Chemical Equilibrium

Concept Equilibrium: -
The chemical equilibrium may be defined as “The state of reversible reaction when the two
opposing reactions occur at the same rate and the concentration of reactants and products do not
change with time”.
Or
When the rate of forward reaction becomes equal to the rate of backward reaction then the reaction
is said to be in equilibrium or chemical equilibrium.
In most reaction two more substance react to form products which themselves react to give back
the original substances. Thus “ A ” and “ B” may react to form “C ” and “ D ”, which react together to
reform “ A and B”.

A reaction which can go in the forward and backward direction simultaneously is called a reversible
reaction. Such a reaction is represented by writing a pair of arrows between the reactants and
products.

e.g.

Nature of Chemical Equilibrium: -

Let us consider the reaction.

If we start with A and B in a closed vessel the forward reaction begins to from C and D . The
concentrations of A and B decrease and those of C and D increase continuously. As a result, the
rate of forward reaction also decreases and the rate of reversible reaction increases. Finally, the rate
of reversible reaction equals, and the system attains a state of equilibrium.
Furthermore, the equilibrium of a reaction can be attained from both sides. Thus, the equilibrium
concentrations of the reactants and products are the same whether we start with A and B or C and
D.
Characteristics of Chemical Equilibrium: - (Nature)
There are same important characteristics of chemical equilibrium.
1. Constancy of Concentration: -
The concentrations of the substance involved in the reaction remain constant indefinitely at
a given temperature. The reaction mixture at equilibrium is known as equilibrium mixture.
The concentrations at equilibrium are called equilibrium concentrations.

2. Equilibrium can be Initiated from Either Side: -

The state of equilibrium of a reversible reaction can be approach e.g. we start with reactants
or products.
e.g.

The equilibrium is established if we start the reaction with 1 mole of I 2 and 1 mole of H2 or
with 2 moles of HI in vessel of the same volume the same mixture of H2, I2 and HI is obtained.

3. Equilibrium Cannot be Attained in an Open Vessel: -

The equilibrium cannot be established in an open vessel, the gaseous reactants or product
may escape into the atmosphere leaving behind no possibility of attaining equilibrium. In
case of liquid phase substance, the equilibrium is possible in open container.

4. A Catalyst Change the Equilibrium Point: -

 When a catalyst is added to a system in equilibrium, it speeds up the rate of both the
forward and the reverse reaction to an equal extant. Therefore, a catalyst cannot change the
equilibrium point except that it is achieved earlier. This enhances the rate of the reaction.
5. Value of Equilibrium Constant is Independent of Concentration of Initial
Concentration: -
The value of equilibrium constant does not depend upon the initial concentration of
reactants. It has been found that equilibrium constant must be the same when the
concentration of reacting species is varied over a wide range.
6. Gibbs Free Energy ∆ G = 0 at Equilibrium: -
At equilibrium the Gibbs free energy (G) is minimum and any change taking place at
equilibrium proceeds without change in free energy i.e. ∆ G = 0.
7. Rate Equality: -
At equilibrium the rate of forward and backward reaction is always equal.
8. Dynamic Equilibrium: -
The reversible reaction occurs simultaneously, and the equilibrium conditions are
maintained by the dynamic balance and the chemical equilibrium is dynamic equilibrium in
nature.
9. Chemical Equilibrium is Direction Independent: -
The equilibrium state is independent of the direction in which the reaction is occurs.

Types of Chemical Equilibrium: -

Chemical equilibrium may be classified into two groups.
1. Homogeneous Equilibrium.
2. Heterogeneous Equilibrium.
1. Homogeneous Equilibrium: -
When a chemical reaction occurs in a system consisting of a single phase, gas liquid or solid
and equilibrium is established it is homogenous equilibrium e.g.

2. Heterogeneous Equilibrium: -
When a chemical reaction occurs in a system consisting of a two or more phase. It is called
heterogeneous equilibrium.
e.g.

