concentration increases when ⍺ increases
as shown in Fig. 7.
For 100% dissociation of reactants, ⍺ = 1.
Therefore, 1 is the maximum value of ⍺.

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This means that the maximum amount of reactant that can be dissociated = The number of
moles of reactant taken.
• ⍺ varies from 0 to 1.
• It can be fractional and has no units.

Total number of moles at equilibrium

Consider the general equilibrium, An(g) ⇌ nA(g) at volume of 1 L.

Before dissociation,
Number of moles of the reactant = a
Number of moles of the product = 0
After dissociation, at any time t,
Number of moles of the reactant = a − x
Number of moles of the product = nx
Total number of moles of reactant dissociated
α=
Initial moles of reactant
x
Thus, ⍺ = a
x = a⍺
The number of moles of the reactant after dissociation at any time = a − a⍺
The number of moles of the product after dissociation at any time = na⍺
An(g) ⇌ nA(g)

Before dissociation (mole) a −

At any time t a − a⍺ na⍺

The total number of moles at any time t = a − aα + naα

= a(1 − ⍺ + n⍺)
= a (1 − ⍺(1 − n))
= a [1 + (n − 1)⍺]
Equilibrium constant for the reaction,
[A]
n

Kc =
[ An ]
(naα )
n
eq
Kc =
a − aα eq

( naα )
n
eq
Kc =
a( 1 − α )eq

(As the volume is 1 litre, the concentration of each component becomes equal to the number of
moles.)

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