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Equilibrium
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 CHEMICAL EQUILIBRIUM
What is Equilibrium ?

EQUILIBRIUM is a state in which opposing forces or

influences are balanced.
By arvind Arora
 Chemical Equilibrium

The rate of the forward reaction is equal to…

the rate of the reverse reaction.

By arvind Arora
 Chemical reaction

Reactants Products

H Cl + Na OH NaCl + H2O

By arvind
A process where one form of substance Arora gets
i.e reactants
converted to another form of substance i.e products with the
help of a chemical change
TYPES OF REACTION

Irreversible reactions
• The reaction takes place in only in forward direction therefore it
is known as irreversible reaction

• It is denoted with the help of a single arrow ( → ) between

reactants and products.
By arvind Arora
In irreversible reaction –
Reactants can be converted to Products but
Products cannot be converted back to reactants.
Irreversible reactions

Example:
Neutralisation HCl + NaOH NaCl + H2O

Precipitation
NaCl + AgNO3 AgCl + NaNO3
By arvind Arora
Combustion 2Mg + O2 2MgO

Redox Reaction Zn + CuSO ZnSO4 + Cu

4
 Reversible reactions

• The reaction takes place in both the direction (forward and backward)
therefore it is known as reversible reaction

• It is denoted with the help of between reactants and

products.
By arvind
• All types of reactants and products Arora
remains in the system even after
infinite length of time i.e Reactants are not exhausted completely even
after very long time
• In Reversible reaction –
Reactants can be converted to Products and Products can be converted
back to reactants
Reversible reactions

Example :
a) N2 + O2 2NO

b) N2 + 3H2 By2NH
arvind
3 Arora
Sr. Reversible Reactions Irreversible Reactions
1 The formed products can react The formed products cannot react
with each other to give with each other to give
the original reactants. the original reactants.
2 Complete conversion of reactants Complete conversion of reactants
into products, is not possible. into products, is possible.
3 It is generally slow It is generally fast.
4 It proceeds in both forward
By arvind Arora
It proceeds in only
and reversible directions. forward directions.
5 Law of mass action Law of mass action
is applicable. is not applicable.
 Reason for attainment of equilibrium
1(reactants)
Equilibrium is a condition
G system 2 (products) when the free energy of the system is minimum

3
Progress of reaction

By arvind Arora
At equilibrium ΔGsystem = 0
 Types of equilibrium

Physical equilibrium Chemical equilibrium

By arvind Arora
Consider a chemical reaction for formation of AMMONIA

N2(g) + 3H2(g) 2NH3(g)

Forward reaction
N2(g) + 3H2(g) → 2NH3(g)

Reverse reaction By arvind Arora

Reversible Reaction takes place in both the
2NH3(g) → N2(g) + 3H2(g) direction (forward and backward)
Graphical representation
N2(g) + 3H2(g) 2NH3(g)
Rate of reaction →

Equilibrium state

N2 By
+ 3Harvind
2
Arora
2NH3

Time →
CHARACTERISTICS OF CHEMICAL EQUILIBRIUM

EQUILIBRIUM
Reactant Product

1. At equilibrium reactants and products both

By arvind Arora
are present
CHARACTERISTICS OF CHEMICAL EQUILIBRIUM
EQUILIBRIUM DYNAMIC IN NATURE
Reactant Product

• Neither the forward reaction nor the reverse reaction is ceased (stopped).

• Since the chemical reaction does not stop………

By arvind Arora
Both the reaction proceed in opposite direction with equal rates
CHARACTERISTICS OF CHEMICAL EQUILIBRIUM

EQUILIBRIUM EQUILIBRIUM
Reactant Product
CONCENTRATION

The concentration of reactants and products

By arvind Arora
does not change
CHARACTERISTICS OF CHEMICAL EQUILIBRIUM

1. All the reactants and products are present at equilibrium.

2. At equilibrium neither the forward reaction nor the reverse reaction has ceased.
Both the reaction continue to proceed in opposite direction with equal rates. Thus
chemical equilibrium is dynamic in nature.

3. The concentration of reactants and products reach

By equilibrium
constant values and these are called arvind Aroraconcentration.