Law of Mass Action: -

In 1864, two Norwegian chemists C . M Goldberg and P .Waage postulated a generalization

called the law of mass action. After studied experimentally many equilibrium reactions.
Law of mass action states that “the rate of a chemical reaction is directly proportional to the active
masses of the reactants”.
OR
“The rate at which a substance reacts is proportional to its active mass and rate of a chemical
reaction is proportional to the product of the active masses of the reacting substance by the term
active mass is meant the molar concentration i.e. number of moles per liter.
Consider the following reversible reaction taking place at constant temperature.

According to the law of mass action the rate (r 1) at which A and B react is given by the equation.

Rate of Forward reaction ∝ [ A ] [ B ]

r 1=K 1 [ A ] [ B ] … … …(1)
[ ]=molar concentration
Where
[ A ]=molar concentration of A
[B]=molar concentration of B
K 1=Proportionality constant known as rate constant .
As the reaction proceeds the molar concentration of A and B decrease and the velocity of forward
reaction goes on decreasing with time.
Similarly, the rate of backward reaction ( r 1 ) is given as
Rate of Backward reaction∝ [ C ] [ D ]
r 2=K 2 [ C ][ D ] … … …(2)
Where
[C]∧[ D]=molar concentrations of C∧D respectively .
K 2=Rate constant of backward reaction .
Finally, a dynamic equilibrium is attained when the rate of the forward reaction becomes equal to
that of the backward reaction i.e.
r 1=r 2
From equation (1) and (2) we get
K 1= [ A ][ B ] =K 2 [ C ][ D ]
Rearranging
K 1 [ C ][ D ]
=
K2 [ A ] [ B]
If
K1
=K c
K2
Then
[ C ][ D ]
K c=
[ A ][ B ]

K c is known as equilibrium constant and it is simply the ratio of the rate constant of reversible
reaction. K c is independent of the concentration of the reactants and products but depends upon
the temperature and the nature of the reaction.

Law of Chemical Equilibrium and Equilibrium Constant: -

Consider the reaction

Rate of Forward reaction=r 1=K 1 [ A ][ B ]

 Rate of backward reaction=r 2=K 2 [ C ][ D ]
Since at equilibrium r 1=r 2
¿ follows that
K 1= [ A ][ B ] =K 2 [ C ][ D ]

K 1 [ C ][ D ]
=
K2 [ A ] [ B]
If
K1
=K c
K2
Then
[ C ][ D ]
K c=
[ A ][ B ]

K c is known as equilibrium constant and it is the ratio of the rate constant of forward reaction to the
rate constant of backward reaction. Where “c ” indicates that the value of equilibrium constant is
taken in terms of concentrations of reactants and product.
[ C ][ D ]
Equilibrium Constant K c =
[ A ][ B ]

Similarly, if a reaction of the types.

K c Will be expressed as

[ C ][ D ]
K c=
[A][A]
[ C ][ D ]
K c= 2
[ A]

So, the equilibrium constant expression for a reaction in general form may be written as

Where a , b , c and d are the coefficient of the substance A , B ,C and D respectively so the
equilibrium constant expression for this reaction will be,

c
K c =[C ] ¿ ¿
So, equilibrium constant in terms of concentration may be defined as
“The product of the equilibrium concentration of the products divided by the product of the
equilibrium concentration of the reactants with each term raised to a power equal to the coefficient of
the substance in the balanced equation”.
e.g.

K c =¿ ¿
The equilibrium constant is also expressed in different units of the reactants and products depending
upon the unit used.
When reactants and products are measured in terms of concentration units the equilibrium constant
is expressed by K c .
 [ C ]c [ D]d
K c= a b
[ A ] [B]
When reacting substances are in gaseous state then they can have measured in partials pressure
unit the equilibrium constant is expressed by K P.
c d
PC P D
K P= a b
PA PB
When the reacting substance are measured in moles fraction then equilibrium by K X .
c d
XC X D
K X= a b
X A XB
Similarly, the reacting substance can also be measured in molar units the equilibrium constant is
represented by K n.
c d
nC n D
K n= a b
nA nB

Relationship between K c , K P , K X ∧K n :-
Relation between KP and KC: -
Let us consider a general reaction

When all the substance (reactants and Products) are gases then equilibrium constant in terms of
partial pressure is written as,
c d
PC P D
K P= a b
… … …(1)
PA PB
If all the gases reacting are ideal, then according to ideal gas law.

