Chemical Equilibrium

Chemical reactions are of two types:

Irreversible reaction

Chemical reactions in which the reactants are completely converted into the products are
called irreversible reaction. These reactions proceed in one direction, they occur
spontaneously and fast.

Examples:

i. 2 KClO3  2KCl + 3O2

ii. Cu2+(aq) + Fe (s)  Fe2+ (aq) + Cu (s)

iii. CaCO3 (s)  CaO (s) + CO2 (g) [in open vessel]

Reversible reaction

The chemical reactions which take place in both directions under the same conditions are
called reversible reaction.

Example:

i. CaCO3 (s) ↔ CaO (s) + CO2 (g) [in close vessel]

ii. NH4Cl (s) ↔ NH3 (g) + HCl (g) [in close vessel]

Chemical Equilibrium

Chemical equilibrium may be defined as the state of a reversible reaction, when the two
opposite reactions occur at the same rate and the concentrations of reactants and products not
change with time.

Let us consider the reaction

A+B C+D

At equilibrium,

The rate of forward reaction (rf) = The rate of backward reaction (rb)

If we start with A and B in a closed vessel, the forward reaction proceeds to form C and D.
The concentration of A and B decrease and those C and D increase continuously. As a result
the rate of forward reaction also decreases and the rate of the reverse reaction increases.
Eventually the rate of the two opposing reactions equals’ and at this point the reaction is said
to have reached the state of chemical equilibrium.

Md. Masudur Rahman |Assistant Professor (Chemistry), BEC

The state of chemical equilibrium can be shown graphically as follows:

Chemical equilibrium is Dynamic:

Let us consider a reaction A+B ↔ C+D which attains equilibrium, the concentration of A and
B, as also of C and D remain constant with time. Apparently it appears that the equilibrium is
dead. But it is not so. The equilibrium is dynamic, actually the forward and the reverse
reaction are taking place at equilibrium but the concentrations remain unchanged.

A C

↔ C + D ↔ A + B

B D

The dynamic nature of chemical Equilibrium can be easily understood on the basis of the
kinetic molecular model. The molecules of A and B in the equilibrium mixture collide with
each other to form C and D. Likewise C and D collide to give back A and B .Therefore
collisions of A and B giving C and D and collisions of C and D giving back A and B
continue to occur even at equilibrium while concentration remain unchanged.

Characteristic of chemical equilibrium:

1. Reversibility: Chemical equilibrium can only be established in case of
reversible reactions.
2. Incomplete reaction: The amount of reactants that react to produce the
product, the same amount of product is converted into the reactants again, i.e.;
the reaction never completes.
3. Position of equilibrium state: Either from the ractants or products but
equilibrium will be established always at the same position.
4. Reaction system: The raction system must be closed.

Md. Masudur Rahman |Assistant Professor (Chemistry), BEC

 5. Effect of diferent factors: At constant temperature and pressure.
6. Effect of catalyst: Catalyst have no effect on equilibrium.

Law of mass action

On the basis of observations of many equilibrium reactions, two Norwegian chemists

Goldberg and Waage suggested (1864) a quantitative relationship between the rates of
reactions and the concentration of the reacting substances. This relationship is known as law
of mass action. It states that-

The rate of a chemical reaction is proportional to the active masses of the reactants present
in it at constant temperature.
By the term active mass is meant the molar concentration i,e; the number of moles per liter.
Let us consider a general reaction,
A + B ↔C + D
And let [A], [B], [C], and [D] are the molar concentrations of A, B, C and D component.
According to the law of mass action,

Rate of forward reaction, rf α [A] [B]

= K1 [A] [B]

Rate of reverse reaction, rb α [C] [D]

= K2 [C] [D]

Where K1 and K2 are rate constants for the forward and reverse reaction.
At equilibrium,
Rate of forward reaction = Rate of reverse reaction

Therefore,
K1 [A] [B] = K2 [C] [D]

or K1 
C D
K 2
A B
C D
or, K  A B
C
[ K C
is called equilibrium constant. ]

The equation is known as equilibrium constant expression.

Example
Give the equilibrium constant expression for the reaction:
N2(g) + 3H2(g) ↔ 2NH3 (g)

K C
 [NH3]2 / [N2] [H2]3

Md. Masudur Rahman |Assistant Professor (Chemistry), BEC

Relation between Kc and Kp:

Let us consider a general gaseous reversible reaction-

aA(g) + bB(g) ↔ lL(g) + mM(g)

We can write the equilibrium constant in terms of concentration

L  Ml m

…………… (1)
K
A  B
C
= a b

Here, [A], [B], [L] and [M] are molar concentration of A, B, L and M respectively.