4. A catalyst does not affect the position of equilibrium.

CHARACTERISTICS OF CHEMICAL EQUILIBRIUM

5. The change in concentration, pressure, volume may change the equilibrium

but temperature always changes the equilibrium position

6. Equilibrium cannot be attained in open vessel.

7. It is the state of minimum Gibb’s energy i.e. G = Minimum ; ΔG = 0

By arvind Arora
 Rate of Reaction
Average Rate = Change in concentration/Time Taken = Dc/Dt

Dc = Final Concentration – Initial concentration

Dt = Final Time – Initial Time

Instantaneous rate Lim Dc/Dt = dc/dt

Dt → 0
By arvind Arora
 Overall Rate of a Reaction

Example A + 2B → 3C + 4D

Rate of disappearance of B = 2 × Rate of disappearance of A

Rate of formation of C = 3 × Rate of disappearance of A

Rate of formation of D = 4 × Rate of disappearance of A

• So different reactants and products will give different rate for the same reaction
By arvind Arora
• To get a single value for rate of reaction we define overall rate of reaction

• To get overall rate we divide individual rates by the respective coefficients

Overall Rate = – ΔA/Δt = – 1 ΔB/Δt = + 1 ΔC/Δt = + 1 ΔD/Δt
2 3 4

For reversible reactions

Overall rate = Rate of forward reaction – Rate of backward reaction

“At equilibrium the overall rate of a reversible reaction becomes zero”

By arvind Arora
aA + bB cC + dD

1
Overall Rate = – 1 ΔA/Δt = – ΔB/Δt = + 1 ΔC/Δt = + 1 ΔD/Δt
a b c d

Instanteneous Rate = – 1 dA/dt = – 1 dB/dt = + 1 dC/dt = + 1 dD/dt

a b c d
By arvind Arora
 LAW OF MASS ACTION
Is the quantitative equilibrium expression was obtained in 1864.

aA + bB Products
a b
Rate α [A] [B] [A] and [B] are the active masses
or molar concentration of reactants A and B
By ‘a’
arvind Arora
Rate = k [A]a [B]b and ‘b’ are the stoichiometric
coefficient of reactants A and B

The proportionality constant

‘k’ is known as rate constant.
 LAW OF MASS ACTION
a b
Rate α [A] [B]
STATEMEN
T
The RATE of a chemical reaction is directly proportional to the product of
Active masses of reactants, with eachByactive
arvind Arora
mass term raised to the power
equal to its stoichiometric coefficient in the balanced equation.
 Mathematical expression of Law Of Mass Action

aA + bB
Consider a reversible chemical reaction cC + dD
aA + bB cC + dD
Applying LOMA to forward reaction

Ratef α [A]a [B]b [A] and [B] are the molar concentration
of A and B respectively.
a b
By arvind Arora
rf = kf [A] [B] ‘a’ and ‘b’ are the stoichiometric
coefficient of A and B respectively.

• rf and kf are the rate and rate constant of reactants A and B.

Mathematical expression of Law Of Mass Action

aA + bB cC + dD
Applying LOMA to reverse reaction reaction

cC + dD aA + bB
Rater α [C]c [D]d By arvind Arora
[C] and [D] are the molar concentration of C
and D respectively.
rr = kr [C]c [D]d ‘c’ and ‘d’ are the stoichiometric coefficient of
C and D respectively.
rr and kr are the rate and rate constant of
products C and D.
 Mathematical expression of Law Of Mass Action

rf = kf [A]a [B]b rr = kr [C]c [D]d

At equilibrium , rf = rr

kf [A]a [B]b = kr [C]c [D]d Rearranging the above equation

kf [C]c [D]d By arvind Arora

=
kr [A]a [B]b

[C]c [D]d kf / k r = Kc
kc =
[A]a [B]b equilibrium constant of the reaction
• The subscript ‘c’ in kc indicates molar concentration of substance
Units
Units of concentration is mol/dm3

[C]c [D]d
kc =
[A]a [B]b
3 c 3 d
kc = (mol/dm ) (mol/dm )
(mol/dm3)a (mol/dm3)
b
3 (c + d) – (a + b)
By arvind Arora
kc = (mol/dm )
kc = (mol/dm3) Δn

where Δn is difference in number of moles of gaseous product

and number of moles of gaseous reactant
Example

Write the equilibrium equation for each of the following reactions :

(a) N2(g) + 3H2(g) 2 NH3(g)

(b) 2 NH3(g) N2(g) + 3H2(g)

By arvind Arora
Solution

Coefficient of NH3
[NH3]2
Kc =
[N2][H2]3
Coefficient of H2

Coefficient of H2
3
[N2][H2]
Kc = By arvind Arora
[NH3]2
Coefficient of NH2
Kc depends on two factors

