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Characteristics of Equilibrium Constant

1. It is fixed for a particular reversible reaction at certain temperature.

2. Its value does not depend upon the initial concentration of reactants.
3. Value of equilibrium constant is not affected by use of catalyst.
4. It gives relative idea about the extent to which the reaction proceeds. If K>1, the
reaction is more in forward direction and if K<1, the reaction is less in forward
direction.
5. It depends upon the temperature. For endothermic reversible reaction, it is directly
proportional to the temperature and for exothermic reversible reaction, it is
inversely proportional to the temperature.
6. Equilibrium constant for the forward reaction is reciprocal to the equilibrium
constant for backward reaction i.e. if equilibrium constant is large in one direction it
will be small in opposite direction.

Equilibrium Constant in terms of partial pressure (KP)

Equilibrium constant of reversible reaction can be expressed in terms of concentration of

the chemical species. For gaseous reaction, the equilibrium constant can also be expressed
in terms of partial pressure of chemical species.

Partial pressure of gaseous substance is directly proportional to its molar concentration

which is given as:

PV = nRT
n
P= RT, i.e. P = CRT. So, P∝ C [Since, RT = constant]
V

Where, P = Partial pressure

V = Volume in L

n = No. of moles

R = Universal gas constant

T = Absolute temperature

C = Molar concentration of chemical species

For a reversible reaction,

aA(g) + bB(g) cC(g) + dD(g)

Using law of mass action, at equilibrium state

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(PC )c (PD )d
Equilibrium const. in terms of pressure (KP) =
(PA )a (PB )b

Where PA, PB, PC and PD are the partial pressure of A, B, C and D respectively.

Relationship between KC and KP

For given reversible reaction,

aA(g) + bB(g) cC(g) + dD(g)

Applying law of mass action at equilibrium,

[C]c [D]d
Equilibrium const. in terms of concentration, Kc = . . . . . . . . . . . . . (i)
[A]a [B]b

Where [C], [D], [A] and [B] are molar concentrations of C, D, A and B respectively.

(PC )c (PD )d
Similarly, equilibrium const. in terms of pressure, (KP) = . . . . . . . . . . . . . . . (ii)
(PA )a (PB )b

Where PC, PD, PA and PB are partial pressure of C, D, A and B respectively.

From ideal gas equation,

PV = nRT
n
P= RT
V

Or, P = CRT [C = n/V = molar concentration]

∴ PA = CART, PB = CBRT, PC = CCRT and PD = CDRT

Substituting the value of PA, PB, PC and PD in equation (ii)

(CC RT)c (CD RT)d

KP =
(CA RT)a (CB RT)b

(CC )c (CD )d (RT)c (RT)d

or, KP = ×
(CA )a (CB )b (RT)a (RT)b

[C]c [D]d
or, KP = × (RT)(c + d) – (a + b) . . . . . . . . . . . . . . . (iii)
[A]a [B]b

Here, CC, CD, CA and CB are molar conc. of C, D, A and B respectively. Hence, they are
replaced by the concentration terms [C], [D], [A] and [B] respectively.

[C]c [D]d
From equation (i), Kc = . So, equation (iii) will be
[A]a [B]b
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∴ KP = KC (RT)∆n . . . . . . . . . . . . . . . . (iv)

Where, ∆n = (No. of moles of gaseous products) – (No. of moles of gaseous reactants)

Equation (iv) is the expression that relates KP and KC.

Cases:

(a) When ∆n = 0 then Kp = Kc

(b) When ∆n = +ve then Kp > Kc
(c) When ∆n = -ve then Kp < Kc

Le-Chatelier’s Principle
Effect of change in temperature, pressure and concentration on equilibrium state of
reversible reaction was studied by Henry Le-Chatelier in 1884 and put forward a
generalization called Le-Chatelier’s principle.
The principle states that- When a system at equilibrium is subjected to change in
concentration, temperature and pressure then the equilibrium shifts in that direction
where the effect of change can be minimized.
The principle can be explained as below.
(a) Effect of change in concentration:
When concentration of any chemical substance is increased then the quilibrium
shifts to opposite side to minimize the effect of change in concentration. If
concentration of reactants is increased then equilibrium shifts to the right hand side
that is product side.
(b) Effect of change in temperature:
On increasing the temperature of a system the equilibrium shifts to the direction
where heat is absorbed. Hence, in endothermic reaction when temperature is
increased then the equilibrium shifts to the product side and in exothermic reaction
equilibrium shifts to the reactant side on increasing temperature.
(c) Effect of change in pressure:
Increase in pressure shifts the equilibrium to that direction where volume is
decreased. So the reaction which proceeds by the decrease in the volume is
favoured at high pressure.

Applications of Le-Chatelier’s principle

This principle is applicable to the physical as well as chemical equilibrium as

explained below.

[A] In physical equilibrium:

1. Let us consider the equilibrium state in melting of ice

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Ice + heat water (liquid)

 Effect of change in temperature:

Since melting of ice is endothermic process when temperature is increased then the
equilibrium shifts to the product side by forming more water.
 Effect of change in pressure:
As we know the volume of ice is higher than the volume of water, when pressure is
increased then equilibrium shifts to the product side by forming more water. This is
why at higher pressure melting temperature of water decreases.

2. Dissolution of gas in water

Gas + water aqueous solution of gas + heat

 Effect of change in temperature:

Since dissolution of gas in water is exdothermic process when temperature is
increased then the equilibrium shifts to the reactant side. Hence, the process is
favoured at low temperature.
 Effect of change in pressure:
As the dissolution of gas in water decreases the volume, high pressure is in favour of
the process. It means increase in pressure shifts the equilibrium to the product side.
This is why aerated drinks are kept under high pressure.

[b] In chemical equilibrium:

1. Let us take the example of formation of ammonia from nitrogen and hydrogen

N2 + 3H2 2NH3 + heat (i.e. ∆H = -ve)

(a) Effect of change in concentration:

When concentration of N2 or H2 is increased at equilibrium then the quilibrium shifts
to the forward side to minimize the effect of change in concentration. Thus higher
concentration of reactants is in favour of better yield of ammonia.
(b) Effect of change in temperature:
As the reaction is exothermic in nature, on increasing the temperature of the system
the equilibrium shifts to the reactant side that is backward side. Therefore, high
temperature is not in favour of better yield of NH3.
(c) Effect of change in pressure:
In above reaction 1 volume of N2 reacts with 3 volumes of H2 to produce 2 volumes
of NH3. So, when pressure is increased then the equilibrium shifts to the product side
as the volume of product side is low. Hence, high pressure is in favour of better yield
of ammonia.