UNIT 6.

EQUILIBRIUM
Reversible and irreversible reactions

A reaction that takes place in only one direction is called an irreversible reaction.

e.g. NaOH + HCl → NaCl + H2O

Reversible reactions are those which take place in both directions. i.e. here reactants combined to form
products and the products recombine to form reactants. E.g. Haber process for the preparation of ammonia
N2(g) + 3H2(g) → 2 NH3(g)

The process by which reactants are converted to products is called forward reaction and the process by
which products recombine to form reactants is called backward reaction. After sometimes, the rate of
forward reaction becomes equal to the rate of backward reaction and the reaction attains equilibrium.

Equilibrium is a state at which the concentration of reactants and products do not change with time.
Equilibrium is a state at which the rates of forward and backward reactions are equal.

Equilibrium is dynamic in nature. i.e. at equilibrium the reaction does not stop. The reactant molecules
collide to form products and the product molecules collide to form the reactants and the rates of these
reactions are equal.

Chemical Equilibrium :Equilibrium associated with chemical reactions is called chemical equilibrium.
Consider a hypothetical reaction, A + B→ C + D
As the reaction proceeds, the concentration of the reactants decreases and that of the products increases.
After sometimes, the two reactions occur at the same rates and an equilibrium state is reached. This can be
illustrated by the following graph.

After the equilibrium is attained, the concentration of the reactants and products become constant. At
equilibrium, the rate of forward reaction (rf) = the rate of backward reaction (rb)

Law of mass action: It states that the rate of a chemical reaction is directly proportional to the product of
the molar concentration of the reactants at constant temperature at any given time. The molar concentration
is also called active mass.

aA + bB → products , Rate of the reaction , r ∝ [A]a [B]b or r = k[A]a [B]b

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Law of Chemical Equilibrium and Equilibrium Constant

A + B →C + D
According to law of mass action,
Rate of forward reaction, rf = kf [A][B]
Rate of backward reaction, rb = kb[C][D]
At equilibrium,
the rate of forward reaction (rf) = the rate of backward reaction (rb).

Where Kc is called the equilibrium constant.

For a general reaction, aA + bB → cC + dD,

Law of Chemical Equilibrium :

It states that at constant temperature, the product of concentration of the products to that of the
reactants, in which each concentration terms is raised to a power which is equal to the stoichiometric
coefficients in the balanced chemical equation, has a constant value

➢ Equilibrium constant for the reverse reaction is the inverse of that for the forward reaction.
i.e. if the equilibrium constant for the reaction H2 + I2→ 2HI is Kc, then that for the reverse reaction
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2HI→ H2 + I2 is K’c = 𝐾𝑐

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3. Calculation of equilibrium concentrations

By knowing the value of equilibrium constant, we can calculate the equilibrium concentrations of reactants
and products.

Relationship between equilibrium constant (Kc), reaction quotient (Qc) and Gibbs energy (ΔG)

ΔG0 = – 2.303RT logKc

If ΔG is negative (<0), the process is spontaneous
If ΔG is positive (>0) , the process is non spontaneous.
Factors affecting equilibrium

The important factors affecting equilibrium are temperature, pressure, concentration and catalyst. The
effect of these factors on equilibrium state can be explained by using Le Chatlier’s Principle.

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Le Chatlier’s Principle.: It states that whenever there is a change in concentration, pressure or
temperature of a system at equilibrium, the system will try to readjust in such a way so as to cancel
the effect of that change.

1. Effect of concentration change

If we change the concentration of reactants or products in an equilibrium process, then according to Le

Chatlier’s principle, the system will try to reduce the effect of that change. For this the rate of either
forward or backward reaction changes.

In general, an increase in concentration of reactants increases the rate of forward reaction (i.e. the
equilibrium is shifted to the forward direction) and an increase in concentration of products increase the
rate of backward reaction rate (i.e. the equilibrium is shifted to the backward direction).

Eg1: N2(g) + 3H2(g) ⇌ 2NH3(g) (Haber process)

In Haber process for the preparation of ammonia, the amount of ammonia formed can be increased by
increasing the concentration of N2 or H2 or by removing NH3 from the reaction mixture.

2. Effect of temperature change

According to Le Chatlier’s principle, increase in temperature favours endothermic process and

decrease in temperature favours exothermic process. In a reversible reaction, if the forward reaction is
endothermic, the backward reaction will be exothermic.