1. Reaction stoichiometry

2. Temperature

By arvind Arora
Effect of Stoichiometric coefficients

If K1 be the equilibrium constant for A + B C + D, then

Equilibrium constant for (reverse reaction) C + D A + B is 1/K1

If K1 be equilibrium constant for P Q and K2 be the equilibrium constant

for R S then equilibrium constant for P + R Q + S is K1. K2

If K1 be the equilibrium constant for A B and K2 be

the equilibrium constant for C ByDarvind Arora
Then equilibrium constant for the reaction

Κ1
A+D B + C is
Κ2
Inference from Kc values
At any instant At equilibrium
[C]c [D]d [C]c [D]d
aA + bB cC + dD Q = a b
Kc =
[A] [B] [A]a [B]b
High Value of Kc (Kc > 103) → At equilibrium reaction is forward dominant

Low Value of Kc (Kc < 10-3) → At equilibrium reaction is backward dominant

By arvind Arora
Moderate Value of Kc (between 103 and 10–3)
At equilibrium neither direction dominates
Reaction Quotient (Q)

Q has same expression as Kc

Q can be defined at any stage of the reaction but its value will become equal to K c only at
equilibrium condition.

If we vary the concentration of any component the value of Q will change

By arvind Arora
A + 2B 3C + D
Kc = [C]3[D]/[A][B]2

Q = [C]3[D]/[A][B]2
Q > Kc: Reaction will tend towards backward direction

Q < Kc: Reaction will tend towards forward direction

Q = Kc: Reaction will be at equilibrium

By arvind Arora
Equilibrium Constant Kp
• For gas phase reaction equilibrium constant is expressed in terms of
partial pressure.
• Concentration of reactants and products in gaseous phase is expressed
in partial pressures.

• kc and kp have same form.

By arvind
• The expression of kp is obtained from kArora
c
by replacing molar concentration
by partial pressure.
• The subscript ‘p’ in kp indicates partial pressure.

• kc is expressed in terms of molar concentration while kp is expressed in terms

of partial pressure
 Consider a reversible chemical
reaction
aA(g) + bB(g) cC(g) + dD(g)
[C]c [D]d ‘a’, ‘b’, ‘c’ and ‘d’ are the stoichiometric
kc = coefficient of A, B, C and D respectively.
[A]a [B]b

c
kp = (PC) (PD)
d
Since the expression of kp is obtained from kc by
By arvind Arora
replacing molar concentration by partial pressure(p).
(PA)a (PB)b

pA, pB, pC and pD is the partial pressure of of A, B, C and D respectively.

EQUILIBRIUM CONSTANT (kp) aA(g) + bB(g) cC(g) + dD(g)
Units
c d
kp = (PC) (PD)
Units of partial pressure is atm or bar (PA)a (PB)b
c d
kp = (atm) (atm)
(atm)a (atm)b

kp = (atm)(c+d) – (a+b) By
kp =arvind
atmΔn or Arora
barΔn

where Δn is difference in number of moles of gaseous product

and number of moles of gaseous reactant
 Relation between kp and kc`

Relationship between k and k

p c
Consider a reversible chemical
reaction (p ) c
(p ) d
aA(g) + bB(g) cC(g) + dD(g) kp = C D
(pA)a (pB)b
The partial pressure of each component in the mixture of ideal gases is directly
proportional to its concentration at constant temperature.

For component A, the partial pressure can be expressed as …

By arvind Arora
pAV = nART ……Ideal Gas Equation
where, pA is the partial pressure of component A
V = volume of gas R = gas constant (R=0.08206 L atm K-1 mol-1)
nA = moles of A T = temperature
Relationship between k and k
p c
c d
kp = (PC) (PD) ……mathematical form of
(PA)a (PB)b k
p
pAV = nART ……partial pressure of A

pA = n A R T
Since nA/V = concentration(mol/dm3)
V Simila
By arvind Arora rly
pB = [B] R T
Concentration of A = [A]
pC = [C] R T
pA = [A] R T ……relationship between
pD = [D] R T
partial
pressure and concentration
 (p ) c
(p ) d pA = [A] R T pC = [C] R T
kp = C D
(pA) (pB)b
a
pB = [B] R T pD = [D] R T
Substituting the values of pA, pB, pC
and pD in expression of kp
( [C] RT )c ( [D] RT )d [C]c [D]d
kp = kc =
( [A] RT )a ( [B] RT )b [A]a [B]b

