* CONDITIONS FOR ATTAINMENT OF CHEMICAL

EQUILIBRIA
 Types of Equilibrium
1. A system is said to be in thermodynamic equilibrium when
pressure, temperature and concentrations of species do not change
with time.
2. The equilibrium involving physical processes are referred to as
physical equilibrium. The physical equilibrium involving change in
state may be of the following three types.

* Organized by Lencha Abeya (Bsc in chemistry)

* Organized by Lencha Abeya (Bsc in chemistry)
* Organized by Lencha Abeya (Bsc in chemistry)
Equilibrium in our Daily Life
Examples
• Transport of oxygen by haemoglobin in blood. Oxygen breathed
in combines with the haemoglobin according to the equilibrium:

• Removal of CO2 from tissues by blood. The equilibrium is:

* Organized by Lencha Abeya (Bsc in chemistry)

* Organized by Lencha Abeya (Bsc in chemistry)
3. In a reversible reaction, the state in which both forward and backward
reactions or two opposing reactions occur at the same speed is called as
chemical equilibrium.
* Chemical equilibrium is the state at which concentration of either of
reactants or products do not change with time.
* It is attained when the rate of forward reaction becomes equal to the
rate of backward reaction.
* Chemical equilibria are dynamic in nature. It can be approached from
either side.
* The gaseous phase chemical equilibrium is attained only if a reaction is
made in a closed container, either at constant pressure or at constant
volume.
* Misconception: Equilibrium is the state where the rates of the forward
and reverse reactions are equal, not when the rates reach zero.
(Common misconception: Nothing happens at equilibrium.
 Chemical equilibrium are dynamic equilibria,i.e.,
reactants and products are interconverted continually,
even though the overall composition of the reaction
mixture does not change.
 Once the equilibrium is established, a change in one
direction is balanced by changes in the other direction.
 The rate of the forward reaction depends upon the
concentration of reactants, whereas the rate of the reverse
reaction depends upon the concentration of the products.
* As the reaction progresses, the concentration of the reactants decreases and hence,
the rate of forward reaction also decreases. However, due to the increase in
the concentration of products, the rate of the reverse reaction increases.
For example, synthesis of ammonia from nitrogen and hydrogen is a reversible
process.

 Nitrogen and Hydrogen combine to form ammonia at a large rate. As the reaction
progresses, the concentrations of nitrogen and hydrogen decrease so the rate of
formation of ammonia decreases.
 As more and more ammonia molecules are formed, some of the molecules start
decomposing to give back nitrogen and hydrogen molecules. As the reaction
progresses, the number of ammonia molecules increases, the rate of
decomposition of ammonia also increases.
 As the reaction proceeds, the rate of formation of ammonia decreases while the
rate of decomposition ammonia increases. At a given point the two rates become
equal, and equilibrium is reached
 a reaction at equilibrium has the following characteristics:
 The reaction is reversible in nature.
There is no net change in the concentrations of the reactants and
products of the reaction.
The rates of the forward and reverse reactions are equal.
A system needs to be always closed to achieve equilibrium since
an open system allows the escape of the formed products which
prevents the backward reaction.
The equilibrium is dynamic in nature.
The concentrations of reactants and products are generally not
equal.
Presence of catalyst never affects the equilibrium but it helps in
attaining it rapidly.
* Chemical equilibrium can be attained from either side

* The measurable properties of the system such as pressure, density,

colour or concentration remain constant under a certain set of
conditions.
Class work
* Exercise 5.2 (A and C) and activity 5.3
Activity 5.3
 Equilibrium expression and equilibrium constant

A. LAW OF MASS ACTION

• Mathematically the equilibrium constant is written based on the law
of mass action or law of concentration action proposed by Cato
Maximilian Guldberg and Peter Waage, in 1864.
• The law of mass action states that “the rate at which A and B
combine is directly proportional to the product of their
concentration terms each raised to the power of its respective
coefficient in the balanced chemical reaction.”
*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.
* When the reaction reactants and the products are gaseous, their
concentrations can be expressed in terms of partial pressures. In such
cases, the Keq is denoted by Kp
Example 5.1
* Equilibrium constant for the reverse reaction is the inverse of
the equilibrium constant for the reaction in the forward
direction.
 Class work
1.
2. Equilibrium constant and unit for the reaction:
is ?
* The value of an equilibrium constant is independent of the following factors:
• Initial concentration of the reactants involved.
• The presence of a catalyst.
• The direction from which the equilibrium has been attained.
• The presence of inert materials.
• The equilibrium expression for a given reaction is independent of the
reaction mechanism.
• The equilibrium state is one of minimum Gibbs energy (G) (free energy).
Gibbs energy is the energy associated with a chemical reaction that can be used
to do work.
• Kc does not change with time. It has one unique or definite value for a given
reaction at a given temperature and it depends only on temperature.
• If a reversible reaction has an exceedingly small value of Kc, adding a
catalyst would be of little help.
• The concentrations of pure solid and liquid must be ignored while
writing the equilibrium constant expression.
* When all the reactants and the products are gases, their
concentrations can be written in terms of partial pressures.
* Equilibrium constant for heterogeneous reaction
* In heterogeneous reactions, the reactants and products are present in
more than one physical state. For example, thermal decomposition of
calcium carbonate is an example of heterogeneous reaction. See these
examples:

* When we write the equilibrium constant expression for heterogeneous

reactions, we do not include the concentration of pure solids or pure
liquids in the expression. This is because, the position of equilibrium
does not depend on the amounts of pure solids or pure liquids present.
The molar concentrations of pure solids liquids are constant at a given
temperature.
Relationship Between Kc &Kp
The ideal gas equation is written as,
pV =nRT C = , P = CRT

At constant temperature, the pressure of the gas is proportional to its

concentration i.e., p ∝[gas]
And here Kp = Kc but not always true.
For example in reaction
* So

* Where ∆n = (c + d) – (a + b) for gaseous species

* Therefore, ∆n = 0 and, hence Kp = Kc
Key points
 Many students confuse rate of reaction with extent of reaction.
(i) Rate of Reaction: The reaction rate(rate of reaction) or speed of
reaction for a reactant or product in a particular reaction is intuitively
defined as how fast or slow a reaction takes place.
(ii) Extent of Reaction: The extent of reaction is a quantity that measures
the extent in which the reaction proceeds. It is usually denoted by the Greek
letter ξ. The extent of a reaction has units of amount (moles).
 Equilibrium constants can change with temperature when the activation
energies of forward and reverse reactions are different. (Equilibrium
constants are constant under all conditions.)
 The rate of the forward reaction increases with time from the mixing of
the reactants until equilibrium is established. But note that this is not so.
* The magnitude of K equilibrium constant is a measure of the
extent to which a given reaction has taken place at equilibrium.
* The higher value of equilibrium constant ( or >) for a reaction
indicates that the reaction proceeds more in forward direction.
* The lower values of equilibrium constant (< ) for a reaction
indicates that the reaction proceeds more in backward direction.
* The intermediate value of Kc(to ) shows that concentrations of
products and reactants are comparable.
*
Self test
* Home work
 APPLICATION OF EQUILIBRIUM CONSTANT
Useful information can be obtained from the value of equilibrium
constant of a given reaction at a particular temperature.
The equilibrium constant of a reaction enables us to:
A. predict the composition of an equilibrium mixture (or predict
extent of reaction);
B. predict the direction of the reaction
C. calculate the equilibrium concentrations of reactants and products
from initial concentrations.