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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

form the reactants again 2KClO3 (s) 2KCl (s) + 3O2 (g)

Do not attain equilibrium state

 Examples of Irreversible Reaction

Precipitation
NaCl (aq) + AgNO3 (aq) AgCl (s) + NaNO3 (aq)
reaction

Neutralization
HCl (aq) + NaOH (aq) NaCl (s) + H2O (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) + O2 (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

C2H5OH (l) + CH3COOH (l) ⇌ CH3COOC2H5 (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
factors taking the [P] 0
reaction in the forward &
the backward direction
are balancing each other Rate of the
backward reaction = 0
 Chemical Equilibrium

As reaction proceeds, R ⇌ P
At
[R] [P] equilibrium

[R] Constant

Rate of the forward

reaction [P] Constant

Rate of the forward Rate of the

Rate of the backward reaction (rf ) = backward reaction
reaction (rb )
 Graphical Representation

Concentration
[R]
rf
Rate

rb
[P]

Time Time
 Graphical Representation
Concentration

Concentration
[R] [R]

[P] [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: N2 (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

 CaCO3(s) ⇌ CaO (s) + CO2 (g)
At t = 0, At t = 1 hr, At t = 2 hr,
P=0 P = a bar P = a bar
 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
 Case - I

Let after 75 % conversion equilibrium is achieved

N2 (g) + 3H2 (g) ⇌ 2NH3 (g)

ci 0.2 0.6 0

ceq 0.05 0.15 0.3

 Case - I

Same equilibrium state can be

achieved starting from product

N2 (g) + 3H2 (g) ⇌ 2NH3 (g)

ci 0 0 0.4

ceq 0.05 0.15 0.3

25% conversion
 Case - II
Let after 50 % conversion of N2 equilibrium is achieved

N2 (g) + 3H2 (g) ⇌ 2NH3 (g)

ci 0.3 0.6 0

ceq 0.15 0.15 0.3

This composition cannot be achieved

starting only from NH3 (backward 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
Active Mass
 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]deq
At
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 (K c )

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) + CO2 (g) KC = [CO2(g)]eq

Activity of pure solids is taken as 1

CH3COOC2H5 (aq) + H2O (l) ⇌ CH3COOH (aq) + C2H5OH (aq)

[CH3COOH]eq [C2H5OH]eq
KC =
[CH3COOC2H5]eq
 Example

CH3COOH (l) + C2H5OH (l) ⇌ CH3COOC2H5 (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)beq

Equilibrium constant in terms

of partial pressure
 K p and K c

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)beq
 Relation between K p and K c

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 K p and K c

aA (g) + bB (g) ⇌ cC (g) + dD (g)

(PC)ceq (PD)deq

(RT)c (RT)d
[C]ceq [D]deq KC
KC = (PA)aeq (PB)beq
[A]aeq [B]beq
(RT)a (RT)b

P
C = RT
Relation between K p and K c

(PC)ceq (PD)deq
Kc = RT (a + b) - (c + d)
(PA)aeq (PB)beq

- Δng
Kc = KP (RT)

Δ ng
KP = Kc (RT)
 Δn g

Sum of stoichiometric Sum of stoichiometric

Δng = coefficients of _ coefficients of
gaseous products gaseous reactants

Example: N2 (g) + 3H2 (g) ⇌ 2NH3 (g)

Δng = 2 - (3 + 1) = -2
 Unit of K p
Δng
Unit of Kp (atm)

Example: N2 (g) + 3H2 (g) ⇌ 2NH3 (g)

Δng
Unit of Kp = (atm) = atm-2

Kp can be
When Δng = 0
equal to Kc

For example, H2 (g) + I2 (g) ⇌ 2HI (g)

 KP & K𝝌

aA (g) + bB (g) ⇌ cC (g) + dD (g)

(PC)ceq (PD)deq
KP
(PA)aeq (PB)beq

(𝝌C)ceq (𝝌D)deq
K𝝌
(𝝌A)aeq (𝝌B)beq
 Relation between K P & K 𝝌

Px (𝝌C)ceq (𝝌D)deq (PTotal)eqc+d

𝝌x = KP
PTotal
(𝝌A)aeq (𝝌B)beq (PTotal)eqa+b

(𝝌CPTotal)ceq (𝝌DPTotal)deq
Δ ng
KP KP = K𝝌 (PTotal)eq
(𝝌APTotal)aeq (𝝌BPTotal)beq
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 KCI = = 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

1 1 1
A (aq) + B (aq) ⇌ C (aq) 2
A (aq) +
2
B (aq) ⇌ 2
C (aq)

[C] [C] 1/2

KC = =K KC| = = K1/2
[A] [B] [A] [B]
1/2 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
Temperature Dependence of Equilibrium Constant

If K1 & K2 are the equilibrium

constants at temperature T1 & T2

K2 ΔHo 1 1
log
K1
= 2.303 R T1 T2

ΔHo Standard Enthalpy change

R Universal gas constant

 For the reaction:

A2 (g) + B2 (g) ⇌ 2AB (g)

Given
To calculate
KC = 16
[A2]eq & [B2]eq [A2]0 = 1 M
[B2]0 = 1 M
V=1L

[A2]0 Initial Concentration of A2

[B2]0 Initial Concentration of B2

 A2 (g) + B2 (g) ⇌ 2AB (g)

Concentration at t = 0 1 1 0
( mol L-1 )

Concentration at t = teq
( mol L-1 ) 1-x 1-x 2x

Moles of A2 and B2
x
dissociated
 Calculating Equilibrium Concentrations

[2x]2 [2x]2
KC = = = 16
[1 - x] [1 - x] [1 - x]2

Taking square root on both sides

[2x]
[1 - x]
= 4
Calculating Equilibrium Concentrations

4 - 4x = 2x

6x = 4

2
x = 3
 Calculating Equilibrium Concentrations

x 2 1
[A2]eq = [A2]o
V = 1-
3
= 3
M

x 1
[B2]eq = [B2]o = 1- 2 = M
V 3 3
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
 Reaction Quotient (Q)

Reaction
A ⇌Quotient
B (Q)

Sum of Internal
At any point in a
energy
reaction, ratio of
and PV energy terms
concentration of a QC Qp
system
havingunder a given
the same form Reaction quotient Reaction quotient
set of conditions.
as the equilibrium in terms of in terms of
constant expression concentration partial pressure
 Reaction Quotient (Q)

For a reaction, aA (aq) + bB (aq) ⇌ cC (aq) + dD (aq)

[C]c [D]d These concentrations

QC = [A]a [B]b
are not necessarily
at equilibrium

Reaction
Quotient
Equilibrium
reached

0 Time
 Reaction
A ⇌Quotient
B (Q)

Case 1 Case 2 Case 3

QC > KC QC < KC QC = KC
 Reaction Quotient (Q)

QC > KC

To achieve equilibrium

[Reactants]
Equilibrium proceeds
QC in backward direction

[Products]
 Reaction Quotient (Q)

QC < KC

To achieve equilibrium

[Reactants]
Equilibrium proceeds R ⇌ P
QC in forward direction

[Products]
Reaction Quotient (Q)

QC = KC

Reaction at Equilibrium
 Degree of Dissociation (⍺)
⍺
Fraction of one
mole dissociated
into the products

Number of moles dissociated

Degree of dissociation = Initial number of moles taken

% dissociation = ⍺ ✕ 100
 Degree of Dissociation (⍺)

PCl5 (g) ⇌ PCl3 (g) + Cl2 (g)

At t = 0 10 moles 0 0

At t = teq 5 moles 5 moles 5 moles

5
⍺ = 10
= 0.5
 Degree of Dissociation (⍺)

At t = 0, only PCl5 At t = teq PCl5, PCl3

is present & Cl2 are present
Degree of Dissociation (⍺)

Varies
from
0 to 1

𝛂 Can be
fractional

Has no
units
 Calculating Moles in Terms of ⍺

An ⇌ nA

Before Dissociation
a 0
(mole)

After Dissociation a-x nx

(mole)

After Dissociation
a - a⍺ n a⍺
(mole)
 Calculating Moles in Terms of ⍺

Number of moles dissociated

⍺ = Initial number of moles

x
⍺ = a

Total moles
at equilibrium
= a - a⍺ + na⍺ = a [1 + ( n - 1 ) ⍺]
 Calculating Moles in Terms of ⍺