[C]c [D]d (RT )c+d By arvind Arora

kp =
[A]a [B]b (RT )a+b
kp = kc (RT )(c + d) – (a + b)
where Δn is the difference between the
number of moles of gaseous product and
kp = kc (RT )Δn
number of moles of gaseous reactant
Relationship of Keq and DG

DG = DG0 + RT lnQ

Where Q is the reaction quotient

We know that at equilibrium DG = 0

DG0 = – RT lnKeq = – 2.303RT log10Keq

By arvind Arora
If the standard active masses are taken as 1 M each then we will take Keq =
KC and if they are taken as 1 atm each then we will take Keq = KP.
 Homogenous Equilibria

Those reactions in which all the components are in the same

phase

Homogenous Reactions can further be divided into three sub-categories:

1. Those reactions where gaseous moles increase (Δn = +ve)

By moles
2. Those reactions where gaseous arvind Arora
remain the same (Δn = 0)
3. Those reactions where gaseous moles decrease (Δn = –ve)
Case-1: (Δn=+ve)

PCl5 PCl3 + Cl2 (Δn= +1)

PCl5 PCl3 + Cl2

Initial moles: a 0 0
At equilibrium: a–x x x
Concentration: (a – x)/V x/V x/V
By arvind Arora
Q = [PCl3][Cl2]/[PCl5] = x2/(a – x)V

At equilibrium : Q = x2/(a – x)V = KC

ANALYSI
S
If we increase the concentration of PCl5 then the value of Q<KC and the
reaction will go forward. So on introducing a reactant the reaction will move
forward.

If we increase the concentration of PCl3 or Cl2 then Q>KC and the reaction will
go backwards. By arvind Arora
So on increasing the amount of products the reaction will go backwards.

If we increase the volume of the container Q<KC and the reaction will go
forward in this case. On increasing the volume of the container the reaction
will go towards greater number of gaseous moles.
Case-2: (Δn=-ve)

2NO2 N 2 O4

2NO2 N 2 O4
Initial moles: a 0
At equilibrium: a – 2x x
Concentration: (a – 2x)/V x/V

2 2
By arvind Arora
Q = [N2O4]/[NO2] = xV/(a – 2x)

At equilibrium: Q = xV/(a – 2x)2 = KC-

ANALYSI
S
If we increase the concentration of NO2 then the value of Q<KC and the
reaction will go forward. So on introducing a reactant the reaction will
move forward.

If we increase the concentration of N2O4 then Q>KC and the reaction will
go backwards. So on increasing the amount of products the reaction will go
backwards. By arvind Arora
If we increase the volume of the container Q>KC and the reaction will go
backward in this case. On increasing the volume of the container the
reaction will go towards greater number of gaseous moles.
Case-3: (Δn=0)

H2 + I2 2HI

Q = [HI]2/[H2][I2] = (2x)2/(a – x)2 = KC

By arvind Arora
ANALYSIS

On increasing reactant the reaction will go

forward

On increasing product it will go backward

As volume does not appear in the above equation it won’t disturb the
equilibrium at all. So, there is no effect of volume on those equilibria where
gaseous moles are equal on bothBy arvind Arora
sides of the equation.
 Effect of Pressure

PCl5 PCl3 + Cl2

Initial moles: a 0 0
At equilibrium: a – x x x
Mole Fractions: (a – x)/(a + x) x/(a + x) x/(a + x)
(divide moles by total moles)
Partial pressure: (a – x)P/(a + x) xP/(a + x) xP/(a + x) (multiply by total P)
By arvind Arora
Now we can write the expression for Q in terms of partial pressures:
Q = x2P/(a2 – x2) = KP (Equilibrium condition)

If we increase the Pressure of the system then Q>KP

and the reaction will go backwards.

We can conclude that on increasing the pressure on equilibrium of gases

the reaction moves towards lesser number of gaseous moles.
By arvind Arora
Degree of Dissociation α :

It is defined as the fraction of molecules dissociating i.e. No. of moles dissociating

out of 1 mole

Example

If α = 0.4 ⇒ 0.4 moles are dissociating out of 1 mole

By arvind Arora
 PCl5 PCl3 + Cl2
Initial moles: a 0 0
At equilibrium: a(1 – α) aα aα
Mole Fractions: (1 – α)/(1 + α) α/(1 + α) α/(1 + α)
Partial pressure: (1 – α) P/(1 + α) αP/(1 + α) αP/(1 + α)

pcl2. ppcl3 Divide by total no. of

Q=
ppcl5 moles a(1 + α)
By arvind Arora
αp αp
1+α 1+α α 2P
=
1–α p 1– α2
1+α
Heterogeneous Equilibrium :

All the reactants and products are not in the same phase

we assume the active masses of solids and excess liquids as constant.

