Welcome to
Equilibrium
Equilibrium
State in which Static Dynamic
there are no Equilibrium
Equilibrium Equilibrium
observable
changes with time
State in which observable
properties (pressure,
temperature, volume &
concentration) remain
constant.
Types of
Equilibrium
Static Dynamic
Equilibrium Equilibrium
The dynamic equilibrium can be
In this type of equilibrium, defined as the state of a system at
the system is at rest and no which the rate of movement
actual change is happening in the forward and backward
either at the macroscopic directions (chemical reaction) is
level or the microscopic level. equal and no net change takes
place.
Types of Chemical Reactions
Irreversible Reversible
Irreversible Reaction
Reaction which proceeds
in one direction only
Represented by a single arrow ( )
Reactants are almost completely
converted into products
Products do not react to Δ
2KClO 3 (s) 2KCl (s) + 3O 2 (g)
form the reactants again
Do not attain equilibrium state
Examples of Irreversible Reaction
Precipitation
NaCl (aq) + AgNO 3 (aq) AgCl (s) + NaNO3 (aq)
reaction
Neutralization
HCl (aq) + NaOH (aq) NaCl (s) + H 2 O (l)
reaction
Reversible Reaction
Reaction which proceeds
in both the directions
Represented by a double arrow ( ⇌ )
Reaction never goes to
completion
Products react to
form the reactants again H2 (g) + I2 (g) ⇌ 2HI (g)
Attains equilibrium state
Examples of Reversible Reaction
N2 (g) + O 2 (g) ⇌ 2NO (g)
PCl5 (g) ⇌ PCl3 (g) + Cl2 (g)
Types of Equilibrium
Homogeneous Heterogeneous
Equilibrium Equilibrium
Homogeneous Equilibrium
All reactants and products are in the same phase
C 2 H5 OH (l) + CH3 COOH (l) ⇌ CH3COOC 2H5 (l) + H2O (l)
H2 (g) + Cl2 (g) ⇌ 2HCl (g)
Heterogeneous Equilibrium
Reactants and products are in more than one phase
3Fe (s) + 4H2O (g) ⇌ Fe3O4 (s) + 4H2 (g)
CaCO3 (s) ⇌ CaO (s) + CO2 (g)
C (diamond, s) ⇌ C (graphite, s)
Equilibrium Processes
Physical Chemical
Equilibrium
Equilibrium Equilibrium
Phase Transformation Processes
Sublimation
Melting Evaporation
Freezing Condensation
Deposition
Physical Equilibrium
Equilibrium in physical
processes
Solid ⇌ Liquid
Dissolution of
Physical Liquid ⇌ Vapor
Gases in liquid
Equilibrium
Dissolution of
Solid ⇌ Vapor
Solids in liquid
Chemical Equilibrium
Equilibrium in chemical
processes
R ⇌ P
At t = 0
[R] c
State in which the
driving forces, i.e., the [P] 0
factors taking the
reaction in the forward &
the backward direction Rate of the
backward reaction = 0
are balancing each other
Chemical Equilibrium
As reaction proceeds, R ⇌ P
At
[R] [P] equilibrium
[R] Constant
Rate of the forward
reaction [P] Constant
Rate of the
Rate of the forward
Rate of the backward reaction (r
= backward reaction
f )
reaction (rb )
Graphical Representation
Concentration
[R]
rf
Rate
rb
[P]
Time Time
Chemical Equilibrium
Reactant molecules No change in the
continue to form the concentration of either
product molecules the reactants
and vice versa or the products
Example: N 2 (g) + 3H2 (g) ⇌ 2NH3 (g)
Equilibrium Mixture
Mixture of reactants
& products in the
equilibrium state
Example
N2 (g) + 3H2 (g) ⇌ 2NH3 (g)
Conditions for Chemical Equilibrium Involving Gaseous Phase
Reversible
reaction
Essential
conditions
Closed
container
Remember!!