2AB2 (g) ⇌ 2AB (g) + B2 (g)

Before Dissociation
a 0 0
(mole)

After Dissociation a⍺
a - a⍺ a⍺
(mole) 2

Total moles a⍺ a 1+ ⍺
at equilibrium
= a - a⍺ + a⍺ +
2
= 2
Equilibrium Molar Mass
and Vapour Density
 Molar Mass of Equilibrium Mixture

Total moles at equilibrium

An (g) ⇌ nA (g)

ninitial a 0 a - a⍺ + na⍺

neq a (1 - ⍺) n a⍺
a [1 + (n - 1) ⍺]
 Molar Mass of Equilibrium Mixture

From the Law of

Initial mass = Final mass
Conservation of mass

Mass = Moles × Molar mass

Let the initial molar mass be M and Mmix

be the molar mass of the mixture
Molar Mass of Equilibrium Mixture

Ma = [ a (1 + (n - 1) ⍺) ] Mmix

M
Mmix = 1 + (n - 1) ⍺

M
Mmix
= 1 + (n - 1) ⍺ Where, n ≠ 1
 Relation between ⍺ and Vapour Density

Molar mass = 2 × Vapour density

Let, D Vapour density of gas

d Vapour density of mixture

D Not applicable for n = 1

d
= 1 + (n - 1) ⍺
E.g.: Dissociation of HI (g) & NO (g)
Plot of Vapour Density vs ⍺

D
d
= [1 + (n - 1) ⍺]

Slope: [n - 1]
D
d

⍺
 Thermodynamics of Equilibrium

Consider a reversible reaction,

aA (aq) + bB (aq) ⇌ cC (aq) + dD (aq)

ΔG = ΔGo + RT ln Q

ΔG = ΔGo + 2.303 RT log Q

 Thermodynamics of Equilibrium

At Equilibrium,

ΔG = 0 & Q = Keq

ΔGo = - RT ln Keq

ΔGo = - 2.303 RT log Keq

 Thermodynamics of Equilibrium

ΔGo = ΔHo - TΔSo

- 2.303 RT log Keq = ΔHo - TΔSo

ΔHo ΔSo
log Keq = 2.303 RT
+ 2.303 R
 Thermodynamics of Equilibrium

ΔHo = +ve Endothermic reaction

log Keq

Ө
T Keq

1
T

- ΔHo ΔSo
Slope = 2.303 R
y - Intercept = 2.303 R
 Thermodynamics of Equilibrium

ΔHo = -ve Exothermic reaction

log Keq

Ө
T Keq

1
T

- ΔHo ΔSo
Slope = 2.303 R
y - Intercept = 2.303 R
 Equilibrium Constant & Temperature

- ΔHo ΔSo
log K1 = 2.303 RT1
+ 2.303 R
…… (1)

- ΔHo ΔSo
log K2 = 2.303 RT2
+ 2.303 R
…… (2)

K1 Equilibrium constant at T1

K2 Equilibrium constant at T2
Equilibrium Constant & Temperature

Assuming ΔHº and ΔSº remains constant

in this temperature range

⇒ Eq. (1) - (2)

K1 ΔHo 1 1
log =
K2 2.303 R T2 T1

van’t Hoff equation

 Remember!!

<0 Spontaneous
Reaction at constant
T & P is feasible in the
direction which leads
ΔG =0 Equilibrium to a lowering of Gibbs
free energy.

>0 Non-spontaneous
 For a reaction R ⇌ P

Equilibrium occurs at
a minimum value of Gibbs
energy
Δr G < 0
Gibbs Δr G < 0
energy P

ΔrG = 0

Extent of reaction
Le-Chatelier’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.
 Le Chatelier’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
Temperature Dependence of Equilibrium Constant

If K1 & K2 are the equilibrium

constants at temperature T1 & T2

K2 ΔHo 1 1
log −
K1 = 2.303 R T1 T2

ΔHo Standard Enthalpy change

R Universal gas constant

 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)

Δng = 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)

Δng = + ve ⇒ QP ∝ PTotal

Reaction goes
Pressure QP QP > KP
backward
 Effect of Change in Pressure
PB 𝜒B PTotal
For the reaction, QP
= PA2 = 𝜒A PTotal
2

2A (g) ⇌ B (g)
1
Δng = - ve ⇒ QP ∝ PTotal

Reaction goes
Pressure QP QP < KP
forward
 Example

N2 (g) + O2 (g) ⇌ 2NO (g)

If P ⇒ No Shift as Δn g =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)

⇌
Δng = 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)

Δng = +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)

Δng = -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

nH nN nNH
2 2 3
 Example

NH4COONH2 (s) 2NH3 (g) + CO2

⇌
(g)

V ⇒ Forward shift

nCO nNH
2 3

[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., QP 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

On addition 2A (g) B
nTotal ⇌ Δng = - ve
of an inert gas (g)

Equilibrium shifts backward

V

Equilibrium shifts in that direction

where the moles of gas is more
 Application of
Le Chatelier’s Principle:
Practical Equilibrium
Situations
 Phase Transition

In phase transition
processes, the increase in
pressure shifts the
equilibrium towards the
denser phase.
 Phase Transition

C (Graphite, s) ⇌ C (Diamond, s) Δr H = + 1.9 kJ mol-1

 Phase Transition

Increase in pressure favours the formation

of the denser state, i.e. diamond

P
 Phase Transition

As ΔH is +ve, the increase in temperature

favours the formation of diamond

T
 Phase Transition

H2O (s) ⇌ H2O (l)

ΔrHo = + 6 kJ mol-1

Increase in pressure favours the

formation of the denser state, i.e. water

As ΔH is +ve, the increase in temperature

favours the formation of water
 Phase Transition

H2O (l) ⇌ H2O (g)

High Low density

density High
Low volume volume

Pressure Equilibrium shifts where the volume

is decreasing i.e., backward

Boiling
Pressure
point
 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
Simultaneous Equilibria
 Simultaneous Equilibria

Container with two or more equilibria

existing simultaneously involving one or
more common species

Then in all equilibrium, the

concentration of the common species
is the total concentration of that
species due to all the equilibria
 Simultaneous Equilibria

Let's look at these two equilibria

established simultaneously in a vessel

A (s) ⇌ X (g) + Y (g)

B (s) ⇌ Z (g) + Y (g)

 Simultaneous Equilibria

A (s) ⇌ M (g) + N (g) B (s) ⇌ W (g) + N (g)

At t = 0 a 0 0 b 0 0

-w p1 p1 + p2 -q p2 p 2 + p1
At t = teq

Kp1 = (p1)(p1 + p2) Kp2 = (p2)(p2 + p1)

Ionic Equilibrium
 Ionic Equilibrium

Sum of Internal energy

Equilibrium between
and
thePV energy
ionized andofthe
a _
system under form
a given AB (aq) ⇌ A+ (aq) + B (aq)
non-ionized of a
set of species
conditions.

Non-electrolytic Substance which Electrolytic

substance dissolves in water substance
 Quick Contrast

Non - electrolytic
Electrolytic substances
substances

Do not produce ions Have tendency to produce

in H2O ions in H2O

Their solutions do not Their solutions conduct

conduct electricity electricity

E.g: Urea, Glucose E.g: Acids, Bases, Salts

 Electrolytes

𝛂 << 1 Weak Electrolyte

Electrolytes Degree of
Ionization

𝛂≈1 Strong Electrolyte

 Electrolytes

Weak Electrolytes Strong Electrolytes

Examples: H2CO3, NH4OH Examples: HCl, NaOH

_ _
NH4OH (aq) ⇌ NH4 + (aq) + OH (aq) HCl (aq) H+ (aq) + Cl (aq)
 Ionic Equilibrium

Equilibrium is observed in Weak electrolytes

Weak electrolytes undergo partial

ionization in aqueous solutions
Acid - Base Concept
 Acid-Base Concepts

Acid-Base Concepts

Arrhenius Bronsted - Lowry Lewis

 Arrhenius Concept

Arrhenius Acid

Substances that dissociates

in water to give hydrogen
ion or H+ (aq)

HA (aq) H+ (aq) + A– (aq)

 Types of Acids

Monobasic Gives single H+

1 (or per molecule
Monoprotic)

Dibasic Gives a maximum

Arrhenius
2 (or Diprotic) of two H+ per
Acid
molecule

Tribasic Gives a maximum

3 (or Triprotic) of three H+ per
molecule
 Examples

HCl (aq) H+ (aq) + Cl– (aq)

H2SO4 (aq) 2H+ (aq) + SO42– (aq)

H3PO4 (aq) ⇌ 3H+ (aq) + PO43– (aq)

 Arrhenius Acid

HA + H2O H3O+ + A–

H+ ions in water are extremely

hydrated (in form of H3O+, H5O2+,
H7O3+) due to its high charge density

H+ ions form bonds with the

oxygen atoms of the solvent water
molecules to form trigonal
pyramidal hydronium ions.