CaCO3(s) CaO(s) + CO2(g)

KC = [CO2] By arvind Arora

Kp = PCO2
 LE CHATELIERS PRINCIPLE – EFFECT OF CONCENTRATION

Le Chateliers Principle
If a system at equilibrium is subjected to change in one or more variables such as
Concentration, temperature, pressure or no. of moles then equilibrium shifts in such way so
as to undo the effect of the change.

By arvind Arora
Effect of concentration

N2(g) + 3H2(g) 2NH3(g)

Increase in the
Shifts the Forward
Concentration of
Equibrium in direction
any REACTANT
By arvind Arora
Increase in the
Shifts the Reverse
concentration of
Equibrium in direction
any PRODUCT
 Effect of temperature

Effect of temperature depends upon the type of reaction Whether it is

exothermic or endothermic But at equilibrium temperature remains constant
N2(g) + 3H2(g) 2NH3(g)
Lets say that given reaction is in equilibrium. Now if this equilibrium is subjected to change

By arvind Arora
N2(g) + 3H2(g) → 2NH3(g) + heat This reaction is exothermic in
forward direction
2NH3(g) + heat → N2(g) + 3H2(g) And is endothermic in
reverse direction
Effect of temperature

N2(g) + 3H2(g) 2NH3(g)

Endothermic reaction Favours forward reaction
Increase in the
temperature of
any system Exothermic reaction Favours Reverse reaction
By arvind Arora
Endothermic reaction Favours Reverse reaction
Decrease in the
temperature of
any system Exothermic reaction Favours Forward reaction
Effect of pressure
For an ideal gas
Pressure (P) α number of moles (n)
PV = nRT

The equilibria involving only solid are not affected by change of pressure.
By arvind Arora
The equilibrium involving liquids or gases where the number of moles before
and after attainment of equilibrium remains same (∆n = 0) is also not affected
by change of pressure.
Effect of pressure When Δn = 0

H2 + I2 2 HI
1 mol 1 mol 2 mol
∆n = no. of mole of product – no. of mole of reactant
=2–2 = 0
By arvind Arora
Since there is no change in the number of mole
The equilibrium does not change with the change in pressure

For the reaction where ∆n≠0 the equilibria are greatly influenced by
change in pressure of system.
 Effect of pressure When Δn ≠ 0
When pressure of equilibrium system is increased
N2(g) + 3H2(g) 2NH3(g)
1 mol 3 mol 2 mol
According to principle an increase of pressure on gaseous system will shift the
By arvind
equilibrium in a direction of decrease in moles. Arora

• From reactant to product n decreases Hence the equilibrium will shift in

forward direction
The equilibrium will shift in the forward direction by increasing pressure .
Effect of pressure

Increase Towards lesser number

in of gaseous moles
pressure

By arvind Arora
Decrease Towards greater number
in of gaseous moles
pressure
 Effect of Volume

Increase in volume will take the reaction towards greater

number of gaseous moles

Since pressure and volume are inversely proportional

By arvind Arora
Effect of catalyst

An addition of catalyst to the reaction system at equilibrium increases the

rates of forward and reverse reactions equally .

Catalyst has no effect on the equilibrium

By arvind Arora
It simply helps in the attainment of equilibrium state faster.
Effect of adding of inert gas

At constant volume

Addition of inert gas at constant volume

Does not affect the equilibrium
At constant pressure
By arvind Arora
Addition of inert gas at constant pressure
This increases the volume
Thus equilibrium shifts in the direction where the number of moles of
gases are more
Physical Equilibrium
Equilibrium also exists in physical processes like evaporation, sublimation,
condensation,freezing etc.

BOLLING

L V ΔH = + ve

By arvind
On increasing the temperature Arora
reaction will move in the
forward direaction.

On increasing the pressure reaction will move towards lesser number of

gaseous moles i.e.backward and more of liquid is formed.
MELTING

S L Δ H = + ve

On increasing the temperature reaction moves forward.

On increasing the pressure reaction moves towards lesser volume.

S L
Density is more By
Density arvind
is less Arora
volume is less volume is more

So on increasing the pressure reaction moves backward

 Ice water
Density is less Density is more
volume is more volume is less

On increasing the pressure reaction moves towards lesser

volume i.e. forward in this case

By arvind Arora
 Arvind Arora

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