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Chemical reactions that proceed to completion forward direction only are known as irreversible
reactions.
Examples:
Precipitation reactions:
Ag+NO-3(aq) + Na+Cl−(aq) AgCl(s) + Na+NO−3 (aq)
Gas liberation reactions:
Zn + 2HCl ZnCl2 + H2 ↑
Neutralization reaction between strong acid and strong base:
HCl + NaOH NaCl + H2O

Chemical reaction that never go to completion in a definite direction and proceed in forward as
well as backward direction are known reversible reactions.
Examples:
Formation of Hydrogen Iodide
H2 + I2 ⇌ 2HI
Synthesis of Ammonia by Haber’s process
N2 + 3H2 ⇌ 2NH3
Formation of Ethyl Acetate ( Ester)
CH3COOH + C2H5OH ⇌ CH3COOC2H5 + H2O
Formation of Sulphur trioxide:
2SO2 + O2 ⇌ 2SO3

Definition:
“ A reversible reaction is said to be in a state of dynamic equilibrium when the rate of forward
reaction becomes equal to the rate of reverse reaction and concentration of all the substance
involved in the reaction remains unaltered.”
Explanation with the help of graph:

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Consider the following reversible reaction:

● At T=0 seconds concentration of products is zero.

● At T=0 seconds concentration of reactants is maximum.
● As the time passes, the rate of forward direction is decreased, and the rate of backward
reaction is increased. Eventually two reactions occur with the same rate. This is known as
Chemical Dynamic equilibrium.

Statement
“The rate of which a substance reacts is proportional to its active mass and the rate of chemical
reaction is proportional to the product of the active masses of the reactants.”
Explanation
By the term active mass, we mean molar concentration (Molarity), i.e no of mole per
liter.
Consider the following reversible reactions.

According to the law of mass action:

Rate α [A][B]
Rate = K [A][B]
Equilibrium constant expression ( Kc ) for a general reversible reaction:
Consider the following reversible reactions.

Consider a forward reaction

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According to the law of mass action:
Rate α [A]m [B]n
Rate = K1 [A]m [B]n
Consider backward reaction:

According to the law of mass action:

Rate α [C]x [D]y
Rate = K2 [C]x [D]y
At equilibrium
Rate of forward reaction = Rate of backward reaction
K1 [A]m [B]n = K2 [C]x [D]y

K1 = [C]x [D]y
K2 [A]m [B]n

[C] x[D] y
Kc = [A ]m [B] n

Definition of Kc
It is defined as,
“Equilibrium constant is the ratio of active masses of products and reactants at
equilibrium”
For a general reversible reaction

Kc = [C]x [D]y
[A]m [B]n
Definition of kp
In case of gaseous equilibrium, a partial pressure is used instead of concentration because
at a given temperature, the partial pressure of a gas is proportional to its concentration.
In this case, the equilibrium constant is expressed as Kp instead of Kc.
Kp is defined as,
“Equilibrium constant is the ratio of partial pressures of product and reactants at
equilibrium.”

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Consider the following gaseous equilibrium.

[P c] [P D ]
Kp = [P ] [P ]
A B
Relationship between Kc and Kp
There are three possibilities.
I. Kp = Kc-------------- ( a )
II. Kp > Kc -------------- ( b )
III. Kp < Kc -------------- ( c )
(a) When the reaction occurs with no change in volume of reactants and products then Kp will be
equal to Kc.
E.g H2 + I2 2HI
1 vol. 1 vol 2vol.
2vol. 2vol.
Volume on both sides is equal.
(b) When reaction with increase in volume, then Kp will be larger than Kc.
E.g 2NH3 N2 + 3H2
2 vol. 1vol. 3 vol.
2 vol. 4 vol.
2 volume of reactant produces 4 volume of products.
(c) When there is a decrease in volume then Kp will be smaller than Kc.
E.g 2SO2 + O2 2SO3
2 vol. 1 vol. 2 vol.
3 vol. 2 vol.
3 volume of reactant produces 2 volume of product.

