Revision Notes

Class 11 Chemistry
Chapter 7 – Equilibrium

Introduction:
An important in numerical and biological process is meant to be chemical
equilibrium. When a liquid evaporates in a closed container, molecules with
relatively higher kinetic energy escape the liquid surface into the vapour phase
and number of liquid molecules from the vapour phase strike the liquid surface
and are retained in the liquid phase. It gives rise to a constant vapour pressure
because of an equilibrium in which the number of molecules leaving the liquid
equals the number returning to liquid from the vapour. Then the system has
reached equilibrium state at this stage. Thus, at equilibrium, the rate of
evaporation is equal to the rate of condensation. It may be represented by
H 2O(l) H 2O(vap)
The above double arrow indicates that the process simultaneously going in both
directions. The equilibrium mixture means the mixture of reactants and products
in the equilibrium state is called an equilibrium mixture.

Equilibrium in physical process:

we observe some physical process then the characteristics of system at
equilibrium are better understand. The most important and familiar examples are
phase transformation process. Eg.
solid liquid
liquid gas
solid gas

a) Solid-liquid equilibrium:
At particular temperature and pressure the ice and water are in equilibrium. The
normal melting point or normal freezing point of the substance is the temperature
at which the solid phase and liquid phases are equilibrium for any pure substance
at atmospheric pressure. When the system at dynamic equilibrium will follow the
conditions:
• Both the opposing processes occur simultaneously
• Both the process occurs at the same rate then the amount of ice and water
remains constant.

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b) Liquid-vapour equilibrium:
The number of water molecules from the gaseous state into liquid state increases
until the equilibrium reached.
i.e rate of evaporation = rate of condensation
H 2O(l) H 2O(vap)
The equilibrium water pressure means at which pressure the water molecules
remains constant at given temperature and vapour pressure of water increase with
temperature. The evaporation of liquid depends on,
● The nature of the liquid
● The amount of liquid
● The applied temperature
For example in a closed vessel water and water vapour are in equilibrium position
at atmospheric pressure (1.031 bar) and at 1000 C . Which means that for any pure
liquid at one atmospheric pressure (1.0301 bar), then the normal boiling point is
said to be the temperature at which liquid and vapours are at equilibrium.

c) Solid – vapour equilibrium:

The examples of this type system considered when solids sublime to vapour
phase.
I 2 (solid) I 2 (vapour)
Camphor(solid) Camphor(vapour)
NH 4Cl(solid) NH 4Cl(vapour)

General characteristics of Equilibrium involving physical processes:

Following characteristics are common to the system at equilibrium for which the
physical processes are discussed above:
● At a given temperature, the equilibrium possible only in closed systems
● If both the opposing processes occur at the same rate then the system is
dynamic at stable condition.
● In a system, all measurable properties are remains constant.
● Equilibrium is characterized by constant value of one of its parameters
given, and then it is attained for a physical process.

Equilibrium in chemical processes:

Compared to physical systems chemical reactions also attain a state of
equilibrium. Those chemical reactions can occur both in forward and backward
directions. The chemical equilibrium is dynamic in nature when the rates of
forward and backward become equal with the concentrations and products are
remains constant.
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 ● Reversible reactions
Consider a general case of a reversible reaction
A+B C+D
With passing time, there is decrease in the concentration of reactants A and B,
the increase in the concentration of products C and D which leads to a decrease
in the rate of forward reaction and an increase in the rate of backward reaction.

When the two reactions occur at the same rate and system will reaches a state
of equilibrium.
● Irreversible reactions
The products formed will not react back the reactants under same
conditions; it is called the Irreversible reaction. These reactions cannot take
place in the reverse direction.
A+ B→C+ D
● It is state of minimum Gibb’s energy
● dG = 0andG = 0 at this state
● Rate of forward reaction = rate of backward reaction
● This equilibrium is dynamic and stable in nature

Dynamic Nature of Chemical Equilibrium:

This dynamic nature of chemical equilibrium can be explained by the synthesis
of ammonia by Haber’s process. This process is starts with definite amounts of
N 2 & H 2 and carrying out reaction when equilibrium is attained at particular
temperature. At equilibrium the concentrations of N 2 ,H 2 & NH 3 are remains
constant.