H3O+ or [H (H2O)]+
Existence of H+ in Water

Generalised formula
of hydronium ion:

[H (H2O)x]+ where 'x' is the

number of water molecules
attached

H5O2+, H7O3+, H9O4+

etc.
 Existence of H+ Ion in Water

H5O2+

H9O4+
 Arrhenius Concept

Arrhenius Base

Substances that dissociates in

water to produce hydroxyl ions
or OH- (aq)

BOH (aq) B+ (aq) + OH– (aq)

 Types of Bases
Arrhenius Bases

Monoacidic Diacidic Triacidic

Gives a maximum
Gives single OH- Gives a maximum of three OH-
of two OH- per
per molecule per molecule
molecule

KOH Ca(OH)2 Al(OH)3

NaOH (aq) Na+ (aq) + OH– (aq)

Examples:
+
NH4OH (aq) ⇌ NH4 (aq) + OH– (aq)
 Limitations of Arrhenius Theory

Limited to aqueous
solutions only Does not account for the basic
nature of substances that do not
contain hydroxide ion (E.g. NH3)
 Bronsted - Lowry Concept

Species which can

Bronsted Acid
donate H+
X= HCl B= NH3

HX + B HB+ + X– Acid Base

Species which can

Bronsted Base
accept H+

HX + B HB+ + X–
 Bronsted - Lowry Concept

Addition of proton

HCl + NH3 ⇌ NH4+ + Cl–

Removal of proton
 Conjugate Acid-Base Pair

Acid-base pair, related

Conjugate
through the loss or gain
pair
of a proton

Example
H2O & H3O+ ; CH3COOH & CH3COO−
s
 Conjugate Acid-Base Pair

Conjugate Acid-Base pair

_
CH3COOH (aq) + H2O (l) ⇌ H3O+ (aq) + CH3COO (aq)

Conjugate Acid-Base pair

 Conjugate Acid
+ H+
NH3 NH4+

Species formed by the Base Conjugate

gain of a proton by a base Acid
is called the conjugate
acid of that base. H

+
N N
H H H
H
H H
 Conjugate Base

- H+ _
CH3COOH CH3COO

Acid Conjugate
Base
O O
H H
H H
C C C C

H O −
H
O
H
 Conjugate Acid-Base Pairs

Conjugate base of Conjugate base of

Very weak Strong
strong acid is very weak acid is

Strong acid Very Weak acid

_
HCl H+ + Cl– CH4 ⇌ H+ + CH3

Very weak base Strong base

Relative Strength of Acid - Base Pair

Acidic strength

HA1 > HA2

Reaction will always favour in a direction
from a stronger acid to a weaker acid or
from a stronger base to a weaker base
Basic strength

_ _
A2 > A1
 Amphiprotic Species

Species which can act as

an acid as well as a base

HCl (aq) + H2O (aq) ⇌ H3O+ (aq) + Cl– (aq)

Acid Base Water is

amphiprotic

NH3 (aq) + H2O (aq) ⇌ NH4+ (aq) + OH– (aq)

Base Acid
 Acid-Base Concepts

Acid-Base Concepts

Arrhenius Bronsted - Lowry Lewis

 Lewis Acids

BF3, AlCl3
Incomplete
Sum of Internal energy octet
Species which can
and PV energy of a
accept
system under a given set
a pair of electrons from
of conditions.
another species
Positively
charged
species H+, Fe3+
Lewis Acids

Molecules
CO2, SO2
with multiple
bonds with
E.N. atom

Empty d
orbitals on
the central
atom SiCl4, PCl3
 Lewis Bases

NH3, H2O
With
lone pair
Sum of Internal energy
Species which can
and PV energy of a
donate its pair of Lewis With -ve
system under a given
electrons to other Bases charge OH _ , SH _
set of conditions.
species

With 𝜋
electrons
CH2= CH2
 Properties of Water

Water acts as an acid as well as base

according to Arrhenius & Bronsted-Lowry
theory, but according to Lewis concept it is
a base, not an acid

Self ionization of water or Autoprotolysis

H2O (l) + H2O (l) ⇌ H3O+ (aq) + OH– (aq) Or H2O (l) ⇌ H+ (aq) + OH– (aq)
 Properties of Water

In self-ionization Equal number of

of water ions are formed

[H+] = [OH–]

So, pure water is neither acidic nor basic

 Molar Concentration

Number of moles
Molarity of water =
Volume of the solution

For water

● Density = 1 g/cc
● Molar mass = 18 g/mol
● Volume = 1 L
 Molar Concentration

1000/18
Molarity = 1

moles
Molarity = 55.55
Litre

Molarity = 55.55 M
 Ionization Constant of Water (K W)

H2O (l) ⇌ H+ (aq) + OH– (aq)

Kw = Keq [H2O] constant

[H+] [OH–] Ionic product or Ionisation

Keq = [H2O]
Kw
constant of water

Kw = [H+] [OH–]
Keq [H2O] = [H+] [OH–]
Ionization Constant of Water (K W)
At 25 oC

Experimental data
Kw
-14
Kw = [H+] [OH–] = 10

The product of the Pure water contains

molar concentrations
of H+ and OH– ions [H+] = [OH–] = 10–7 M
 Degree of Ionization of Water

H2O (l) ⇌ H+ (aq) + OH– (aq)

Number of moles dissociated [H+] = [OH–] = 10–7 M

⍺ = Number of moles initially taken

10–7 55.55
⍺ = 55.55
 Degree of Ionization of Water

At 25 oC

⍺ = 1.8 × 10–9 = 1.8 × 10–7 %

Absolute Dissociation Constant of Water
H2O (l) ⇌ H+ (aq) + OH– (aq)
Neutral
solution [H+] = [OH–]

[H+] [OH–]
Keq = [H2O]
Acidic
solution [H+] > [OH–]
10-7 × 10-7
Keq =
55.55

Basic
solution
[H+] < [OH–]
Keq = 1.8 × 10-16
 pH Scale

pH is defined as negative
logarithm of activity of H+ ions
Concentration of H+
ions is written in a
simplified form
introduced by Sorenson pH = - log a H+
known as pH scale

Sorenson a H+ Activity of H+ ions

 pH Scale

In a dilute solution,

Activity Concentration of free

of H+ ions = H+ ions or H3O+ ions

pH scale was marked from

0 to 14 with the central point at 7 at
25 °C taking water as the solvent
 pH Scale
In general, for any quantity ‘X’,
we can define a term pX as

pX = − log X

pH = − log [H+]

_
pOH = − log [OH ]
 pH Scale

Kw = [H+] [OH–] = 10–14

Taking logarithm and multiplying by (− 1) on both sides,

- log (Kw) = - log [H+] - log [OH–]

= - log (10–14)
 pH Scale

At any temperature,

pKw = pH + pOH

At 25 oC,

pKw = pH + pOH = 14
 pH Scale
At 25 oC

Acidic Neutral Basic

pH < 7 pOH > 7 pH = 7 pOH = 7 pH > 7 pOH < 7

 pH Scale

Acidic strength
Tendency
Tendency of an acid to give pH
to give H+
H3O+ or H+ ions in water

Basic strength

Tendency
Tendency of a base to give _ pH
_
OH ions in water to give OH
 pH Scale

_
H2O (l) ⇌ H+ (aq) + OH (aq)