Again in terms of partial pressure

P P
l m

K P
= L M …………….. (2)
P P
a b
A B
Here, PA , PB , P L
and PM are the partial pressure of A, B, L and M respectively.

We know that for n moles of an ideal gas,

PV = nRT

n n
P= RT = CRT [ C = = conc. In moles / L ]
V V
If we substitute partial pressure P = CRT in equation (2), we get,

K =
CRT  CRT l m

CRT  CRT
L M
P a b

A B

C  C × RT  RT

l m l m

=
C  C RT  RT
L M
a b a b

A B

L  M × RT

l m
l  m a  b 

A  B
= a b

K P
= KC × RT Δn
[ Δn = (l + m) - (a +b) ]

The expressions for Kc and Kp and the relation between them for some reversible reactions
are illustrated below.

Md. Masudur Rahman |Assistant Professor (Chemistry), BEC

 Since Δng = (2) - (1+1) = 0

Kp = Kc

Since Δng = (1+1) - (1) = 1

Kp > Kc

Since Δng = (2) - (1+3) = -2

Kp < Kc

Since Δng = (1+3) - (2) = 2

Kp > Kc
Md. Masudur Rahman |Assistant Professor (Chemistry), BEC
i.e., The expressions for Kc and Kp and the relation between them depends on how we
expressed the reversible reaction as the stoichiometric equation.

KC = [CO2]

Since Δng = (1) - (0) = 1

Kp > Kc

In above expressions, the active masses of solids are taken as one and hence do not appear in
the expressions.

Problem-01 Write the Kc & Kp equation of the following:

2NO2↔N2O4

H2+I2↔2HI

N2+3H2↔2NH3

Problem-02 In the reaction H2 + I2 ↔ 2HI, the concentration of H2, I2 and HI at

equilibrium are 8.0, 3.0 and 28 mol/L. Find its Kc value.

Problem-03 At 298 K N2O4 dissociates into NO2. The partial pressure of N2O4 is 0.8
atm and equilibrium constant, Kp is 0.008 atm. Find out the value of Kc
and partial pressure of NO2 for the dissociation of N2O4.

Le Chatellier’s Principle
In a chemical system at equilibrium the rate of forward reaction is equal to the rate of
background reaction. Once if an equilibrium state is reached in a reversible reaction, it
remains unchanged if the external conditions are not changed. If the external factors like
temperature, pressure or concentration of any of the components of the reactants or products
are changed or a catalyst or inert substances is added, then the position of equilibrium has
been changed. The effect of these factors on equilibrium is explained by a French chemist
Henry Le Chatellier in 1888 in his famous Le Chatellier’s Principle. It states as:

“If a system in equilibrium is subjected to a change in temperature, pressure or

concentration of any of the components of the system, the equilibrium will shift so
as to reduce the effect of that change”

Md. Masudur Rahman |Assistant Professor (Chemistry), BEC

Effect of change of concentration
The change of concentration of any one of the reactants or products at equilibrium will cause
the equilibrium to shift in such a way that the effect of change of concentration is minimized.
Let us consider the dissociation reaction of PCl5 into PCl3 and Cl2:

PCl5 (g) ↔ PCl3 (g) + Cl2 (g)

At the equilibrium mixture the three components have certain concentration. Now if small
amount of Cl2 is added to the mixture, the concentration of Cl2 will increase. As at a constant
temperature, Kc remains constant, according to Le Chatellier’s Principle to keep Kc fixed
some amount of Cl2 will combine with PCl3 to form PCl5 so as to reduce the effect of Cl2
addition. So the position of equilibrium will shift to left side.

So we can write as-

Increase in conc. of any of the reactants shifts the equilibrium to the forward direction.
Increase in conc. of any of the products shifts the equilibrium to the backward direction.

Effect of temperature change

Temperature has dual effect on reversible reaction:
a) Effect on position of equilibrium
b) Effect on equilibrium constant

a) Effect on position of equilibrium

The effect of temperature change can be described on endothermic and exothermic reactions.
(i) Endothermic reaction
Endothermic reaction are those in which heat are required or absorbed. The following
reaction is-
N2 (g) + O2 (g) ↔ 2NO (g) ∆H = 180.75 kJ

In the above reaction the forward reaction proceeds by absorption of heat. According to Le
Chatellier’s Principle if heat is applied to the reaction the applied heat on absorption will shift
to the reaction towards right site and it will lead increase in NO production. As a result
position of equilibrium of equilibrium state shifts to right side.
On the other hand, if the temperature is decreased, then the production of NO also decreases
and equilibrium shifts to left side.