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Representing the attainment of equilibrium for the reaction,
NH 3 (g) + H 2 (g) 2NH 3 (g)

Characteristics of Chemical Equilibrium:

● The concentration of each of the reactants and the products becomes
constant at equilibrium.
● The rate of forward reaction becomes equal to the rate of backward reaction
at equilibrium and hence equilibrium is dynamic in nature.
● None of the products is allowed to escape out or separate out as a solid
then only chemical equilibrium can be established.

Equilibrium constant:
An equilibrium mixture is a mixture of reactants and products in the equilibrium
state.
Consider a general reversible reaction,
A+B C+D
Where A and B are reactants, C and D are products in the above balanced
equation.
[C][D]
Kc =
[A][B]
Where K c is Equilibrium constant and expressed in concentrations of molL−1 .
At a given temperature, the product of concentrations of the reaction products
raised to the respective stoichiometric coefficient in the balanced chemical
equation divided by the product of concentrations of the reactants raised to their
individual stoichiometric coefficients has a constant value. This is known as the
Equilibrium Law or Law of Chemical Equilibrium.
The equilibrium constant for general reaction,

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 aA + bB cC + dD
Equilibrium constant expressed as,
[C]c [D]d
Kc =
[A]a [B]b
Where [A], [B], [C] and [D] are the equilibrium concentrations of the reactants
and products.
The product of the molar concentrations of the products, each raise to the power
equal to its stoichiometric coefficient is divided by the product of the molar
concentrations of the reactants, each raised to the power equal to its
stoichiometric coefficient is constant at constant temperature is called
Equilibrium Constant.

Characteristics of Equilibrium Constant:

● The value of the equilibrium constant for a particular reaction is always
constant depending only upon the temperature of the reaction and is
independent of the concentrations of the reactants with which we start or
the direction from which the equilibrium approached.
● The value of equilibrium constant in inversed when the reaction is
reversed.
● The equilibrium constant for the new equation is square root of K. (i.e,
K ), when the equation is divided by 2.
● The equilibrium constant for new equation is the square of K (i.e, K2 ),
when the equation is multiplied by 2.
● By the addition of catalyst to the reaction will not affect the value of the
equilibrium.

Predicting the Extent of reaction:

If the value of K c  103 will be high, then the equilibrium reaction is forward
dominant.
If the value of K c  10−3 will be low, then the equilibrium reaction is backward
dominant.
Moderate value of K c (between 103 and 10−3 ) dominates equilibrium neither
directions.

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Predicting the Direction of the Reaction- Reaction Quotient:
We can predict the direction in which reaction will proceed at any stage with the
help of the equilibrium constant. Reaction Quotient Q will calculate for this
purpose. The same way as the equilibrium constant K c , Reaction Quotient will
define are not necessarily equilibrium values.

aA + bB cC + dD
[C]c [D]d
Qc =
[A]a [B]b
● the reaction proceeds in the direction of reactants when Q c  K c
● the reaction proceeds in the direction of products when Q c  K c
● the reaction mixture is already at equilibrium when Q c = K c

Calculating Equilibrium Concentrations:

In case of a problem in which we know the initial concentrations but do not know
any of the equilibrium concentrations, the following three steps shall be followed:
Step 1. Write the balanced equation for the reaction.
Step 2. Under the balanced equation, make a table that lists for each substance
involved in the reaction:
(a) The initial concentration,
(b) The change in concentration on going to equilibrium, and
(c) The equilibrium concentration.
In constructing the table, define x as the concentration (mol/L) of one of the
substances that reacts on going to equilibrium, then use the stoichiometry of the
reaction to determine the concentrations of the other substances in terms of x.
Step 3. Substitute the equilibrium concentrations into the equilibrium equation
for the reaction and solve for x. If you are to solve a quadratic equation choose
the mathematical solution that makes chemical sense.
Step 4. Calculate the equilibrium concentrations from the calculated value of x.
Step 5. Check your results by substituting them into the equilibrium equation.