PV =nRT
Or
n
P= RT
V
As
n
C=
V
P=CRT
Thus, the partial pressure of each substance will be
P A =[ A] RT ∨C A RT
PB =[B] RT∨C B RT
PC =[C] RT ∨CC RT
P D=[D ]RT ∨C D RT
Putting the value of each in equation (1)
K P=¿ ¿ ¿

c c d d
[C] [RT ] [D] [ RT ]
K P= a a b b
[ A ] [ RT ] [B] [RT ]
 c d c d
[C] [D] (RT ) (RT )
K P=
[ A ]a [ B]b (RT )a (RT )b
We know
K c =¿ ¿
So, the above equation becomes
c d
(RT ) (RT )
K P=K c
¿¿
c+d
(RT )
K P=K c
(RT )a+b
K P=K c ¿
If
∆ n=(c+ d)−( a+b)
Then
∆n
K P=K c (RT )
If
∆ n=0
Then
K P=K c
Relationship between KP and KX: -
Consider a reaction

Then KP will be
c d
PC P D
K P= a b
… … …(1)
PA PB
According to the Dalton Law of Partial pressure
Pi= X i P
Pi=∂ Pressure of a gas i.
X i =Moles Fraction of a gas i .
P=Total Pressure of the gases .
We can write the partial pressure of each gas A , B ,C and D .

P A =X A P
PB =X B P
PC = X C P
P D= X D P
Putting these values of each gas in equation (1) we get
K P=¿ ¿ ¿
Equation (2) can be written
c c d d
XC P . X D P
K P= a a b b
X AP . XBP
c d
X C X D P c Pd
K P= a b . a b … … …(3)
X A XB P P
We know
c d
XC X D
K X= a b
X A XB
Equation (3) takes the form
 c d
P P
K P=K X a b
P P
c+d
P
K P=K X a +b
P
(c+d )−(a +b)
K P=K X P
if
(c +d )– (a+b)=∆ n
∆ n=the difference ∈moles of product∧reactant .
∆n
K P=K X P
If
∆ n=0
K P=K X

Relation between KP and Kn: -

Consider the reaction

Equation constant for the above reaction in terms of partial pressure may be written as,
c d
PC P D
K P= a b
… … …(1)
PA PB
According to the Dalton’s Law of partial Pressure

Pi= X i P … … … (2)

Pi=∂ Pressure of i gas .

X i =Mole Fraction of i gas .
P=Total Pressure .
Mole Fraction for the above reaction of each gas is given
nA nA
X A= ∨
n A + nB + nC + n D N
As
N=n A +n B +nC + nD
The equation (2) for each reacting substance will be

nA
PA= P
N
nB
PB = P
N
nC
PC = P
N
nD
P D= P
N
Putting these values in equation (1) we get
K P=¿ ¿

c
K P=nC ¿ ¿
 c+d
P
c )d (
n n N
C D
K P= a a +b
b
n n P
( )
A B
N
Where
c d
nC n D
K n= a b
nA nB
Then
K P=K n ¿

∆n
P
K P=K n ( )
N
Where
∆ n=(c+ d)−(a+b)
When
∆ n=0
Then
K P=K n
We know
K P=K c ¿
K P=K X ¿
∆n
P
K P=K n ( ) if ∆ n=0then K P =K n
N
So
If
∆ n=0
Then
K P=K c =K X =K n

Example: -
3 o
4.0 g of H 2∧128 g of HI were taken∈a d m container at 40 0 C .
Calculate their active masses.
Solution:
No .of moles of H 2
The active mass of hydrogen[ H 2 ]= 3
Volume dm
4
2
The active mass of hydrogen[ H 2 ]= =1.0 g mol d m−3
2
No . of moles of HI
The active mass of the hydrogeniodide [ HI ]= 3
Volume dm
128
128 1
The active mass of the hydrogeniodide [ HI ]= =
2 2
−3
The active mass of the hydrogeniodide [ HI ]=0.5 g mol d m