N2(g) + 3H2(g) ⇌ 2NH3(g) ∆H = -92.38kJ/mol

Here since ∆H is negative, the forward reaction is exothermic. So to increase the production of NH3,
temperature should decrease. At higher temperature, the rate of backward reaction increases. i.e. the
ammonia formed is decomposed to N2 and H2.

3. Effect of pressure change

Pressure has its role only in gaseous reactions. In general, an increase in pressure shifts the equilibrium
in the direction of lesser number of gaseous and vice versa.
Thus in the reaction, N2(g) + 3H2(g) ⇌ 2NH3(g)
When the pressure increases, the system will try to reduce the pressure. This can be achieved by shifting
the reaction into the direction in which no. of moles decreases (since pressure is directly proportional to the
number of moles). So in this reaction, the equilibrium will shift to the forward direction.
If the volume of the reaction mixture is halved, the concentration and the partial pressure become doubled.
So the reaction is shifted to the direction in which the number of moles or volume decreases.
4. Effect of catalyst

A catalyst increases the rate of forward and reverse reactions that pass through the same transition state and
does not affect equilibrium

Ionic Equillibrium

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Acid – base concepts:

1. Arrhenius concept:

According to this concept,

Acids are substances which give hydrogen ion (H+ ) or hydronium ion (H3O + ) in aqueous solution.
e.g. HCl is an acid since it produces H3O + in aqueous solution.
HCl(l) + H2O(l) ⇌ H3O + (aq) + Cl- (aq)
Bases are substances which give hydroxyl ion (OH- ) in aqueous solution.
e.g. NaOH is a base
NaOH(s) + H2O(l) ⇌ Na+ (aq) + OH- (aq)
Note: H+ ions exist in water as hydronium ions (H3O + )
H+ + H2O ⇌ H3O +
Limitations: This concept is applicable only to aqueous solutions. Also it could not account for the
basicity of substances like NH3 which do not possess OH- ion.

2. The Bronsted – Lowry concept:

A substance which can donate a proton is called acid.

Eg: HCI + H2O ⇌ CI- + H3O+ (HCI is an acid)
A substance which can accept a proton is called base.
NH3 + H2O ⇌ NH4 + + OH- (NH3 is a base)

Conjugate Acid of the Base. The acid formed by a base by accepting proton is called conjugate acid of the
base. e.g. H3O+ is conjugate acid of H2O,

Conjugate Base of the Acid. The base formed by an acid by donating a proton is called conjugate base of
that acid, e.g. CI- is conjugate base of HCI

e.g: HCI + H2O ⇌ CI- + H3O+

Acid Base ( Conjugate base) (conjugate acid)
NH3 + H2O ⇌ NH4 + + OH-
Base Acid (conjugate acid) ( Conjugate base)
Here NH3 is a base since it accepts an H ion to form NH4 + and H2O is an acid since it donates an H+ ion
+

to form OH- . In the reverse reaction, NH4 + is an acid and OH- is a base.

The acid base pair that differs by only one proton is called a conjugate acid – base pair.
➢ If the acid is strong, its conjugate base is weak and vice versa. So in the above example Cl - is a weak
conjugate base of the strong acid HCl.
➢ Water can act both as acid and base. So it is an amphoteric substance.

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 *(More examples- Refer Notebook) Problems 6.12,6.13,6.14

3. Lewis concept:

➢ Substances which donate electron pair are called Lewis bases

➢ Substances which accept electron pair are called Lewis acids.

Eg: for Lewis acids are BF3, AlCl3,FeCl3 H+ , Co3+, Mg2+ Ag+ etc. (all cations)
Eg: for Lewis bases are NH3, H2O, OH-, Cl-, Br- etc.(all anions)
For a substance to act as Lewis acid, it should contain vacant orbitals and for a substance to act as Lewis
base, it should contain lone pairs of electrons.

e.g. BF3 + NH3 → BF3←NH3

The pH scale

pH is defined as the negative logarithm of the hydrogen ion or hydronium ion concentration in moles per
litre (i.e. molarity).

pH = - log[H+ ] or pH = - log[H3O +]

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Negative logarithm of hydroxyl ion concentration in mol/L is called pOH .

pOH = -log[OH- ]
➢ For pure water, at 298K , [H+ ] = 10-7. Therefore pH of pure water is 7.
➢ The pH scale was introduced by Sorensen. It contains numbers from 0 to 14.
➢ If the pH is less than 7, the solution is acidic, if it is greater than 7, it is basic and if it is 7, the solution
is neutral. If the pH is 0, 1, 2 etc., the solution is a strongly acidic and if it is 12, 13, 14 etc, it is strongly
basic.
➢ The pH of our blood is 7.4 and that of our saliva is 6.4. So blood is slightly basic and saliva is slightly
acidic.