Relationship between equilibrium constant and Gibbs free energy:

The value of equilibrium constant for a reaction does not depend on the rate of
reaction.
● If change in Gibbs free energy G is negative, then the reaction proceeds
in the forward reaction with spontaneity.
● If change in Gibbs free energy G is positive, the products of the forward
reaction shall be converted to reactants with non-spontaneous process.
● If the change in Gibbs free energy is Zero, then the reaction at equilibrium
and there is no longer any free energy left to drive the reaction.
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A mathematical expression of this thermodynamic view of equilibrium can be
described by the following equation:
G = G  + RT ln Q
Where Q is Reaction Quotient. And G  is standard Gibbs free energy.
At equilibrium, when G = 0 and Q c = K c
G = G  + RT ln K c = 0
G  = − RT ln K c
G 
ln K c = −
RT
G 
−
K=e RT

from the above equation, from the values of G , the reaction spontaneity can
be interpreted.

Homogeneous Equilibria:
In a equilibrium system, all the reactants and products are in same phase is known
as Homogenous system.
For example,
N 2 (g) + 3H 2 (g) 2NH 3 (g)
In the above reaction all reactants and products are in gaseous phase.
CH 3COOC 2 H 5 (aq) + H 2O(l) CH 3COOH(aq) + C 2H 5COOH(aq)
In the above reaction, all reactants and products are homogeneous solution phase.

Heterogeneous Equilibria:
In a equilibrium system having more than one phase is called heterogeneous
equilibrium. The familiar example for this type of system is the equilibrium
between water vapour and liquid water in a closed container.
H 2O(l) H 2O(vap)
Similarly, there is equilibrium between a solid and its saturated solution is a
heterogeneous equilibrium.
Ca(OH) 2 (s) Ca +2 (aq) + 2OH − (aq)

Le Chatelier’s principle:
This principle helps to decide what course of reaction adopts and make a
qualitative prediction about the effect of changes in conditions on equilibrium.
It states that, “a change in any of the factors that determine the equilibrium
conditions of a system will cause the system to change in such a manner so as to

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reduce or to counteract the effect of the change.”
This principle is applicable for all physical and chemical equilibrium systems.
a) Effect of concentration change:
Generally equilibrium disturbed by addition or removal of any reactant or
product. The Le Chatelier’s principle predicts that:
● The concentration of added reactant or product is relieved by the
direction of net reaction that consumes the added substance.
● The concentration of removed reactant or product is relieved by the
direction of net reaction that replenishes the added substance.
“When the concentration of any of the reactants or products in a reaction at
equilibrium is changed, the composition of the equilibrium mixture changes so as
to minimize the effect of concentration changes”.

b) Effect of temperature change

Because of the Reaction Quotient Q no longer equals to equilibrium constant
when equilibrium is disturbed by change in the concentrations, pressure, or
volume and further the composition of the equilibrium mixture changes.
The value of the equilibrium constant changed when a change in the temperature
observed.
Generally temperature change dependence of equilibrium constant depends on
the sign of the H for the reaction.
● If H is negative, then the equilibrium constant of the exothermic
reaction decreases because of temperature increases.
● If H is positive, then the equilibrium constant of the endothermic
reaction increase because of temperature decreases.

c) Effect of pressure change

When the total number of moles of gaseous products is different, then a
pressure change obtained changing the volume can affect the yield of
products in case of gaseous reaction. Le-Chatlier’s principle is applied to
heterogeneous equilibrium the effect of pressure changes on solids and
liquids can be ignored because the volume of a solution or liquid is nearly
independent of pressure.

d) Effect of volume change

Effect of increase of pressure is equivalent to the effect of decrease of
volume.
So the effect of decrease in volume will be shifted towards the equilibrium
in the direction in which the number of moles decreases.

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e) Effect a catalyst
The chemical substance which increases the rate of chemical reaction by making
available a new low energy pathway for the conversion of reactants to products.
Catalyst increases the rate of forward and reverse reactions that pass through the
transition state which does not affect the equilibrium.
For example: contact process
2SO 2 (g) + O 2 (g) 2SO3 (g);K c = 1.7  10 26
the oxidation of sulphur di oxide to sulphur trioxide partially very slow.
So, Platinum or divanidium pentaoxide ( V2O5 ) is used as catalyst to increase the
rate of reaction.

f) Effect of inert gas addition

If an inert gas such as argon is added and the volume kept constant this does not
take any part in the reaction. Thus, the equilibrium remains undisturbed. Because
the addition of inert gas does not change the partial pressures or the molar
concentrations of substances involved in the reaction at constant volume.