(Uses of equilibrium constant expression Kc )

The knowledge of chemical equilibrium expression of a particular reaction is very important for
us because from the value of equilibrium constant Kc , we can judge the following two things and
in this way, we will get more knowledge about a particular reaction.
1. Prediction of direction of reaction.
2. Prediction of extent of reaction.

1. PREDICTION OF DIRECTION OF REACTION:

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Consider a gas phase reaction:
aA (g) + bB (g) cC (g) + dD (g)
For the above reaction
[C]c [D]d
Kc =
[A]a [B]b
Now we came across three possibilities.
[Initial conc. C]c [Initial conc. D]d
i) If > Kc
[Initial conc A]a [Initial conc B]b
The reaction will proceed to the left, i.e backward direction in order to achieve equilibrium state.
cC + dD aA + bB
[Initial conc. C]c [Initial conc. D]d
ii) If < Kc
[Initial conc A]a [Initial conc B]b
The reaction will proceed to the right, i.e forward direction in order to achieve equilibrium state.
aA + bB cC + dD
[Initial conc. C]c [Initial conc. D]d
iii) If = Kc
[Initial conc A]a [Initial conc B]b
The system is already at equilibrium and the concentrations of the reactants and products remain
constant.
2. PREDICTION OF EXTENT OF REACTION
From the value of Kc , we can predict the extent to which a reaction will occur.
(a) Large value of Kc
If Kc is very large the forward reaction is almost complete and reverse reaction does not
occur to an appreciable extent.
E.g 2O3 ) 3O2
C D

A B
For the above reaction, larger value
[O2]3
Kc = = 1055 Kc > 100
[O3]2
Ozone is almost completely decomposed into oxygen.
(b) Smaller value of Kc
If K is very small, it is predicted the forward reaction proceeds with negligible speed.
E.g 2HF H2 + F2
A B

C D
For the above reaction, smaller value
[H2] [F 2}
Kc = = 10-13 Kc < 1
[HF ]2

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HF is very stable unlike H2 and F2.
(c) Moderate value of Kc
If Kc is neither very large nor very low, the reaction occurs in both directions with the same
speed.
E.g N2 + 3H2 2NH3
C D

A B
For the above reaction,
[NH3]2
Kc = [N ] [H ] = 10
2 2
The equilibrium will be attained after a certain period.
DETERMINATION OF EQUILIBRIUM CONSTANT (KC) FOR HI SOLUTION
H2 + I2 2HI
i) Suppose ‘a’ mol/ dm of H2 and ‘b’ mol/ dm of I2 react in a sealed tube at 444 °C in the
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boiling Sulphur for some time.

ii) After some time, the equilibrium is established between the reactants and products.
iii) The equilibrium mixture is cooled to fix the equilibrium
iv) The tube bulb are opened in the solution of NaOH which absorbs only HI and I2.
v) The amount of unused H2 at equilibrium is ( a - x) moles/dm3 and the amount of unused I2 at
equilibrium is (b - x) moles / dm3.
vi) Thus 2x moles / dm3 of HI is produced.
vii) The equilibrium constant Kc is calculated.
H2 + I2 2HI
Initial concentration: a + b NIL
Equilibrium concentration: a-x +b-x 2x
According to the law of mass action,
[HI]2
Kc = [H2] [I2 ]
(2x)2
Kc = (a−x) (b−x)

4x2
Kc= ( a − x ) ( b − x)