Dissociation of water is endothermic

⇒ T Kw

T Kw
 pH Scale

25 oC 10-14

Kw 40 oC 2.916 ✕ 10-14

90 oC 38.02 X 10-14
 pH Scale

T Kw

Kw decreases from 10-14 at 25 oC to (0.293 x 10-14) at 10 oC

[H+] = Kw = 0.293 x 10-14 = 0.541 x 10-7

pH = - log [H+] = 7.27

⇒ Now 7.27 is the midpoint of the new pH scale

 pH Scale

T Kw

Kw increases from 10-14 at 25 oC to 38.02 x 10-14 at 90 oC

[H+] = Kw = 38.02 x 10-14 = 10–6.21

pH = - log [H+] = 6.21

⇒ Now 6.21 is the midpoint of the new pH scale

 Strong Acid Solution

[H+]Strong acid > 10-6 M

H+ ions coming from water can be neglected

Molarity of the Number of H+

[H+] = strong acid x ions per acid
solution molecule
 Strong Acid Solution

[H+]Strong acid < 10-6 M

H+ ions coming from water cannot be neglected

[H+] coming from

[H+] from water in the
[H+] = strong acid + presence of the
strong acid
 Mixture of Two Strong Acids

Strong acid Strong acid Mixture

V1 + V2 V1 + V2
[H+]1 [H+]2 [H+]f

Ⅰ - solution Ⅱ - solution
 Mixture of Two Strong Acids

Number of H+ ions
[H+] = Molarity x per acid molecule

Moles of H+ ions
from Ⅰ - solution = [H+]1V1

Moles of H+ ions
from Ⅱ - solution = [H+]2V2
 Mixture of Two Strong Acids

Vf = V1 + V 2

[H+]f Vf = [H+]1 V1 + [H+]2 V2

[H+]1 V1 + [H+]2 V2
[H+]f =
V1 + V 2
 Mixture of Two Strong Bases

Strong Strong
Mixture
base base
V1
+ V2
V1 + V2
_
_ _ [OH ]f
[OH ]1 [OH ]2

Ⅰ - solution Ⅱ - solution

_ _
_ [OH ]1 V1 + [OH ]2 V2
[OH ]f =
V1 + V 2
Mixture of a Strong Acid and a Strong Base

Acid - base neutralization

reaction will take place

Solution will be acidic or

basic depending upon which
is taken in excess
 Mixture of a Strong Acid and a Strong Base

Strong acid Strong base

Mixture
V1 + V2
_ V1 + V2
[H+] [OH ]

Ⅰ - solution Ⅱ - solution

Moles of H+ ions
from Ⅰ - solution = [H+] V1

_
Moles of OH ions _
from Ⅱ - solution = [OH ] V2
Mixture of a Strong Acid and a Strong Base

_
_ If [H+] V1 < [OH ] V2
If [H+] V1 > [OH ] V2

_ _
[H+] V1 - [OH ] V2 _ [OH ] V2 - [H+] V1
[H+]f = [OH ]f =
V1 + V 2 V1 + V 2

Final solution will be acidic in nature Final solution will be basic in nature
 Weak Acid

For weak acids, pH can’t

be calculated directly

. ⍺ < 1
:

[HA] ≠ [H+]
Factors Affecting Degree of Ionization

Temperature

Nature of the Presence of

Solvent Degree of other solutes
Ionization

Nature of the
Dilution
Electrolyte
 Ionization of Weak Acids

Consider a weak acid ‘HA’

HA (aq) + H2O (l) ⇌ A– (aq) + H3O+ (aq)

[H3O+] [A–]
Keq =
[HA]

Keq Equilibrium constant for

the dissociation of HA
 Ionization Constant of Weak Acids (K a )
For a weak acid Ka

Ionization constant for

Keq = Ka
weak acids and it is a
measure of its strength.

[H3O+] [A–]
Ka = [HA] Acidic
Ka pKa
strength

pKa = − log Ka
 pH of Weak Acids

HA (aq) + H2O (l) ⇌ A– (aq) + H3O+ (aq)

Initial
Concentration __
c 0 0
(t = 0)

Equilibrium
Concentration (c - c⍺) __ c⍺ c⍺
(t = teq)
 pH of a Weak Acid

[H3O+] [A–] c⍺2

Ka = = If ⍺ << 1, it can
[HA] (1 - ⍺)
be neglected

1−⍺ ≈ 1

Ka = c⍺2
 Ostwald’s Dilution Law

1
Ka 2 1
⍺ =
c ⍺

On 0.1
dilution;
c ⍺
c

At infinite dilution, ⍺ reaches its maximum value, i.e. unity.

Weak electrolyte starts behaving like a strong electrolyte!
 pH of a Weak Acid

1
Ka 2
⍺ = Valid if ⍺ < 0.1 or 10%
c

[H+] = c⍺

1
[H+] = (Ka x c) 2
 pH of a Weak Acid

1
Taking logarithm and multiplying by −1 on both
[H+] = (Ka x c) 2 sides
1
- log [H+] = - log (Ka x c) 2

pH of a weak acid

1
Valid if ⍺ < 0.1 or 10%
pH = 2
(pKa − log c)
 pH of a Weak Acid

Ka
If 𝛂 obtained from is greater than 0.1,
c
solve quadratic equation and get accurate 𝛂

Then; [H+ ] = c𝛂

Now pH calculation can be done

 Ionization Constant of Weak Bases (K b)
Consider a weak base
‘MOH’
Kb
MOH (aq) + H2O (l) ⇌ M+ (aq) + OH– (aq)
Ionization constant
for weak bases and a
[M+] [OH–]
Kb = measure of its strength
[MOH]

pKb = − log Kb Basic

Kb pKb
strength
pH calculation of Weak Base
 Weak Base

For weak bases, pH can’t

be calculated directly

⍺ < 1

[MOH] ≠ [OH–]
 Ionization Constant of Weak Bases (K b)

MOH (aq) + H2O (l) M+ (aq) + OH–

⇌
(aq)

Initial
Concentration
c __ 0 0
(t = 0)

Equilibrium
Concentration (c - c⍺) __ c⍺ c⍺
(t = teq)
 Ionization Constant of Weak Bases (K b)

[M+] [OH–] c⍺2

Kb = [MOH] =
(1 - ⍺)

1
Kb 2
If ⍺ << 1 ⍺ =
c

[OH–] = (Kb x c)
 pH of Weak Bases

1
pOH of a weak base pOH = 2
(pKb − log c)

1
pOH = 2
(pKb − log c)
At 25℃, pH + pOH = 14

pH = 14 - pOH
Valid if ⍺ < 0.1 or 10%
 Remember!!

Kb
If 𝛂 obtained from is greater than 0.1,
c
solve quadratic equation and get accurate 𝛂

_
Then; [OH ] = c𝛂

Now pOH calculation can be done

 Relation between pK a and pK b

Consider a weak acid HA,

Conjugate base of HA is A–

HA (aq) ⇌ H+ (aq) + A– (aq)

A– (aq) + H2O (l) ⇌ OH– (aq) + HA (aq)

[H+] [A–] (i
Ka = [OH–] [HA]
[HA] ) Kb = (ii)
[A–]
 Relation between pKa and pKb

Multiply equation (i) and (ii)

[H+] [A–] [OH–] [HA]

Ka x Kb = x
[HA] [A–]

Ka x Kb = [H+] [OH–]

For an acid-base
conjugate pair
Ka x Kb = Kw
 Relation between pK a and pK b

Taking logarithm and multiplying by −1 on both sides

- log (Ka × Kb) = - log (Kw)

- log (Ka) - log (Kb) = - log (Kw)

At 25oC
pKa + pKb = pKw = 14
Common Ion Effect
 Dissociation of Electrolytes in Water

Strong
HCl (aq) H+ (aq) + Cl– (aq)
electrolyte

Weak CH3COOH (aq) ⇌ CH3COO– (aq) + H+ (aq)

electrolyte
 Dissociation of CH 3 COOH & HCl

Weak
CH3COOH (aq) ⇌ CH3COO– (aq) + H+ (aq)
electrolyte

Strong
electrolyte HCl (aq) Cl– (aq) + H+ (aq)

Common Ion
 Common Ion Effect

CH3COOH (aq) ⇌ CH3COO– (aq) + H+ (aq)

On adding HCl (aq) Cl– (aq) + H+ (aq)

HCl,

Concentration of the
common ion (H+ )
 Common Ion Effect

Based on Le Chatelier’s Principle

When a substance is present in
a solution, it may affect the
CH3COOH (aq) ⇌ CH3COO– (aq) + H+ (aq)
dissociation of another
substance.