At equilibrium, all macroscopic properties such as
Pressure Concentration
Density Colour
of the system appear to be constant
Extent of the Reaction
01 Reactions that proceed nearly
to completion ([R] is very less)
Extent of the reaction 02
Reactions that barely proceed
at equilibrium
([P] is very less)
varies with the
experimental
conditions 03
such as pressure, Reactions in which the [R] & [P] are
temperature, etc. significant at equilibrium
Characteristics of Chemical Equilibrium
1 2
Equilibrium Equilibrium involving
is dynamic in gases is
nature established in a
closed system
Equilibrium state is
unaffected by catalyst’s System moves toward
presence, but is attained an equilibrium
faster/slower depending state spontaneously
4 on catalyst type 3
Characteristics of Chemical Equilibrium
5 At equilibrium, the 6
Rate of forward concentration of the
reaction = Rate of reactants and the
backward reaction products becomes
constant
Equilibrium can be At equilibrium,
achieved from both free energy change
directions (ΔG) = 0
8 7
Characteristics of Chemical Equilibrium
Sum of Internal energy
In general, the state of
and PV energy of a system
equilibrium in a chemical
under a given set of
reaction can be achieved
conditions.
from either direction
Law of Mass Action
At a particular temperature,
Rate of a chemical reaction is
proportional to the product
of active masses of reactants
raised to the powers of their
stoichiometric coefficients
Proposed by
Guldberg and Waage
Active Mass
Effective amount of reacting
species taking part
in the reaction
Active masses are dimensionless quantities but
for our purposes we generally take them with
dimensions of molarity, partial pressure etc.
Active Mass
Active masses
of pure liquids = 1
& solids
[Solid] or Moles Mass
[Liquid] = Volume = Molar mass x Volume
Density
= Molar mass
= Constant
Mathematical Expression for Law of Mass Action
aA + bB Products
Rate of reaction (r) ∝ [A]a [B]b
According to law of mass action,
Rate of reaction (r) = k [A]a [B]b
Rate of reaction (r) ∝ [A]a [B]b
k Rate constant
Molar
[A] & [B]
concentration
Mathematical Expression for Law of Mass Action
aA + bB ⇌ cC + dD
According to law of mass action,
Rate of forward
reaction ∝ [A]a [B]b = kf [A]a [B]b
Rate of backward
reaction ∝ [C]c [D]d = kb [C]c [D]d
Application of Law of Mass Action
kf [C]ceq [D]d
At eq
Equilibrium
=
kb [A]aeq [B]beq
Rate of
Rate of forward
reaction
= backward kf
reaction = KC
kb
kf [A]eq [B]eq = kb [C]eq [D]eq
KC Equilibrium Constant
Equilibrium Constant
Equilibrium constant in
terms of concentration
KC
Keq Equilibrium constant in
KP
terms of partial pressure
K𝝌
Equilibrium constant in
terms of mole fractions
KC and KP are temperature
dependent only
Equilibrium Constant (Kc)
KC is the equilibrium constant
when the active masses are
expressed in concentrations N2 (g) + 3H2 (g) ⇌ 2NH3 (g)
[NH3 ]2eq
KC = [N2]eq [H2]3eq
kf and kb depends
only on temperature.
Example
CaCO3 (s) ⇌ CaO (s) + CO 2 (g) KC = [CO2(g)]eq
Activity of pure solids is taken as 1
CH3 COOC 2 H 5 (aq) + H 2 O (l) ⇌ CH3 COOH (aq) + C2H5OH (aq)
[CH3COOH]eq [C2H5OH]eq
KC =
[CH3COOC2H5]eq
Example
CH3 COOH (l) + C 2 H5 OH (l) ⇌ CH3COOC 2H5 (l) + H2O (l)
Here, water is not acting as the solvent
[CH3COOC2H5]eq [H2O]eq
KC =
[CH3COOH]eq [C2H5OH]eq
Equilibrium Constant (KP)
Equilibrium reaction which contains
at least one gaseous component
aA (g) + bB (g) ⇌ cC (g) + dD (g)
(PC )ceq (PD )deq
KP = (PA)aeq (PB)b
eq
Equilibrium constant in terms
of partial pressure
Kp and Kc
aA (g) + bB (g) ⇌ cC (g) + dD (g)
[C]ceq [D]deq
1 KC =
[A]aeq [B]beq
(PC )ceq (PD )deq
2 KP =
(PA)aeq (PB)b
eq
Relation between Kp and Kc
For an ideal gas
P = CRT
PV = nRT Where, P Partial pressure of Gas
n C Concentration of Gas
P = V RT
R Universal Gas Constant
P = CRT T Temperature
Relation between Kp and Kc
aA (g) + bB (g) ⇌ cC (g) + dD (g)
(PC)ceq (PD)d
eq
(RT)c (RT)d
[C]ceq [D]d
eq KC
KC = (PA)aeq (PB )beq
[A]aeq [B]beq
(RT)a (RT)b
P
C = RT
Relation between Kp and Kc
(PC )ceq (PD )deq
Kc = (PA)aeq (PB)b
RT (a + b) - (c + d)
eq
- Δng
Kc = KP (RT)
Δng
KP = Kc (RT)
Δng
Sum of stoichiometric Sum of stoichiometric
Δn g = coefficients of _ coefficients of
gaseous products gaseous reactants
Example: N2 (g) + 3H2 (g) ⇌ 2NH3 (g)
Δn g = 2 - (3 + 1) = -2
Characteristics of Equilibrium Constant
If reaction is reversed, the equilibrium
1 constant is reciprocated
A (aq) + B (aq) ⇌ C (aq) C (aq) ⇌ A (aq) + B (aq)
[C] [A] [B] 1
KC = =K KC I = = K
[A] [B] [C]
Characteristics of Equilibrium Constant
If a reaction is multiplied by a factor ‘n’,
2 the value of the equilibrium constant
becomes KI = (K)n
⇌ C (aq) 1 A (aq) + 1 B (aq) 1 C (aq)
A (aq) + B (aq) ⇌
2 2 2
[C] [C]1/2
KC =
[A] [B]
=K KC | = = K1/2
[A]1/2 [B]1/2
Characteristics of Equilibrium Constant
If we add two or more equilibrium
3 reactions, final equilibrium constant
is the product of individual constants.