Ionic equilibrium in solution:

The effect of change in the concentration on the direction of equilibrium,
incidentally come across the following equilibrium which involves ions:
Fe+3 (aq) + SCN − (aq) [Fe(SCN]2+ (aq)
There are equilibria reactions involve ions only. According Micheal Faraday,
classified the substances two categories based on their ability to conduct
electricity. Those are electrolytes and non-electrolytes. Because of presence the
ions, the solution of electrolytes conduct electricity.
For example an aqueous solution of NaCl is dissociated completely into Na + and
Cl− ions, because of almost 100% ionization in case of sodium chloride. But in
case of acetic acid which is weak electrolyte, 5% ionization takes place. Hence,
equilibrium is established between ions and unionized molecules in weak
electrolytes. This type of equilibrium involving ions in an aqueous solution is
known as Ionic Equilibrium.

Classification of electrolytes:
Based on the strength of electrolytes are classified into two categories:
a) Strong electrolytes
The electrolytes which are easily break into ions with complete dissociation are
known as strong electrolytes.
Eg: HCl, NaCl, NaOH,HNO3 ,HClO 4 ,H 2SO 4

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b) Weak electrolytes
The electrolytes which are partially dissociation are known as weak electrolytes.
Eg: CH 3COOH, NH 4OH,HCN,H 2C 2O 4 , and all organic acids and bases.

Acids, Bases and Salts:

There are various theories from the explanation of acids and bases.

Arrhenius concept of acids and bases:

According to this theory, acids are the substances which give H+ ions dissociates
in water and bases which produce hydroxyl ions OH− in water.

Arrhenius acids: which increases the H+ ion concentration in water.

The ionization of acids can be represented by the following equations for HX
(aq):
HX(aq) → H + (aq) + X − (aq)
Or
HX(aq) + H 2O(l) → H 3O + (aq) + X − (aq)
Example: HCl, H 2SO 4 ,CH 3COOH etc.

Arrhenius bases: which increases the OH− ions concentration in water.

For example: NaOH,Ca(OH) 2 , NH 4OH etc.
MOH like base molecule ionizes in aqueous solution from the following equation:
MOH(aq) → M + (aq) + OH − (aq)

The Bronsted-Lowry acids and bases:

According to Brönsted-Lowry theory, acid is a substance that is capable of
donating a hydrogen ion H+ and bases are substances capable of accepting a
hydrogen ion, H+. In short, acids are proton donors and bases are proton
acceptors.
For example, consider the dissolution of NH 3 in H 2O represented by the
following equation:

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in this reaction, water molecule acts as proton donor is known as Lowry-Bronsted
acid and ammonia molecule act as proton acceptor is known as Lowry-Bronsted
base.

Lewis Acids and Bases:

According to this theory, acid is a species which accepts electron pair and a base
which donates electron pair.
A typical example is reaction of electron deficient species BF3 with NH 3 .
In this example BF3 does not have proton but acts as Lewis acid and NH 3
accepting lone pairs from Lewis acid. The reaction can be represented as:
BF3 + : NH 3 → BF3 : NH 3
Lewis acids are electron deficient species like AlCl3 ,Co +3 ,Mg +2
Lewis bases are electron pair donating species like H 2O, NH 3 ,OH −

The ionization constant of water and its ionic product:

Some substances are unique ability of acting acid and base like water molecules.
H 2O(l)(acid) + H 2O(l)(base) H 3O + (aq) + OH − (aq)
The dissociation constant is represented by:
[H3O+ ][OH − ]
K=
[H 2O]
The concentrated of water is neglected from the denominator as water is pure
liquid and its concentration remains constant. Then the equilibrium constant is
known as Ionic Product Of Water, K w .