Equilibrium will be shifted backwards

 Common Ion Effect

If H+ is the common ion,

Suppression in Equilibrium Dissociation of

the dissociation But [H+] in
shifts CH3COOH is
of a weak solution
backward suppressed
electrolyte by the
addition of a
strong electrolyte
having a common
ion
pH of the solution
 Mixture of Weak Acid & Strong Acid

Strong acid Weak acid

+ Mixture
c1 c2

Ⅰ - solution Ⅱ - solution

HA (aq) ⇌ H+ (aq) + A– (aq)

Initial
Concentration c2 c1 0
(M) (Comes from
strong acid)

Equilibrium
Concentration c2 (1 - ⍺) c1 + c2⍺ c2⍺
(M)
Mixture of Weak Acid & Strong Acid

[H+] [A–]
Ka = [HA]

(c1 + c2⍺) (c2⍺)

Ka = (i)
(c2 (1 - ⍺))
 Mixture of Weak Acid & Strong Acid

Weak acid’s dissociation will be further suppressed

because of presence of strong acid therefore ⍺ << 1

c1 + c2⍺ ≈ c1 & 1-⍺ ≈ 1

Ka ≈ c1⍺ (ii)
 Mixture of Weak Acid & Strong Acid

If ⍺ from (ii) comes < 0.1 If ⍺ from (ii) comes ≥ 0.1

Solve quadratic equation in ⍺

Assumption is correct
(equation (i) ) to get exact ⍺

[H+]Total = c1 [H+]Total = c1 + c2⍺

 Isohydric
solutions

If the concentration of the

common ions in the solution of
two electrolytes is the same,
then on mixing them, there is
no change in the degree of
dissociation of either of the
electrolytes.
Mixture of Two Weak Monoprotic Acids
Weak acid Weak acid
HA + HB Mixture
c1 c2
Ⅰ - solution Ⅱ - solution

HA (aq) ⇌ H+ (aq) + A− (aq)

t=0 c1 0 0

t = teq c1(1 - ⍺1) c1⍺1 + c2⍺2 c1⍺1

 Mixture of Two Weak Monoprotic Acids

HB (aq) ⇌ H+ (aq) + B− (aq)

t=0 c2 0 0

t = teq c2(1 - ⍺2) c2⍺2 + c1⍺1 c2⍺2

 Mixture of Two Weak Monoprotic Acids
(c1⍺1 + c2⍺2) (c1⍺1)
K a1 = (i)
(c1)(1 - ⍺1)

(c1⍺1 + c2⍺2) (c2⍺2) (ii

K a2 = )
(c2)(1 - ⍺2)

Both acids will dissociate less than

in their individual aqueous solutions Common ion effect exerted
of the same concentration because by H+ ions of one on other
of
 Mixture of Two Weak Monoprotic Acids

For the weak

acid ‘HA’
⍺1 << 1 1 - ⍺1 ≈ 1

For the weak

acid ‘HB’
⍺2 << 1 1 - ⍺2 ≈ 1
Mixture of Two Weak Monoprotic Acids

∴ From (i) and (ii) we get

K a1 c 1 = (c1⍺1 + c2⍺2) (c1⍺1) (iii)

K a2 c 2 = (c1⍺1 + c2⍺2) (c2⍺2) (iv)

 Mixture of Two Weak Monoprotic Acids
Adding (iii) and (iv)

Ka1 c1 + Ka2 c2 = (c1⍺1 + c2⍺2)2

[H+] = c1⍺1 + c2⍺2 = Ka1 c1 + Ka2 c2

pH = log [H+]

1
pH = 2
log K a1c1 + K a2c2
Mixture of Two Weak Monoprotic Acids

If ⍺1 >> ⍺2

Contribution of HB in [H+] can be neglected

[H+] = c1⍺1 + c2⍺2 ≈ c1⍺1

 Acidity of a Base

The total number of ionizable hydroxyl (OH–)

ions present in one molecule of a base

Acidity

NaOH (aq) Na+ (aq) + OH– (aq) 1

Mg(OH)2 (aq) Mg2+ (aq) + 2OH–

2
(aq)
 Polyacidic Base

Ca(OH)2 (aq) Ca2+ (aq) + 2OH– (aq)

Bases which
contain more
than one ionizable
hydroxyl ions Al(OH)3 (aq) ⇌ Al3+ (aq) + 3OH– (aq)
 Basicity of an Acid

The total number of ionizable hydrogen (H+)

ions present in one molecule of an acid

Basicity

HCl (aq) H+ (aq) + Cl– (aq) 1

2– 2
H2SO4 (aq) 2H+ (aq) + SO4 (aq)
 Polybasic or Polyprotic Acid

H3PO4 (aq) ⇌ 3H+ (aq) + PO3–4 (aq)

Acids which
contain more than
one ionizable Number of ionizable protons in H3PO4 = 3
protons
 K a for the Dissociation of a Dibasic Acid

Ionization constant Ionization constant

K a1 Ka2
for the 1st step for the 2nd step

Ka1 Ka2
H2X (aq) H+ (aq) + HX– (aq) HX– (aq) H+ (aq) + X2– (aq)

[H+] [HX–] [H+] [X2-]

Ka1 Ka2
[H2X] [HX–]
 Overall K a for the Reaction

H2X (aq) ⇌ 2H+ (aq) + X2– (aq)

[H+]2 [X2–]
Ka
[H2X]

Ka = Ka1 x Ka2

Where Ka is the ionization constant of H2X

 K a for the Dissociation a Tribasic Acid

H3PO4 (aq) ⇌ H+ (aq) + H2PO–4 (aq) Ka 1

In general, for polybasic acids,

H2PO4– (aq) ⇌ H+ (aq) + HPO2–

4 (aq)
Ka2 If we assume an acid having ‘n’
ionizable protons, for E.g. HnA

HPO42– (aq) ⇌ H+ (aq) + PO3–

4 (aq) Ka3
Ka = Ka 1 x Ka2 x Ka3 x . . . .Kan

Ka = Ka1 x Ka x Ka3
2
Comparison of K a for Polyprotic Acids
Ka 1 >> Ka >> Ka >> Ka4 …..
2 3

H+ is lost much more easily from a

neutral HnA molecule than from a Hn-1A−
ion

[H+]1 >> [H+]2 >> [H+]3 >> [H+]4 ... Ka 1 > Ka 2 > Ka 3...

Because Ka1 is much larger than Ka2,

virtually all the [H+] in a solution comes
from the 1st step of ionization
 Polyprotic Acids

Let’s consider a weak polyprotic acid H2CO3 of concentration c1

H2CO3 (aq) ⇌ H+ (aq) + HCO−3 (aq)

At t = teq c1 (1 - ⍺1) c1 ⍺1 (1 + ⍺2) c1 ⍺1 (1 - ⍺2)

2−
HCO3− (aq) ⇌ H+ (aq) + CO3 (aq)

At t = teq c1 ⍺1 (1 - ⍺2) c1 ⍺1 (1 + ⍺2) c1⍺1⍺2

 Polyprotic Acids

[H+] [HCO3− ] c1 ⍺1(1 + ⍺2) c1 ⍺1(1 - ⍺2)

Ka =
1
[H2CO3] c1(1 - ⍺1)

2−
[H+] [CO3 ] c1 ⍺1(1 + ⍺2) c1 ⍺1⍺2
Ka =
2
[HCO3−] c1 ⍺1(1 - ⍺2)
 Polyprotic Acids

Since (c1 ⍺1) (c1 ⍺1) c1 ⍺12

Ka
1
>> Ka
2 K a1 = =
c1(1 - ⍺1) 1 - ⍺1

⍺1 >> ⍺2 c1 ⍺1 c1 ⍺1⍺2 c1
Ka2 ≈ c1 ⍺1(1 - ⍺2) ≈
⍺1⍺2

∴ c1 ⍺1 (1 + ⍺2) ≈ c1 ⍺1

c1 ⍺1 (1 - ⍺2) ≈ c1 ⍺1
 Polyprotic Acids
Total [H+] released after ionization,

[H+] Total = [H+] first step + [H+] second step

Since Ka
1
>> Ka
2

[H+] second
[H+] first step >> step

∴ [H+] Total ≈ [H+] first step pH = - log c1 ⍺1

Mixture of a Polyprotic Weak Acid & a Strong Acid

pH

Generally, pH can be calculated

by taking the concentration of
strong acid only

Other calculations can be

done by considering the
dissociation equilibria of
the weak polyprotic acid
pH of a Mixture of a Weak Monoprotic &
a Weak Polyprotic Acid

[H+] calculation can be done similar to the case

of a mixture of two weak monoprotic acids
Hydrolysis of Salts and
pH of their Solutions
 Salts and Salt Hydrolysis

Salts formed by the reaction between

an acid & a base in definite proportions
undergo ionization in water
Process of interaction of water
with cations/anions or both of
the salts is called hydrolysis
Ions formed either exist as hydrated
ions or interact with water
 Salt Hydrolysis

Salts of strong acids &

bases only get hydrated and not
hydrolysed, whereas salts of other
types do get hydrolysed.