(ii) Exothermic reaction

Exothermic reaction are those in which heat are released. The following reaction is-

N2 (g) + 3H2 (g) ↔ 2NH3 (g) ∆H = - 92.38 kJ

In the above reaction the synthesis of NH3 from N2 and H2 the forward reaction is exothermic
and the backward reaction is endothermic. If the temperature of the reaction is increased, the
equilibrium shifts. Here, NH3 dissociates give back N2 and H2 by absorbing heat, so that the
supplied heat is minimized. This will lead to decrease in production of NH3.
On the contrary, if temperature of the reaction is decreased the forward
reaction will proceed to evolve heat yielding better production of NH3.

Md. Masudur Rahman |Assistant Professor (Chemistry), BEC

b) Effect on equilibrium constant
Generally, at constant temperature, the value of equilibrium constant of any reaction is
always fixed. But of the temperature is changed the value of equilibrium constant is also
changed. The dependence of equilibrium constant on temperature is clearly understood from
Van’t Hoff’s equation:

ΔH
log Kp = + Constant
2.303RT

This is a linear equation. If we draw log Kp vs 1 / T, then a straight line is obtained. From the
plot it is seen that, with the increase of temperature (1 / T decrease) the equilibrium constant
of endothermic reaction increases whereas the equilibrium constant of exothermic reaction
decreases with the increase of temperature.

Effect of pressure change

The change of pressure has significant effect-
i. If the reactants and the products are gaseous or either of them is gaseous.
ii. The number of moles of reactants and products are not same.

The change of pressure has no significant effect-

i. If one of the reactants or products or both are solids or liquids.
ii. The number of moles of reactants and products are same.

Application of pressure on gaseous reaction will reduce the volume and according to Le
Chatellier’s Principle, reduction of the volume of the gas will neutralize the applied pressure.
So its pressure is applied on the equilibrium of gaseous reactions, then direction of
equilibrium will shift to that side where total volume of the reaction components decreases.
Hence effect of pressure on equilibrium is of two types-

(a) Reactions involving reduction of volume

Consider the following reaction-

N2 (g) + 3H2 (g) ↔ 2NH3 (g)

Md. Masudur Rahman |Assistant Professor (Chemistry), BEC

In the above reaction of ammonia synthesis by Haber-Bosh method there are four (1+3)
moles of reactants and two moles of product. So, in a reaction vessel of fixed volume, the
pressure decreases due to decrease molar volume of the products.
Thus if the pressure is increased the equilibrium shifts to right and the effect of the increase
of pressure is minimized. The production of NH3 will be increased by increased pressure. On
the other hand, at decreased of pressure the equilibrium shift to left.

(b) Reactions involving volume expansion

Consider the following reaction-

2N2O5 (g) ↔ 4NO2 (g) + O2 (g)

In the above reaction the number of moles of reactant is 2 whereas the number of moles of
products is 5 (4+1). So, here the volume expands. Hence, if pressure is applied here there will
be reduction of volume to minimize the effect of pressure. As a result the position of
equilibrium will shift to the left (backward) that means production will decrease.

Problem: what will be the effect of pressure on the equilibrium of

a. CH4 (g) + 2O2 (g) ↔ CO2 (g) + 2H2O (g)
b. NO (g) + ½ O2 (g) ↔ NO2 (g)

Application of Le Chatellier’s Principle in industrial production

Production of ammonia of Haber-Bosh process:

The manufacture of ammonia by Haber-Bosh process is represented by the following way

N2 (g) + 3H2 (g) ↔ 2NH3 (g) ∆H = - 92.38 kJ

The above equation provides the following information

a. The reaction is exothermic

b. The reaction proceeds with a decrease in the number of moles.

(1) Low temperature: By applying Le Chatellier’s Principle, low temperature will

shift the equilibrium to the right. This gives greater yield of ammonia.

(2) High pressure: High pressure on the reaction at equilibrium favors the shift of the
equilibrium to the right. This is so because the forward reaction proceeds with a
decrease in the number of moles.

From the above points it is clear that low temperature is necessary for higher yield of
ammonia. But at relatively low temperature, the rate of reaction is slow and the equilibrium is
attained in a long time. So, for this reason an optimum condition is established for the
maximum production of ammonium. This are-

Optimum temperature: 450 - 550ºc

Pressure: 200 atm
Catalyst: Finely divided iron (Fe) containing molybdenum (Mo)
Md. Masudur Rahman |Assistant Professor (Chemistry), BEC