Chemical equilibrium

In Chemistry, we define chemical equilibrium as a state in which the rate of the forward reaction is equal
to the rate of the backward reaction. In other words, we can say it refers to the state of a system in which
the concentration of the reactant and the concentration of the products do not change with time. After that,
the system will not display any further change in their properties and it becomes constant. Here we will
study what is chemical equilibrium, what is equilibrium in Chemistry, and various factors affecting
chemical equilibrium.
Equilibrium Meaning in Chemistry
Chemical equilibrium definition refers to the state of a system where the concentration of the reactant and
the concentration of the products do not change with respect to time and the system does not display any
further change in properties. Chemical equilibrium is said to be achieved by the system when the rate of
the forward reaction is equal to the rate of the reverse reaction. When there is no further change in the
concentrations of the reactants and the products due to the equal rates of the forward and reverse
reactions, at the time point of time the system is said to be in a dynamic state of equilibrium.
Define Equilibrium
Let’s understand this with an example. Consider hydrogen and iodine gas. These gases react to form
hydrogen iodide. Here the reaction is given below:

H2(g) + I2(g) ⇌ 2HI(g)

Reaction A: Forward reaction H2(g) + I2(g) → 2HI(g)
Reaction B: Reverse reaction 2HI(g) → H2(g) + I2(g)
Initially, only the forward reaction occurs because HI was not present. As soon as some HI is formed, it
begins to decompose back into H2 and I2. After that, the rate of the forward reaction decreases while the
rate of the reverse reaction keeps on increasing. In the long run, the rate of the combination of H2 and I2
to produce HI becomes equal to the rate of decomposition of HI into H2 and I2. When the rates of the
forward and rate of reverse reactions become equal to one another, then the reaction has achieved its state
of balance.

Law of Mass Action

At constant temperature, the rate at which a substance reacts is proportional to its
active mass and the rate of a chemical reaction is proportional to the product of the
active masses of the reactants.

The mass action of a substance is expressed in parentheses by writing the formula or

symbol of the substance.

Applying Law of mass action for general reversible reaction

aA + bB cC + dD
Rate of forward reaction [A] a[B] b
or R f = K f [A] a [B] b
Similarly for backward reaction
R b = K b[C] c [D] d
At equilibrium K f [A] a[B] b = K b[C] c[D] d
 The active mass of a substance usually refers to its molar concentration. The molar
concentration of a substance is equal to the number of moles in that substance present in a
1 litre solution. Therefore

Active mass of a substance = molar concentration of a substance

= Number of moles of substance / absolute volume in litres

= Volume in grams of substance / Molecular weight of substance / Full volume in litres
The unit of active mass is mole/liter or M.

Active mass

 In gaseous reactions, the active masses of gases are equal to their molar concentrations.
 In dilute solutions, the active masses of solute are equal to their molar concentrations.
 In concentrated solutions, the active masses of solute are less than their molar concentrations. The reason
for this is that in concentrated solutions, the molecules of solute do not separate and remain as groups or
aggregates.

If a solid or liquid is present in the hetrogeneous phase, ie, it is not soluble in the phase in which the reaction
takes place, its molar concentration is constant and its active mass is assumed to be 1
Numerical example:

500 ml of a solution contains 15 grams of acetic acid and 8 grams of methanol. What
will be its active mass?

Answer: molecular weight of acetic acid (CH 3 COOH) = 2 x 12 + 4 x 1 + 2 x 16 = 60

Active mass of acetic acid (CH 3 COOH) = weight of (CH 3 COOH) in grams / atomic mass of
(CH 3 COOH) / full volume in litres

= 15/60/½

= 0.5 mole/litre
Molecule of Methanol (CH 3 OH) = 12 + 4 x 1 + 16 = 32
Active mass of methanol (CH 3 OH) = weight of (CH 3 OH) in grams / atomic mass of
(CH 3 OH) / full volume in litres
= 8/32 / ½
= 0.5 mole / litre

Types of Chemical Equilibrium

There are two types of chemical equilibrium:
i)Homogeneous Equilibrium
ii)Heterogeneous Equilibrium
Homogeneous Chemical Equilibrium
In this type of reaction, the reactants and the products of chemical equilibrium are all in the same phase It
is also divided into two types: (i) Reactions having the number of molecules of the products is equal to
the number of molecules of the reactants.