Introduction

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 The equilibrium state of a chemical system varies with change in conditions such as
concentration, temperature, and pressure. The effect of such changes on the equilibrium state can
be predicted by Le-Chatelier’s principle.
Statement
“ If a system in equilibrium is altered in any way the system will be shift so as to
minimize or undo the effect of change.”
OR
“ If a system in equilibrium is distributed in anyway, e.g by changing the pressure
temperature or concentration, the system will respond in such a way as to minimize the effect of
the change.”
FACTORS AFFECTING THE BALANCE OF EQUILIBRIUM
1. Effect Of Concentration Change
a) By Increasing The concentration Of Reactants:
If an additional amount of any reactant A or B is added to the system, then the stress is
relieved as the forward reaction proceeds to a greater extent than the reverse reaction until
equilibrium is reestablished.
aA + bB cC + dD
b) By Increasing The Concentration Of Products:
If an additional amount of product C or D is added to the system, then the stress is
relieved as the reverse reaction proceeds to a greater extent than the forward reaction until
equilibrium is reestablished.
aA + bB cC + dD
2. Effect Of Pressure Change
A change of pressure on a system in equilibrium can affect the yield of products in a
gaseous reaction.
When a pressure on a gaseous system is increased, the system tends to reduce the volume to
undo the effect of increase in pressure. Thus, an increase in pressure will favour the reaction in
the direction that produces the smaller number of moles of gases.
If there is no change in number of moles of gases in a reaction, a pressure (volume) change does
not affect the equilibrium.
E.g 2NH3 N2 + 3H2
The increase of pressure shifts the equilibrium towards the reactant side to remove the constraint
of increased pressure. This is in accordance with the Le-Chatelier’s principle.
E.g PCl3 + Cl2 PCl5
The increase of pressure forces the equilibrium to be driven to the right hand side.
E.g H2 + I2 2HI
If volume is the same on both sides, pressure will have no effect on equilibrium.
3. Effect Of Temperature Changes:

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If the temperature of a system at equilibrium is changed, the magnitude of Kc changes and the
direction of equilibrium shift may be predicted.
There are two types of reversible reactions that are affected by Change in temperature.
(a) Exothermic reactions ( Heat liberating reactions )
A+B C + D + heat
OR
A+B C + D ; 𝚫H = -ve
Exothermic reaction are favoured at low temperature
(b) Endothermic reaction ( Heat absorbing reaction)
A + B + heat C +D
OR
A+B C + D ;H = +ve
Endothermic reaction are favoured at high temperature.
4. Effect Of Catalyst
A catalyst is a substance that affects the rate of a reaction without itself being consumed
in the process.
A catalyst has no effect on the equilibrium composition of a reaction mixture. In fact a catalyst
affects forward and reverse rate equally.

Ammonia By Haber’s Process

N2 (g) + 3H2 (g) 2NH3 (g) ; 𝚫H = -46.2 K.J/ mol
1vol + 3 vol 2 vol
4 vol 2 vol
The reaction between N2 and H2 to produce NH3 is accompanied by a decrease in volume and it
is exothermic.
1. Effect Of Concentration Change
If more N2 is added at equilibrium then according to Le-Chatelier’s principle, the
equilibrium is forced in forward direction in order to reduce the concentration of N2. This
increase the yield of NH3.
In actual practice however, there is no practical advantage in using excess N2 or H2. The two
gases are mixed in the theoretical ratio of 1:3 by volume.
2. Effect Of Pressure Change
The formation of ammonia proceeds with decrease in volume ( 4 volume on the reactant
side and 2 volume on the product side). The reaction is therefore carried out under high pressure.
The pressure varies from 400 - 1000 atm.
3. Effect Of Temperature Change

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 The formation of NH3 is exothermic, i.e heat is liberated in forward reaction. If at
equilibrium, temperature is kept low then according to Le-Chatelier’s Principle, the equilibrium
shift to forward direction where heat is liberated.
In actual practice, the reaction is carried out at high temperature of 450 - 500 ℃ which produces
and reduced yield at high rate.
A catalyst of finely divided iron is used to speed up the reaction.

Sulphuric Acid By Contact Process

2SO2 (g) + O2 (g) 2SO3 (g) ; 𝚫H = -395 K.J/ mol
2 vol. + 1 vol 2 vol
3 vol 2 vol
Formation of So3 is an exothermic reaction and it occurs with the decrease in volume.
1. Effect Of Concentration Change
If more O2 is added at equilibrium then according to Le-Chatelier’s principle, the
equilibrium is forced in forward direction in order to reduce the concentration of SO2 and O2 .
This increase the yield of SO3.
2. Effect Of Pressure Change
The formation of SO2 proceeds with decrease in volume ( 3 volume on the reactant side
and 2 volume on the product side). The reaction is therefore carried out under high pressure. The
pressure varies from 1.6 - 1.7 atm.
3. Effect Of Temperature Change
The formation of SO3 is exothermic, i.e heat is liberated in forward reaction. If at
equilibrium, temperature is kept low then according to Le-Chatelier’s Principle, the equilibrium
shift to forward direction where heat is liberated.
In actual practice, the reaction is carried out at high temperature of 450 - 500 ℃ which produces
and reduced yield at higher rate.