Cation of weak base on reaction with water

will produce H+ ions and the anion of weak
acid on reaction with water produce OH- ions

pH of the solution is affected

by this interaction.
 Salt Hydrolysis

Cationic Hydrolysis
B+ (aq) + 2H2O (l) BOH (aq) + H3O+
⇌(aq)

Anionic Hydrolysis

A– (aq) + H2O (l) ⇌ HA (aq) + OH– (aq)

 Types of Salts

Salt of Salt of Salt of Salt of

SA + SB WA + SB SA + WB WA + WB

SA Strong Acid SB Strong Base

WA Weak Acid Weak Base

WB
 Types of Salts

Salt of Salt of Salt of Salt of

SA + SB WA + SB SA + WB WA + WB

NaCl CH3COONa NH4Cl CH3COONH4

 Salt of Strong Acid - Strong Base

Solution involves only

Neither of the ions will
Salt of SA + SB the equilibrium of
undergo hydrolysis
ionization of water

NaCl
2H2O (l) H3O+ (aq) + OH–
⇌ (aq)

At 25oC, pH = 7
NaOH HCl
 Salt of WA + SB

CH3COONa

CH3COOH NaOH
Hydrolysis of Salt of Weak Acid & Strong Base
Salt of WA + SB
Completely ionised in
an aqueous solution

CH3COONa

CH3COONa

CH3COOH CH3COONa (aq) CH3COO– (aq) + Na+ (aq)

NaOH
 Hydrolysis of Salt of Weak Acid & Strong Base
CH3COONa (aq) CH3COO– (aq) + Na+ Acetate ion formed
(aq) undergoes hydrolysis in water

CH3COO– (aq) + H2O (l) ⇌ CH3COOH (aq) + OH– (aq)

CH3COO− (aq) + H2O (l) ⇌ CH3COOH (aq) + OH− (aq)

[CH3COOH] [OH−]
Kh Kh Hydrolysis constant of the salt
=
[CH3COO−]
Hydrolysis of Salt of Weak Acid & Strong Base

CH3COOH (aq) ⇌ CH3COO− (aq) + H+ (aq)

[CH3COO−] [H+]
Ka =
[CH3COOH]

H2O (l) ⇌ H+ (aq) + OH− (aq)

Kw = [H+] [OH−]
Hydrolysis of Salt of Weak Acid & Strong Base

[H+] [OH−]
Kw
= [CH3COO−] [H+]
Ka
[CH3COOH]

Kw [CH3COOH] [OH−]
=
Ka [CH3COO−]

Kw
Kh =
Ka
Hydrolysis of Salt of Weak Acid & Strong Base

CH3COO− (aq) + H2O (l) CH3COOH (aq) + OH− (aq)

t=0 c 0 0

t = teq c (1 - h) ch ch

[CH3COOH] [OH−]
Kh = [CH3COO−]
Hydrolysis of Salt of Weak Acid & Strong Base

ch × ch ch2
Kh = =
c (1 − h) (1 - h)

If h << 1

Kw
Kh = ch2 =
Ka
Hydrolysis of Salt of Weak Acid & Strong Base

Kh Kw
h = =
c Kac

[OH–] = ch

Kw Kwc
[OH–] = c× [OH-] =
Kac Ka
Hydrolysis of Salt of Weak Acid & Strong Base

Kw KwKa
[H+] = =
[OH−] c

Taking logarithm on both sides and multiplying by (-1)

1 1 1
-log [H+] = −
2
log Kw −
2
log Ka +
2
log c
Hydrolysis of Salt of Weak Acid & Strong Base

1 Valid if,
pH = 2
[pKw + pKa + log c]
h < 0.1 or 10%

1
pH = 7+
2
[ pKa + log c]

At 25 0C Kh
If h obtained from > 0.1 , then solve [H+] = ch
c
the quadratic equation and get h
 Salt of SA + WB

NH4Cl

NH4OH HCl
Hydrolysis of Salt of Strong Acid & Weak Base

Salt of SA + WB
Completely ionised in
an aqueous solution

NH4Cl
NH4Cl

NH4OH HCl NH4Cl (aq) NH4+ (aq) + Cl– (aq)

Hydrolysis of Salt of Strong Acid & Weak Base

NH4Cl (aq) NH4+ (aq) + Cl– (aq)

Ammonium ion formed

undergoes hydrolysis in water

NH4+ (aq) + H2O (l) ⇌ NH4OH (aq) + H+ (aq)

Hydrolysis of Salt of Strong Acid & Weak Base

NH4+ (aq) + H2O (l)⇌ NH4OH (aq) + H+ [NH4OH] [H+]

(aq) Kh =
[NH4+]

NH4OH (aq) ⇌ NH4+ (aq) + OH− (aq)

[NH4+] [OH−]
Kb =
[NH4OH]

H2O (l) ⇌ H+ (aq) + OH− (aq) Kw = [H+] [OH−]

Hydrolysis of Salt of Strong Acid & Weak Base
[H+] [OH− ]
Kw
Kb
= [NH4+] [OH− ]
[NH4OH]

Kw [NH4OH] [H+]
=
Kb [NH4+]

Kw
Kh =
Kb
Hydrolysis of Salt of Strong Acid & Weak Base

NH4+ (aq) + H2O (l) ⇌ NH4OH (aq) + H+ (aq)

c ___ 0 0

c (1 - h) ___ ch ch

[NH4OH] [H+]
Kh =
[NH4+]
Hydrolysis of Salt of Strong Acid & Weak Base

ch × ch ch2 Kh Kw
Kh = = h = =
c (1 − h) (1 - h) c Kbc

If h << 1
[H+] = ch

Kw
ch2 = Kh =
Kb Kw
[H+] = c×
Kbc
Hydrolysis of Salt of Strong Acid & Weak Base

Kwc Taking logarithm on both sides and multiplying by -1

[H+] =
Kb
- log [H+] = − 1 log Kw − 1 log c + 1 log
2 Kb 2 2

1 Valid if
pH = 2
[pKw − pKb − log c]
h < 0.1 or 10%

1
pH = 7-
2
[ pKb + log c] At 25 0C
 Hydrolysis of Salt of Weak Acid & Weak Base

Salt of WA + WB Completely ionized in an

aqueous solution

CH3COONH4

CH3COONH4

CH3COONH4 (aq) CH3COO– (aq) + NH4+

CH3COOH NH4OH (aq)
 Hydrolysis of Salt of Weak Acid & Weak Base
Ions formed undergo hydrolysis as

CH3COONH4

CH3COO– (aq) + NH4+ (aq) + H2O (l) ⇌ CH3COOH (aq) + NH4OH (aq)

NH4+ (aq) + CH3COO− (aq) + H2O (l) ⇌ CH3COOH (aq) + NH4OH (aq)

[NH4OH] [CH3COOH]
Kh =
[NH4+] [CH3COO−]
Hydrolysis of Salt of Weak Acid & Weak Base

CH3COOH (aq) ⇌ CH3COO− (aq) + H+ (aq)

[CH3COO−] [H+]
Ka =
[CH3COOH]

NH4OH (aq) ⇌ NH4+ (aq) + OH− (aq)

[NH4+] [OH−]
Kb =
[NH4OH]
Hydrolysis of Salt of Weak Acid & Weak Base
H2O (l) ⇌ H+ (aq) + OH− (aq) [CH3COOH] [NH4OH]
Kw
= [CH3COO−] [NH4+]
KaKb

Kw = [H+] [OH−]
Kw
Kh =
[H+] [OH−] KaKb
Kw
KaKb
= [CH3COO−] [H+] [NH4+] [OH−]
×
[CH3COOH] [NH4OH]
Hydrolysis of Salt of Weak Acid & Weak Base
NH4+ (aq) + CH3COO− (aq) + H2O (l) CH3COOH (aq) + NH4OH
(aq)⇌

c c 0 0

c (1 - h) c (1 - h) ch ch

[NH4OH] [CH3COOH]
Kh =
[NH4+] [CH3COO−]
 Remember!!