Le Chatelier’s Principle and the effect of variable: -

 (Temperature, Concentration and Pressure on Equilibrium Constant)

In 1884, H .≤Chatelier a noted French chemist put forward a general principle which applies to all
system in equilibrium. He studied the effect of concentration temperature and pressure on many
chemical equilibriums.
Henry Le Chatellier Principle states that
“when a stress is applied on a system in equilibrium the system tends to adjust itself as to reduce the
stress”.
OR,
“If a system at equilibrium is subjected to a change of concentration, pressure or temperature, the
equilibrium shifts in the direction that tends to undo the effect of the change”.
If we add or remove some of a substance or some energy in any form, from a system or increase
or decrease pressure of a system at equilibrium and the equilibrium of system is there by disturbed,
the system will spontaneously readjust itself by shifting its equilibrium in the direction that will tend
to undo the imposed disturbance. There are many ways in which the stress can be cause on a
chemical equilibrium some of the are given below.
i. Changing the concentration of a reactant∨ product .
ii. Change the pressure of the system∨(Volume).
iii. Changing the temperature.

i. Effect of a change in Concentration: -

When the concentration of a system at equilibrium is changed either by adding reactant
or removing product, the rate of the reaction is increased in the direction as to produce
more product and regains equilibrium and the effect is minimized.
Let consider the effect of concentration on Ammonia Syntheses reaction.

When the amount of N 2 or H 2 is increased the amount of ammonia increase and the
rate of reversed reaction increases as to minimize the change in the concentration in the
reactants. Similarly, if N H 3 is removed the formation of the N H 3 increase in both
cases the equilibrium shifts to the right and the equilibrium is regained. If N H 3 is added
in the above reaction the backward reaction will increase and the equilibrium is shifted
to left and equilibrium is attained.
( a ) System at equilibrium with10 H 2 , 5 N 2 ,∧3 N H 3 for a total of
18 molecules .
( b ) The same molecules are forced into a smaller volume , creating
stress on the system.
( c ) Six H 2∧2 N 2 have been converted ¿ 4 N H 3 . A new equilibrium has
been established with 4 H 2 , 3 N 2∧7 N H 3 , a total of 14 molecules .
The stressis partially relieved by thereduction∈the total number of
molecules .

ii. Effect if a Change in Pressure: -

When a system of gaseous reactants and products at equilibrium is subjected to pressure
increase the equilibrium will shift in a direction which tends to decrease the pressure. The effect of
pressure is greater when there is difference in the number of moles of reactants and products.
Let consider a general reaction

When the number of the reactants is more than products in this case the increase in pressure
will favor the increase in concentration of the product and move and more products are formed, the
pressure effects is minimized. Similarly, if the pressure is decreased the rate of backward reaction is
increased and more and more product is decomposed, and the reactants concentration is increased,
and the effect is minimized.
 If the numbers of moles of the products are greater than reactants then increase in pressure will
increase the concentration of the reactants and hence the equilibrium is shifted to left and decrease
in pressure will shift, then equilibrium to the right and hence greater product is obtained. If the
number of moles of the reactants and products is the same, then there is no effect of pressure on
equilibrium.

iii. Effect of a Change of Temperature: -

When a system is at equilibrium upon changing the temperature i.e. increase in temperature
the equilibrium shift in a direction in which heat is absorbed. There are two types of reaction.
1. Exothermic Reactions .
2. Endo Thermic Reaction .
Exothermic Reactions .
Exothermic Reaction release heat so increase in temperature will not favor the reaction.

Equilibrium shifts to left and more reactants are reformed.

Endo Thermic Reaction .
The endothermic reaction the equilibrium shifts to right and more product are formed.
When forward reaction is endothermic the increase of the temperature will be given high yield of
product and vice versa.

In case of Ammonia the forward reaction is exothermic thus increase of temperature will favor the
backward reaction to get high yield of ammonia temperature must be decreased.