*(Numericals-Refer note book)

Ionization constant (dissociation constant) of weak acid

Ka = cα2/ 1-α where c is the initial concentration of acid and α is the degree of ionization of weak acid
pKa = -log Ka
Larger the value of Ka or smaller the value of pKa, stronger is the acid

Ionization constant (dissociation constant) of weak base

Kb = cα2/ 1-α where c is initial concentration of baseand α is the degree of dissociation of weak base
pKb = -log Kb
Larger the value of Kb or smaller the value of pKb, stronger is the acid
Factors affecting acid strength

➢ Strength of H-A bond decreases the energy required to break the bond decreases and H+ is easily
released and acidic strength increases.
➢ Polarity of H-A bond increases, there is significant charge separation and acidic strength increases
➢ In the same group H-A bond strength is more important and acidic strength increases as the size of
anion increases.
HF < HCl < HBr < HI
➢ In the same period H-A bond polarity becomes the deciding factor for acidic strength.
CH4 <NH3 <H2O < HF

Common Ion Effect

It is the suppression of the dissociation of a weak electrolyte by the addition of a strong electrolyte
containing a common ion.

For e.g. consider the dissociation of acetic acid (a weak electrolyte).

CH3COOH(aq) ⇌ CH3COO--(aq) + H+ (aq)
If we add some sodium acetate (CH3COONa) to the above equilibrium reaction, the concentration of
acetate ion increases. Then according to Le-Chatlier’s principle, the equilibrium will shift towards left or,
the rate of forward reaction decreases. i.e. the dissociation rate of acetic acid decreases. This is known as
common ion effect.

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Another example is the dissociation of the weak base ammonium hydroxide
NH4OH ⇌ NH4 + (aq) + OH- (aq)
If we add some NH4Cl tothe above equilibrium process, the concentration of NH4 + increases and hence the
equilibrium shifted to the left. i.e. the dissociation rate of NH4OH decreases.

➢ Common ion effect is applicable in salting out of soap and in precipitation of group III cations

Buffer Solutions

Solution which resists the change in pH on dilution or with the addition of small amount of acid or
base is called Buffer solution.

There are two types of buffer solutions – acidic buffer and basic buffer.
1)Acidic buffer is a mixture of a weak acid and its salt with a strong base.
E.g. a mixture of acetic acid and sodium acetate acts as an acidic buffer around p H 4.75.
2)Basic buffer is a mixture of a weak base and its salt with a strong acid.
E.g. a mixture of NH4OH and NH4Cl acts as a basic buffer around pH 9.25.

Henderson-Hasselbalch equation for acidic buffer

Henderson-Hasselbalch equation for basic buffer

Solubility Equilibrium

The solubility of a salt in solvent mainly depends on the lattice enthalpy and solvation enthalpy. As a
general rule, for a salt to be able to dissolve in a particular solvent its solvation enthalpy must be greater
than its lattice enthalpy. Each salt has its characteristic solubility which depends on temperature.

We can classify salts on the basis of their solubility in the following three categories.

Solubility Product Constant

Consider the dissociation of a sparingly soluble salt in water. Since it dissolves only partially, there exists
an equilibrium between the undissolved solid and the ions.

E.g. Solution of barium sulphate (BaSO4)

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 Where Ksp is called the solubility product
constant or simply the solubility product.
Solubility product is defined as the product of the molar concentration of ions of a sparingly soluble
salt in a saturated solution.
If S is the molar solubility of BaSO4,
Then Ksp = S x S = S2
For a general salt AxBy, its dissociation can be denoted as:
AxBy(s) →xAy+ (aq) + yBx- (aq);

* Ksp = [Ay+] x [Bx- ] y

If the concentration in the above equation is not the equilibrium concentration, then Ksp is given by Qsp (
ionic produt).

At equilibrium, Ksp = Qsp

If Ksp > Qsp, the dissolution process occurs
If Ksp < Qsp, the precipitation of the salt occurs.

Solubility product and common ion effect found application in the purification of NaCl. If we take a
saturated solution of NaCl and pass HCl gas through it, then NaCl gets precipitated due to the increased
concentration of Cl- ions. NaCl thus obtained has very high purity

REFER THE NUMERICALS DONE IN THE NOTE BOOK