For numerical analysis, even if Ka of

weak acid & Kb of weak base
are different.

Degree of hydrolysis of cations &

anions are taken equal as they are
very close to each other.
Hydrolysis of Salt of Weak Acid & Weak Base

ch × ch h2 h
Kh = = = Kh
c2 (1 − h)2 (1 - h)2 (1 − h)

[CH3COO−] [H+] c (1 − h) [H+]

Ka = Ka =
[CH3COOH] ch

h
[H+] = Ka
1−h
⇒ [H+] = Ka Kh
Hydrolysis of Salt of Weak Acid & Weak Base

1
pH = 2
[pKw + pKa - pKb]

1
pH = 7+
2
[ pKa - pKb ] At 25 oC

This formula is always valid for any Ka and Kb at

1 any temperature and for any value of h.

pH is independent of the concentration

2 of the salt solution
Hydrolysis of Salt of Weak Acid & Weak Base

If Ka = Kb pH = 7 Neutral solution

If Ka > Kb pH < 7 Acidic solution

If Ka < Kb pH > 7 Basic solution

 Type Expressio Expression
Expression for pH
of Salt n for Kh for h

Kw 1
Salt of K pH = [pKw + pKa + log c]
Kh = h= 2
WA & SB Ka h (if h < 0.1)
c
Kw 1
Salt of K pH = [pKw - pKb - log c]
Kh = h= 2
SA & WB Kb h
(if h < 0.1)
c

Salt of Kw h 1
Kh = = Kh pH = [pKw + pKa - pKb]
WA & WB K aK b 1- 2

h
 Remember!!

If h is not less than 0.1, then solve

quadratic equation in order to obtain
h and then determine [H+] or [OH–].
 Salt of Weak Polyprotic Acids
Consider H3PO4

_
H3PO4 (aq) ⇌ H+ (aq) + H2PO4 (aq) Ka1
Hydrolysis of polyvalent
ions

_
H2PO4 (aq) ⇌ H+ (aq) + HPO2−
4 (aq) Ka2
Ions like PO4 3–, CO32–, Zn2+,
Fe3+ etc. form salts like
K3PO4, Na2CO3, ZnSO4,
2− 3−
FeCl3 HPO4 (aq) ⇌ H+ (aq) + PO4 (aq) Ka3
 Salt of Weak Polyprotic Acids

Kw
2−
PO43−(aq) + H2O (l) ⇌ HPO4 (aq) + OH– (aq) Kh1 =
K a3

–
Kw
HPO42−(aq) + H2O (l) ⇌ H2PO4 (aq) + OH– (aq) Kh2 =
Ka2

H2PO
– 4 (aq) + H2O (l) H3PO4 (aq) + OH– Kw
⇌
(aq)
Kh3 =
Ka1
 Salt of Weak Polyprotic Acids
Since, Thus, pH is calculated only using
Ka1 >> Ka2 >> Ka3
the first step of hydrolysis

⇒
Kh 1 >> Kh 2 >> Kh 3

Consider a salt Na3PO4 of concentration = c

3–
PO4 (aq) + H2O (l) ⇌ HPO42– (aq) + OH– (aq)

c 0 0

c (1 - h) ch ch
 Salt of Weak Polyprotic Acids

If h << 1

ch.ch
Kh 1 = = ch2
c(1 - h)

Kh 1 Kw
3
h = =
c Ka c
 Salt of Weak Polyprotic Acids

Kw
[OH–] = c ×
Ka 3 c

Kwc
[OH–] =
Ka3

Kw KwK
[H+] = = 3
[OH–]
a

c
 Salt of Weak Polyprotic Acids
Taking logarithm on both sides and multiplying by (-1)

1 1 1
-log [H+] = −
2
log Kw −
2
log Ka3 +
2
log c

1
pH = 2
[pKw + pKa3+ log c]

If h > 0.1

Then its exact value should be Then [OH–] = ch

obtained by solving quadratic
equation.
 Amphiprotic Ions

But in Na2HPO4 and

To calculate the pH when NaH2PO4, the ions 2-
Na3PO4 is hydrolyzed, we hydrolyzed are HPO 4 and
_
3-
can say that only PO4 is H2PO4.
hydrolyzed. Both are amphiprotic ions.
 Amphiprotic Ions

+ H+ (aq)
H3PO4 (aq)
H2PO4
(aq)
2-
HPO4 (aq)
- H+ (aq)
 Amphiprotic Ions

Assuming Degree of Degree of

ionization (⍺)
=
hydrolysis (h)

2–
or [HPO4 ] = [H3PO4]

1
pH = pK a + pKa
2 1 2
 Amphiprotic Ions

+ H+ (aq)
H2PO4– (aq)

HPO42– (aq)
3–
PO4 (aq)
- H+ (aq)

1
pH = pK a + pK a
2 2 3
 Buffer Solution

Solutions which resist a change

in pH upon addition of small
amount of acid or base

pH of a buffer solution changes on the

addition of an acid or a base, but it would
be less than the change that would have
occurred had it not been a buffer
 Types of Buffer Solutions

Buffer Solutions

Mixed Buffer Simple Buffer

Acidic Salt of
Basic Buffer
Buffer WA & WB
 Acidic Buffer Solutions

Solution of a weak
acid and its salt with
a strong base

CH3COOH +
H3PO4 + NaH2PO4
CH3COONa
 pH Calculation
Buffer solution consisting of a
weak acid ([CH3COOH] = c1) & its salt ([CH3COONa] = c2)

CH3COOH (aq) ⇌ CH3COO– (aq) + H+ (aq)

Initial
Concentration c1 c2 0
(t = 0)

Equilibrium
Concentration c1(1 - ⍺) c 2 + c 1⍺ c1⍺
(t = teq)
 pH Calculation

[CH3COO–] [H+] (c2 + c1⍺) c1⍺

Ka = = ..…(i)
[CH3COOH] c1 (1 - ⍺)

Assuming ⍺ << 1

Ka
⍺ = c2
…..(ii)
 pH Calculation

c1
[H+] = c1⍺ = Ka
c2

Taking logarithm on both the sides and multiplying by (-1),

[Acid]
-log [H+] = -log Ka + -log [Anion of
salt]
 pH Calculation

[Anion of
log salt] Henderson – Hasselbalch
pH = pKa + equation
[Acid]

Mixing a weak acid solution and a

solution of its salt with a strong base

For e.g.: Mixture of 1 mol CH3COOH and 1 mol

CH3COONa
Dissociation of a Weak Electrolyte in Water
CH3COOH (aq) CH3COO– (aq) + H+
(aq)
⇌

Adding CH3COONa to CH3COOH solution

CH3COOH (aq) + CH3COONa (aq) + H2O (l)

 Preparation of Acidic Buffer
Mixing a weak acid solution and lesser amount of a strong
base solution than that required for neutralization

For e.g. Mixture of 1 mol CH3COOH and 0.5 mol NaOH

Mixing a salt solution of a weak acid and a strong

base with lesser amount of a strong acid
solution than that required for complete reaction

For e.g.: Mixture of 1 mol CH3COONa and 0.5 mol HCl

 Basic Buffer Solutions

Solution of a weak
base and its salt
with a strong acid

NH4OH + NH4Cl NH4OH + (NH4)2SO4

 pOH Calculation
Buffer solution consisting of a
weak base ([NH4OH] = c1) & its salt ([NH4Cl] = c2)

NH4OH (aq) ⇌ NH4+ (aq) + OH– (aq)

Initial
Concentration c1 c2 0
(t = 0)

Equilibrium
Concentration c1(1 - ⍺) c 2 + c 1⍺ c1⍺
(t = teq)
 pOH Calculation

[NH4+] [OH–] (c2 + c1⍺) c1⍺

Kb = = ..…(i)
[NH4OH] c1 (1 - ⍺)