For example,H2(g) + I2(g) ⇌ 2HI(g)

N2(g) + O2(g) ⇌ 2NO(g) (ii)

Reactions having the number of molecules of the products is not equal to the total number of reactant
molecules.

For example, 2SO2 (g) + O2 (g) ⇌ 2SO3 (g)

COCl2(g) ⇌ CO(g) + Cl2(g)

Heterogeneous Chemical Equilibrium
In this type of reaction, the reactants, as well as the products of chemical equilibrium, are present in
different phases. Examples are given below:

CO2(g) + C(s) ⇌ 2CO(g)

CaCO3(s) ⇌ CaO(s) + CO2(g)

Heterogeneous equilibrium:
For example, if we take a container with ice and water at a temperature that is allowing the existence of
both the phases simultaneously, both ice and water are present in a state of equilibrium.
Problems on equilibrium constant
1. The equilibrium constant for the reaction of N2 with O2 to form NO equals
Kc = 1 × 10–30 at 25 °C:
N2(g) + O2(g) ⇌ 2NO(g)
Using this information, write the equilibrium constant expression and calculate
the equilibrium constant for the following reaction:
2NO(g) ⇌ N2(g) + O2(g)
2. Write the equilibrium-constant expression for Kc for each of the following

CO2(g) + H2(g) ⇌ CO(g) + H2O(l)

reactions:

(ii) SnO2(s) + 2CO(g) ⇌ Sn(s) + 2 CO2(g)

(i)

(iii) Cr(s) + 3Ag+(aq) ⇌ Cr3+(aq) + 3Ag(s)

(iv) 3Fe(s) + 4H2O(g) ⇌ Fe3O4(s) + 4H2(g)
(v) P (s) + 6Cl2(g) ⇌ 4PCl3(g)
3. A closed system initially containing 1.000 × 10–3 M H2 and 2.000 × 10–3 M I2
at 448 °C is allowed to reach equilibrium. Analysis of the equilibrium
mixture shows that the concentration of HI is 1.87 × 10–3 M. Calculate Kc at

H2(g) + I2(g) ⇌ 2HI(g)

448 °C for the reaction taking place, which is : ( ans: 51)

4. At 448 °C the equilibrium constant Kc for the reaction is 50.5.

H2(g) + I2(g) ⇌ 2HI(g)
Predict in which direction the reaction will proceed to reach equilibrium at 448 °C
if we start with 2.0 × 10–2 mol of HI, 1.0 × 10–2 mol of H2, and 3.0 × 10–2 mol of I2
in a 2.00-L container.
Reaction quotient Q
In chemistry, the reaction quotient Q relates the amounts of products and reactants
in a chemical reaction at a given point in time. If the reaction quotient is compared
with the equilibrium constant, the direction of the reaction may be known. This
example problem demonstrates how to use the reaction quotient to predict the
direction of a chemical reaction towards equilibrium.
 Problems on reaction quotient
1. Hydrogen and Iodine gas react together to form hydrogen iodide gas. The
equation for this reaction is:
H2(g) + I2(g) ↔ 2HI(g)
The equilibrium constant for this reaction is 7.1 x 102 at 25 °C. If the current
concentration of gases are
[H2]0 = 0.81 M
[I2]0 = 0.44 M
[HI]0 = 0.58 M
what direction will the reaction shift to reach equilibrium?
2. What is the Q value for this equation? Which direction will the reaction shift?
Given: CO(g)+H2O(g)⇌CO2(g)+H2(g) Kc = 1.0

[CO2(g)]= 2.0 M ; [H2(g)]= 2.0 M; [CO(g)]= 1.0 M;[H2O(g)]= 1.0 M

Find the value of Q and determine which side of the reaction is favored.Given K=0.5

HCl(g)+NaOH(aq)⇌NaCl(aq)+H2O(l) [HCl]=3.2;[NaOH]=4.3;
[NaCl]=6
Applications of Le-Chatelier's Principle

The principle may be stated as, 'if a system at equilibrium is subjected to a change in one or
more variables such as, pressure, temperature, and/or concentration, then the equilibrium shifts in
such a way so as to undo the effect of the change'.

I. In the Study of Physical Equilibrium

(A) Effect of temperature on solubility: Some solids absorb heat while some evolve heat on
dissolution. Hence according to this principle solubility of the former class of solids increases
with rise of temperature.

For example:

(i)

(ii)

With rise of temperature solubility of increases while that of decreases.