A +B ⇌ C C ⇌ D A +B ⇌ D
[C] [D] [D]
K1 = K2 = K = K1 × K2 =
[A] [B] [C] [A] [B]
Characteristics of Equilibrium Constant
Equilibrium constant does not depend upon
4 concentration of reactants, presence of catalyst,
direction from which equilibrium is reached
It depends only on the temperature
5 and the stoichiometric coefficients
Applications of Equilibrium Constant
Case 1
1 Predicting the extent of reaction
Keq > 103
Predicting the direction
2 of equilibrium
For the reaction,
[P]eq >> [R]eq
R ⇌P
[P]eq
Keq = Reaction proceeds
[R]eq nearly to completion
Case - II
Keq < 10-3
[P]eq << [R]eq
Reaction barely
proceeds
Case - III
10-3 < Keq < 103
Appreciable values
of [P]eq & [R]eq
If Keq = 1 [P]eq = [R]eq
Predicting the Extent of Reaction
Negligible Keq ( KC or Kp ) Very Large
< 10-3 10-3 - 103 > 103
Reaction
Reaction Significant
proceeds
barely values of
almost to
proceeds [R] & [P]
completion
Applications of Equilibrium Constant
Predicting the extent of reaction
1
Predicting the direction
2 of equilibrium
Le - ch at e le i r‘ s
Principle
Industrially, the aim is to have maximum product
yield with minimum energy expenditure
And reaction can be
After equilibrium is Equilibrium can be
carried out in the
established, more disturbed
desired direction
product formation
stops.
LeChatelier’s Principle
If a change is applied In which it can
to the system at minimise the effect of
equilibrium, then the the change applied
equilibrium will be and the equilibrium is
shifted in that established again
direction under new conditions.
Factors Affecting Equilibrium
Change in the Effect of
Change in Change in addition of
concentration
pressure volume inert gas
of reactant or
product
Change in Effect of
temperature addition
of catalyst
Effect of Change in Concentration
If the concentration
of a component is
increased, reaction
shifts in a direction
which tends to decrease
its concentration
Effect of Change in Concentration
[C] [D]
A (aq) + B (aq) ⇌ C (aq) + D (aq) QC = [A] [B]
Addition of A or B
Qc ⇒ Qc < Kc
Equilibrium shifts in the
forward direction
Effect of Change in Concentration
[A] [B]
[C] [D]
Concentration of the added species ([A] or [B])
will be more at new equilibrium than that at the
old equilibrium under the same set of conditions.
Effect of Change in Concentration
[C] [D]
A (aq) + B (aq) ⇌ C (aq) + D (aq) QC = [A] [B]
Addition of C or D
Qc ⇒ Qc > Kc
Equilibrium shifts in the
backward direction
Effect of Change in Concentration
[C] [D]
[A] [B]
Concentration of the added species ([C] or [D])
will be more at new equilibrium than that at the
old equilibrium under the same set of conditions.