A catalyst V2O5 is used to speed up the reaction.

SOLUBILITY PRODUCT
Definition
1. Solubility
“The amount of solute present in a specific amount ( 100gm ) of solvent at a particular
temperature at saturation is known as Solubility.”
It is usually expressed in gm / dm3 or moles / d3.
2. Solubility Product (Kp)
“The product of molar concentration of ions of electrolyte in the saturated solution is
known as Solubility Product”

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 It is denoted by Ksp.
3. Saturated Solution
“The solution that contains the maximum amount of solute that it can hold at a particular
temperature is known as Saturated Solution.”

4. Unsaturated Solution
“The solution that contains less solute than that it can hold at a particular temperature is
known as Unsaturated Solution.”
5. Supersaturated Solution
“The Solution that is more concentrated than a saturated solution at a particular
temperature is known as Supersaturated Solution.”

Explanation / General Derivation Of Ksp

Consider a supersaturated solution of AgCl.
AgCl (s) Ag+(aq) + Cl-(aq)
(Undissociated) (Dissociated)
According to the law of mass action.
[Ag]+[Cl]−
Kc = [AgCl]
In a supersaturated solution, concentration of AgCl is constant ( K’ ) at a given temperature.
[Ag]+[Cl]−
Kc =
K′
’
Kc × K = [Ag+] [Cl-] [□ Kc × K’ = Ksp]

Ksp = [Ag+] [Cl-]

Application / Use Of Solubility Product
The solubility product Ksp is used to determine whether a precipitate should form from a
solution known ionic concentrations. The value of Ksp represents saturated solution.

(a) If Ionic Product = Solubility Product

If the product of ionic concentrations is equal to the solubility product, the solution is
saturated and no precipitation takes place.
(b) If Ionic Product < Solubility Product
If the product of ionic concentration is less than the solubility product, the solution is
unsaturated and no precipitation take place, and more amount of the solute can go into the
solution.
(c) If Ionic Product > Solubility product
If the product of ionic concentration is greater than the solubility product, the solution is
supersaturated and precipitation takes place until the ionic product is equal to Ksp.

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 Criteria For Precipitation
When ionic product is greater than the solubility product, the solution is supersaturated and
precipitation takes place.

Definition
“The suppression of ionization of an electrolyte by adding common ion ( positive or
negative) is known as Common ion effect.’’
OR
“ The decrease in the solubility of salt in a solution that already contains an ion common
to that salt is known as Common ion effect.”

Explanation
AgCl (s) Ag+(aq) + Cl-(aq)
(Undissociated) (Dissociated) [□common ion Cl-]
KCl (s) K+ (aq) + Cl- (aq)
Precipitation of AgCl is caused by adding Cl- or Ag+, With the addition of common ion [Cl- or
Ag+], the ionization of AgCl is suppressed. This is known as common ion effect.

Application Of Common Ion Effect In Salt Analysis

1. Detection Of Cations Of II Group
Cation of II and IV groups are precipitated as sulphides but under different conditions
due to their solubility products. In fact, the solubility of IV group sulphides is higher than that of
II groups of sulphides
In order to precipitate the sulphides of II group, H2S is passed through the original solution of
(OS) in the presence of HCl.
H2S 2H+ + S-2
HCl H+ + Cl-
Hcl furnishes H+ as common ions that shift the above equilibrium in backward direction
according to Le-Chatelier’s principle. In other words, addition of HCl suppresses the ionization
of H2S there by lowering the concentration of sulphide ions ( S-2 ) that is however just enough to
exceed the solubility product of II group sulphides. In this way, group II cations are precipitated
such as CuS, PbS, CdS etc.

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