(B) Effect of pressure on solubility: Since on dissolution of gas volume decreases, hence on
increasing pressure, solubility of gas increases. On the other hand, if volume of the solution
increases on dissolution of solid then solubility of the solid decreases with rise of pressure.

On operating carbonated water (soft drinks) comes out, due to decrease of pressure, it’s
solubility decreases.

(C) Effect of temperature and pressure on melting of ice: Since ice melts with absorption of
heat and decreases in volume, hence both temperature and pressure effect the melting of ice.
Since the change of ice into water is an endothermic process hence with rise of temperature ice
melts into water. Since volume of ice is more than that of water so increase of pressure favour
melting.

(D) Effect of temperature and pressure on vapourization of water: When water changes into
vapour heat is absorbed hence rise of temperature is favourable but in this process volume of
vapour increases hence rise of pressure is not favourable for forward reaction.

II. In the study of Chemical Equilibrium

(A) Formation of ammonia (Haber's Process): The reaction is as follows:

Favourable conditions for forward reaction are:

(i) high pressure

(ii) low temperature and

(iii) excess of .

(B) Formation of nitric oxide:

Favorable conditions for forward reaction are:

(i) No effect of pressure

(ii) high temperature and

(iii) excess of .

(C) Formation of sulphur trioxide:

SO2(g) + O2(g) ⇌ SO3(g) + 196KJ/mole

Favourable conditions for forward reaction are:

(i) High pressure

(ii) low temperature and

(iii) excess of .

(D) Formation of nitrogen peroxide:

2NO2 (g) + ½ O2 (g) ⇌ N2O5 (g) + 55 KJ/mole

Favourable conditions for forward reach” on are as in the case (C)

(E) Oxidation of carbon monoxide by steam:

Favourable conditions for forward reaction are:

(i) no effect of pressure

(ii) low temperature and

(iii) excess of steam and CO.

(F) Dissociation of dinitrogen tetraoxide:

Favourable conditions for forward reaction are:

(i) low pressure

(ii) high temperature and
(iii) excess of .

(G) Dissociation of phosphorus pentachloride:

PCl5 PCl3 +Cl2 – Qk. Cal

Favourable conditions for forward reaction are :

(i) low pressure

(ii) high temperature and

(iii) excess of .
Continuous removal of gaseous product favors formation of more products.

What would happen if you changed the conditions by increasing the concentration of A?
According to Le Chatelier, the position of equilibrium will move in such a way as to counteract
the change. That means that the position of equilibrium will move so that the concentration of A
decreases again - by reacting it with B and turning it into C + D. The position of equilibrium
moves to the right.

This is a useful way of converting the maximum possible amount of B into C and D. You might
use it if, for example, B was a relatively expensive material whereas A was cheap and plentiful.
What would happen if you changed the conditions by decreasing the concentration of A?
According to Le Chatelier, the position of equilibrium will move so that the concentration of A
increases again. That means that more C and D will react to replace the A that has been removed.
The position of equilibrium moves to the left.

This is esssentially what happens if you remove one of the products of the reaction as soon as it
is formed. If, for example, you removed C as soon as it was formed, the position of equilibrium
would move to the right to replace it. If you kept on removing it, the equilibrium position would
keep on moving rightwards - turning this into a one-way reaction.
Using Le Chatelier's Principle with a change of pressure
This only applies to reactions involving gases:

What would happen if you changed the conditions by increasing the pressure?
According to Le Chatelier, the position of equilibrium will move in such a way as to counteract
the change. That means that the position of equilibrium will move so that the pressure is reduced
again.
Pressure is caused by gas molecules hitting the sides of their container. The more molecules you
have in the container, the higher the pressure will be. The system can reduce the pressure by
reacting in such a way as to produce fewer molecules.
In this case, there are 3 molecules on the left-hand side of the equation, but only 2 on the right.
By forming more C and D, the system causes the pressure to reduce.
Increasing the pressure on a gas reaction shifts the position of equilibrium towards the side with
fewer molecules.

What would happen if you changed the conditions by decreasing the pressure?
The equilibrium will move in such a way that the pressure increases again. It can do that by
producing more molecules. In this case, the position of equilibrium will move towards the left-
hand side of the reaction.
What happens if there are the same number of molecules on both sides of the equilibrium
reaction?
In this case, increasing the pressure has no effect whatsoever on the position of the equilibrium.
Because you have the same numbers of molecules on both sides, the equilibrium can't move in
any way that will reduce the pressure again.