Conclusions
Addition of any solid
component does not affect
the equilibrium
[Reactant] Equilibrium shifts in the
forward direction
Equilibrium shifts in the
[Product]
backward direction
Effect of Temperature
T T
Reaction shifts in that Reaction shifts in that
direction where direction where
temperature temperature
decreases increases
Exothermic Reaction
For the reaction, A (aq) + B (aq) ⇌ C (aq) + D (aq)
ΔH = − ve
If T
Reaction shifts in that
direction where temperature
decreases
Exothermic Reaction
If Forward reaction Exothermic
Then Backward reaction Endothermic
Reaction shifts
backward direction
Endothermic Reaction
For the reaction, A (aq) + B (aq) ⇌ C (aq) + D (aq)
ΔH = + ve
If T
Reaction shifts in that
direction where temperature
decreases
Endothermic Reaction
If Forward reaction Endothermic
Then Backward reaction Exothermic
Reaction shifts
forward direction
Effect of Change in Pressure
On increasing pressure, equilibrium will
shift in the direction in which pressure
decreases i.e., number of moles in the
reaction decreases and vice versa
Number of
P ∝ moles of gas
Effect of Change in Pressure
For the reaction,
A (g) ⇌ B (g)
Δn g = 0
If pressure changes
No shift in equilibrium
H2 (g) + I2 (g) 2HI
(g)
⇌
Effect of Change in Pressure
2
PB2 𝜒B PTotal
For the reaction, QP = PA = 𝜒A PTotal
A (g) ⇌ 2B (g)
Δn g = + ve ⇒ QP ∝ PTotal
Reaction goes
Pressure QP Q P > KP
backward
Effect of Change in Pressure
PB 𝜒B PTotal
For the reaction, QP = = 2
PA2 𝜒A PTotal
2A (g) ⇌ B (g)
1
Δn g = - ve ⇒ QP ∝ PTotal
Reaction goes
Pressure QP Q P < KP
forward
Example
N2 (g) + O 2 (g) ⇌ 2NO (g)
If P ⇒ No Shift as Δng = 0
P ⇒ V ⇒ [NO]
Effect of Change of Pressure
Change in pressure
Solids & liquids are has no effect on
incompressible or negligibly equilibria involving
compressible. solid & liquid
Effect of Change in Volume
Volume Pressure
Hence, the reaction will shift
in the direction in which pressure
increases i.e., in the direction in which the
number of moles of gases increases and
vice versa.
Effect of Change in Volume
For the reaction, A (g) B (g)
⇌
Δn g = 0
If volume changes
No shift in equilibrium
H2 (g) + I2 (g) 2HI
⇌
(g)
Effect of Change in Volume
For the reaction,
A (g) ⇌ 2B (g)
Δn g = +ve
If Volume Reaction shifts where
the moles of gas
Reaction goes forward
Effect of Change in Volume
For the
reaction,
2A (g) ⇌ B (g)
Δn g = -ve
If Volume Reaction shifts where
the moles of gas
Reaction goes backward
Example
For the
reaction,
3H2 (g)+ N2 (g) ⇌ 2NH3 (g)
V or P ⇒ Backward shift
nH2 nN2 nNH3
Example
NH 4 COONH 2 (s) 2NH3 (g) + CO 2
⇌
(g)
V ⇒ Forward shift
nCO2 nNH3
[NH3] and [CO2] remains same
Catalyst and Effect of Catalyst
Substance which can alter the
speed of a chemical reaction
without itself getting consumed
at the end of the reaction
Due to the catalyst, the state of equilibrium is not affected
Catalyst lowers the It alters the
activation energy of both forward and the reverse
the forward and the reverse rate equally and hence,
reactions by the same the equilibrium will be
amount, attained faster
Effect of Addition of an Inert Gas
Addition of an inert gas increases
the number of moles of the gas in
the system
Addition of an
inert Gas
Inert gas molecules do not
interact with the reactant or the
product molecules
At constant
At constant P
V
No change in the moles of
the reactants & the products
Effect of Addition of an Inert Gas
At constant
V
Partial pressures of the
When ΔV = 0 gaseous reactants & No disturbance
products do not change in equilibrium
i.e., Q P do not change
A (g) ⇌ B (g) A (g) ⇌ 2 B (g) 2 A (g) ⇌ B (g)
Effect of Addition of an Inert Gas
At constant P PTotal = Constant
2A (g)
On addition nTotal ⇌ B
(g)
Δn g = - ve
of an inert gas
Equilibrium shifts backward
V
Equilibrium shifts in that direction
where the moles of gas is more
Formation of Ammonia
N2 (g) + 3H2 (g) ⇌ 2NH3 (g) ΔH = -22.4 kcal/mol
1 2
The reaction will shift
in the forward At high pressure, the
direction at low reaction will shift in
temperature the forward direction