K w = [H + ][OH − ]
The concentration of H+ = 1.0 10−7 M at 298K
As dissociation of water produces equal number of [H + ] = [OH − ] = 1  10 −7 M

K w = [H 3O + ][OH − ] = (1  10−7 ) 2 = 1  10−14 M 2

We can distinguish acidic, neutral, and basic solutions by the relative values of
the H 3O + and OH− concentrations:

Acidic: [H 3O + ]  [OH − ]

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Neutral: [H 3O + ] = [OH − ]

Basic: [H 3O + ]  [OH − ]

The pH Scale:
Hydronium ion concentration in molarity is more conveniently expressed on a
logarithmic scale known as the pH Scale.
From the definition of pH,
pH = − log[H + ]
at 25o C pure water has a concentration of hydrogen ions, [H + ] = 10−7 M
Hence, the pH of pure water is given as:
pH = − log(10−7 ) = 7

Acidic solutions posses a concentration of hydrogen ions, [OH − ]  10−7 M , while

basic solution posses a concentration of hydrogen ions, [OH − ]  10−7 M
Thus, acidic solution has pH < 7
Basic solution has pH < 7
Neutral solution has pH = 7
Then the ionic product of water, K w = [H 3O + ][OH − ] = 10−14
Taking negative logarithms on both sides of equation, we obtain
− log K w = − log{[H3O + ][OH − ]} = − log10−14
pK w = pH + pOH = 14

Ionization constants of weak acids:

Consider a weak acid HX which is partially ionized in the aqueous solution. The
equilibrium can be expressed by:
HX(aq)+ H 2O(l) H 3O + (aq) + X − (aq)
Initial concentration 0 0 0

Let  be the extent of ionization change (M)

HX(aq)+ H 2O(l) H 3O + (aq) + X − (aq)
− C  

HX(aq)+ H 2O(l) H 3O + (aq) + X − (aq)

Equlibrium concentration C−C C C

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Here C is the initial concentration of the undissociated acid HX. Then the
equilibrium constant for the above discussed acid dissociation equilibrium.
C2 2 C 2
Ka = =
C(1 − ) 1 − 
K a is called acid dissociation constant or ionization constant.
the pH scale for the hydrogen ion concentration has been so useful that besides
pK w
pK a = − log(K a )

Ionization constants of weak bases:

The ionization of base MOH can be represented by the following equation:
MOH M + (aq) + OH − (aq)
In a weak base there is partial ionization of MOH into M+ and OH–, the case is
similar to that of acid-dissociation equilibrium. The equilibrium constant for base
ionization is called base ionization constant and is represented by Kb. It can be
expressed in terms of concentration in molarity of various species
in equilibrium by the following equation:
[M + ][OH − ]
Kb =
[MOH]
Alternatively, if c = initial concentration of base and  = degree of ionization of
base i.e. the extent to which the base ionizes. When equilibrium is reached, the
equilibrium constant can be written as:

C2 2 C 2
Kb = =
C(1 − ) 1 − 
The pH scale for the hydrogen ion concentration has been extended to get:

pK b = − log(K b )

Hydrolysis of salts:
The reactions between acids and bases in definite proportions forms salts which
undergo ionize in water. The cations or anions formed on ionization of salts either
exit as hydrated ions in aqueous solutions ions in aqueous solutions or interact
with water to reform corresponding acids or bases depending upon the natural
salts.
Consider three types of hydrolysis of the salts:

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 ● Salts of weak acid and strong base. Eg: CH 3COONa
1 1
pH = 7 + pK a − log C
2 2
● Salts of strong acid and weak base. Eg: NH 4Cl
1 1
pH = 7 − pK b − log C
2 2
● Salts of weak acid and weak base. Eg: CH 3COONH 4
1 1
pH = 7 + pK b − pK b
2 2

Buffer solutions:
Many body fluids e.g., blood or urine have definite pH and any deviation in their
pH indicates malfunctioning of the body. The control of pH is also very important
in many chemical and biochemical processes. Many medical and cosmetic
formulations require that these be kept and administered at a
particular pH. The solutions which resist change in pH on dilution or with the
addition of small amounts of acid or alkali are called Buffer Solutions.

Solubility Equilibria of Sparingly Soluble Salts:

Each salt has its characteristic solubility which depends on temperature. We
classify salts on the basis of their solubility in the following three categories

Category I Soluble Solubility >0.1M

Category II Slightly soluble 0.01M<solubility<0.1M
Category III Sparingly soluble Solubility <0.01M

For example,
AgCl(s)  Ag + (aq) + Cl − (aq)
Solubility product, K sp = [Ag + ][Cl− ] = I.P = Ionic product
If ionic product < K sp , more salt can be dissolved through forward reaction.
If ionic product > K sp , precipitation of solid salt takes place as backward reaction.
If ionic product = K sp no more salt can be dissolved. This stage is saturation
point.

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