Chemical Equilibrium Part 1 PDF

• Whenever questioner doesn't ask about
direction then we take forward direction

only.
• In a reversible reaction if forward reaction
is exothermic then the backward reaction
will be endothermic and
• vice-versa.
• EQUILIBRIUM AND CHEMICAL PROCESS
r1
H2O(l) H2O(vap)
r2
Where r1= rate of evaporation
r2= rate of condensation
At equilibrium r1 = r2
• Equilibrium can be achieved in both Physical and Chemical processes.
Double half headed arrow
The double half headed arrows

indicate that the processes in both
the directions are going on
simultaneously.
• The most important characteristic property of a reversible reaction is
that it always attains a state of chemical equilibrium.
• Consider a general reversible reaction in a closed vessel
• ˆ†
‡ here rf = rate of forward reaction
w
• rb = rate of backward reaction
• Initially reaction occurs in forward direction but as the concentration
of products increases reaction also starts
• in backward direction.
• At a certain stage, rate of forward reaction becomes equal to the rate of
backward reaction called equilibrium
• state.
Dynamic Equilibrium in Chemical Processes
concentration
Reactant (s)
Both A and B
Time
Dynamic Equilibrium in Chemical Processes
 As the time progresses the product concentration which was zero

initially increases and reaches a constant value after some time.
Product C or D or both
concentration
Product (s)
Time
Observe this graph and conclude
 When the forward and backward rates become equal, we can
confirm that the reaction has reached equilibrium state.
Equilibrium state
r1
Forward rate
r1 =r2 at equilibrium
Rate
r2
Backward rate
Time
• The concentrations of the reactants and products do
not change with time.
• At this stage, number of moles of substances

produced per second in the forward reaction is equal
to the number of moles of substances which
disappear per second in the backward reaction.
Characteristics of equilibrium
(a) Chemical equilibrium is dynamic in nature i.e. the reaction although appears
to be stopped but
actually takes place in both the directions with the same speed.
(b) Chemical equilibrium can be approached from both sides
At equilibrium, each reactant and product have a constant concentration and

this is independent of the fact whether the reaction starts from forward
direction or backward direction with the reactant or with the product.
(c) Equilibrium is not affected by the presence of catalyst. The catalyst only helps
in attaining equilibrium rapidly.
(d) The measurable properties of the system like temperature, concentration,
colour, density etc. don't undergo any change with time at the chemical
equilibrium conditions.
Characteristics of equilibrium
(e) Homogeneous equilibrium is the equilibrium in which the reactants and
products are in the same phase.
(f) Heterogeneous equilibrium is the equilibrium in which the reactants and

products are in two or more phases
• ACTIVE MASS : The term active mass means the concentration of the
reactants expressed in moles per litre (molar concentration) or the
pressure of the reacting gas in atmosphere. In case of gases and solutions,
the molar concentration means the number of gram molecules present
per litre.
• Active mass is usually expressed by enclosing the symbol of the reactant in
square bracket [ ].
The active mass of solids and pure liquids is a constant quantity (unity)
because it is an intensive property i.e. number of molecules present per
unit volume do not change because density and molecular weight of solids
and pure liquids are constant. But it does not apply for gaseous substances
because for them number of molecules present per unit volume change
with change in volume of vessel.
• The law of mass action was given by Guldberg and Waage (1864).
• It states that the rate of a chemical reaction is directly proportional
to the product of active masses of the reacting substances raised to a
power equal to the stoichiometric coefficient in the balanced
chemical equation.
A. Derivation of equilibrium constant :-
Consider a reversible homogeneous chemical reaction which has

attained equilibrium state at a particular temperature :
According to law of mass action :-
• K is known as equilibrium constant and has a definite value for every
chemical reaction at particular temperature.
• The equilibrium constant at a given temperature is the ratio of the rate
constants of forward and backward reactions
B. Relation between KP and KC :
Consider a reversible homogeneous chemical equilibrium reaction

Three cases may arise :-
REACTION QUOTIENT (Q)
Factors affecting the equilibrium constant .
(a) The mode of representation of the reaction :
Consider the reversible chemical equilibrium reaction
The equilibrium constant for the reaction is

If the reaction is reversed
The equilibrium constant for the reaction is
The equilibrium constant K'C is actually the reciprocal of KC
Thus, the two equilibrium constants are related as :

(b) Stoichiometry of the reaction :-
When a reversible reaction can be written with the help of two or more
stoichiometric equation then the value of equilibrium constant will be numerically
different in these cases.
For example the dissociation of NO2 can be represented as :
(i) If reaction (1) is divided by 2 -
Then the reaction becomes

Thus, the two equilibrium constants are related as
So if reaction is divided by n then

(ii) If reaction (1) is multiplied by 2
(c) Multi step reaction :
If a reaction can be expressed as the sum of two or more reactions then overall
KC will be equal to the product of the individual equilibrium constants of the
reactions.
(d) Temperature :
The value of equilibrium constant changes with the change of temperature. If K1 and
K2 be the equilibrium constants of a reaction at absolute temperatures T1 and T2K
and △H is the change in enthalpy then
Factors not affecting the equilibrium constant :
The value of equilibrium constant is independent of the following factors.
(a) Concentration of reactants and products.

(b) Pressure
(c) Volume
(d) The presence of a catalyst.
(e) Presence of inert gas.
(f) The value of equilibrium constant depends only on temperature.
LE-CHATELIER'S PRINCIPLE
PRINCIPLE :-
According to this principle, if a system at equilibrium is subjected to a change of
concentration, pressure or temperature then the equilibrium is shifted in such a
way as to nullify the effect of change.
(a) Change in concentration:- In an equilibrium increasing the concentrations

of reactants results in shifting the equilibrium in favour of products while
increasing concentrations of the products results in shifting the equilibrium in
favour of the reactants.
(b) Change in pressure :- When the pressure on the system is increased, the
volume decreases proportionately
i.e. the total number of moles present per unit volume increases. According to
Le-Chatelier's principle, the equilibrium shifts in that direction in which there
is decrease in number of moles.
• If there is no change in number of moles of gases in a reaction then a
pressure change does not affect the equilibrium.
(c) Change in temperature :- If the temperature of the system at equilibrium is
increased then reaction will proceed in that direction in which heat can be used.
Thus increase in temperature will favour the forward reaction for endothermic
reaction.
Similarly, increase in temperature will favour the backward reaction for exothermic
reactions.
Special point :- Le-Chatelier's principle is applicable for both chemical and physical
equilibrium

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• Whenever questioner doesn't ask about

direction then we take forward direction

Where r1= rate of evaporation

r2= rate of condensation

Double half headed arrow

The double half headed arrows

 As the time progresses the product concentration which was zero

• At this stage, number of moles of substances

At equilibrium, each reactant and product have a constant concentration and

(f) Heterogeneous equilibrium is the equilibrium in which the reactants and

A. Derivation of equilibrium constant :-

Consider a reversible homogeneous chemical reaction which has

Consider a reversible homogeneous chemical equilibrium reaction

(a) The mode of representation of the reaction :

Consider the reversible chemical equilibrium reaction

The equilibrium constant for the reaction is

The equilibrium constant for the reaction is

The equilibrium constant K'C is actually the reciprocal of KC

Thus, the two equilibrium constants are related as :

(i) If reaction (1) is divided by 2 -

Then the reaction becomes

So if reaction is divided by n then

(a) Concentration of reactants and products.

(a) Change in concentration:- In an equilibrium increasing the concentrations

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