Assuming ⍺ << 1

Kb
⍺ = c2
…..(ii)
 pOH Calculation

c1
[OH ]
–
= c1⍺ = Kb
c2

Taking logarithm on both the sides and multiplying by (-1),

[Base]
-log
-log [OH ]
–
= Kb
+ -log [Cation of
salt]
 pOH Calculation

[Cation of
pOH = pKb + log salt]
[Base]
 Preparation of Basic Buffer

Mixing a weak base solution and a solution

of its salt with a strong acid

For e.g.: Mixture of 1 mol NH4OH and 1 mol NH4Cl

Dissociation of a Weak Electrolyte in Water
_
NH4OH (aq) ⇌ NH4+ (aq) + OH (aq)

Adding NH4Cl to NH4OH Solution

NH4OH (aq) + NH4Cl (aq) + H2O (l)

 Preparation of Basic Buffer
Mixing a weak base solution and
lesser amount of a strong acid solution
than that required for neutralization

For e.g.: Mixture of 1 mole NH4OH and 0.5 mole HCl

Mixing a salt solution of a weak base and a

strong acid with lesser amount of a strong base
solution than that required for complete reaction

For e.g.: Mixture of 1 mole NH4Cl and 0.5 mole

NaOH
Salt Buffer Solutions

Solution of the salt

of a weak acid and
a weak base

Solution of CH3COONH4
 Buffer Action

Solution of a weak acid (HA) and its highly ionized salt

Addition of acid H3O+ + A– ⇌ H2O + HA

Thus, the solution does not pH value remains

contain excess of H3O+ almost the same
 Buffer Action

Solution of a weak acid (HA) and its highly ionized salt

Addition of base OH–+ HA H2O + A–

Thus, the solution does not pH value remains

contain excess of OH– almost the same
 pH Range of Buffer

Generally, buffer solution can be

used for practical purposes when
Particular weak acid (or base)
that can be employed for
making useful buffer solution of
[Salt] pH (or pOH) lies within the
0.1 ≤ [Acid]
≤ 10
range of
(pKa ± 1) or (pKb ± 1).

pH = pKa - 1 pH = pKa + 1
 Buffer Capacity

It is defined as the moles of

a strong acid or a strong
base required to change the
pH of 1 L of a buffer by one
unit.
 Buffer Capacity

Sum ofratio
The Internal energy
of the small
andamount
PV energy of aor
of acid system
base
undertoathe
added given set ofin pH
change
conditions.
caused in the buffer.

Let there be a buffer solution of volume 1 L with ‘b’ mol

of anion (coming from salt) and ‘a’ mol of weak acid.
If ‘x’ mol of a strong acid (monobasic) is added to it,

dx ab
Buffer Capacity
d(ΔpH)
≈ 2.303
a+b
Maximum Buffer Capacity

Buffer shows maximum buffer

capacity when the amounts of
acid (or base) and the anion
(or cation) from the salt are
the same.

[Acid] = [Anion of salt]

 Maximum Buffer Capacity
For an Acidic
Buffer
solution
[Anion of
pH = pKa + log salt]
[Acid]

If [Anion of salt] = [Acid]

pH = pKa
 Remember!!

Acid whose pKa value

For preparing a buffer is close to the required
solution of the required pH pH is taken
 Application of
Applications ofBuffer
Buffer

In industrial processes
1 e.g. Electroplating, leather industry

In biological processes, e.g., pH of our blood

2 remains constant at about 7.4. Buffer action in
blood is due to H2CO3 + HCO–3 ions
 Acid - Base Titration

Out of an acid & a base solution, taking a known volume

of one of them in a flask & taking the other in a burette
& finding the volume required for complete neutralization.
 Acid - Base Titration

pH calculation at equivalence point

can be done according to the nature
of the species formed at the
equivalence point

If the salt of a weak acid & 1

a strong base is formed
pH = 7 + 2 (pKa + log c)

If the salt of a strong acid

1
& pH = 7 - 2 (pKb + log c)
a weak base is formed
 Acid - Base Titration

Indicator
Phenolphthalein Methyl orange
Substances which indicate the
end point of a titration
generally by changing their Common
colour. acid-base
indicators
 Indicators

Indicators are either weak organic acids or weak

organic bases having characteristically different
colours in their ionised & unionised forms.

_
HIn (aq) + H2O (l) ⇌ H3O+ (aq) + In (aq)

Colour A Colour B
 Indicators

_
HIn (aq) ⇌ H+ (aq) + In (aq)
KIn [HIn]
[H+] = _
[In ]
_
[H+] [In ] Taking logarithm on both the sides and multiplying by (-1)
KIn =
[HIn]
[HIn]
- log [HIn]
- log [H+] = - log KIn + - log [In_-]
[In ]
KIn [HIn]
[H+] = _
[In ]
 Indicators

[HIn]
[In
_
]
pH = pKIn + log
log [In-]
[HIn]

Example:

Phenolphthalein (HPh) is a weak acid;

HPh (aq) + H2O (l) H3O+ (aq) + _Ph

⇌
(aq)

Colourless Pink
 Example

Methyl orange (MOH) is a weak base;

_
MOH (aq) + H2O (l) ⇌ OH (aq) + M+ (aq)

Yellow Red
 Did You Know?

Human eye can’t identify color

change of indicators accurately!!

Solution acquires a distinct

colour characteristic of In–
if

_
[In ] ≥ 10 [HIn]
 Indicators

[HIn]
[In
_
]
pH = pKIn + log
log [In-]
[HIn]

If _
[In ] ≥ 10 [HIn]

pH ≥ pKIn + 1
 Indicators

[HIn]
[In _
]
pH = pKIn + log
log [In-]
[HIn]

_
If [HIn] ≥ 10 [In ]

pH ≤ pKIn - 1
 Indicators

HIn (aq)
_
H+ (aq) + In (aq) pH range of
Indicator

Colour A Colour B
pKIn - 1 ≤ pH ≤ pKIn + 1

pH ≥ pKIn +
pH ≤ pKIn − 1
1
 pH Range of Indicator

14 14

10.0
pH range
between which 8.3
the indicator
4.
changes its
43.
colour.
1
0.0 0.0

Methyl Orange Phenolphthalein

 14 14

8.2 7.6
6.4 6.0

0.0 0.0

Phenol Red Bromothymol Blue

 pH Range of Indicator

pH Range
Indicator Colour changed
of Indicator
Phenolphthalein (8.3 - 10) Colourless to pink

Methyl Orange (3.1 - 4.4) Red to yellow

Phenol Red (6.4 - 8.2) Yellow to red

Bromothymol blue (6 - 7.6) Yellow to blue

Titration of Strong Acid vs Strong Base

Consider 40 mL, 0.1 M HCl vs 0.1 M NaOH

Titration of Strong Acid vs

1 Volume of NaOH added pH of solution
Strong Base
0 mL 1

10 mL 1.22
Eg. HCl vs NaOH
20 mL 1.48

30 mL 1.84
39 mL 2.90
Titration of Strong Acid vs Strong Base

Volume of NaOH added pH of solution

39.9 mL 3.9

40 mL 7
40.1 mL 10.1

41 mL 11.1

50 mL 12.05
Titration of Strong Acid vs Strong Base
 Selection of Indicator

Selected It offers a colour change near

indicator should the vicinity of the pH of the
be such that solution at the equivalence point.

The steep section of the titration curve at the equivalence

point must encompass an interval of pH values at least
as large as the pH transition range of an indicator.

pH transition range of the indicator must coincide

with the steep portion of the titration curve.
 In a Nutshell…

An indicator can be
Some part of pH
considered suitable
range of the indicator
for detecting the
lies within the pH
end-point of a
range of the titration
particular titration if
 Titration of Strong Acid vs Strong Base

pH range of titration: 4 – 10

Almost all common indicators

(E.g.: Phenolphthalein, Methyl
orange, Phenol red) can be
used for endpoint detection.

Bromothymol blue indicator So it will serve as the

has its pH range containing best indicator for
the equivalence point pH. the given titration.
 Titration of Weak Acid vs Strong Base
20 mL, 0.5 M CH3COOH (pKa = 4.7) vs 0.5 M NaOH

Volume of NaOH pH of solution

added
Titration of Weak Acid vs
2 0 2.5
Strong Base
5 mL 4.23

10 mL 4.7 [pH = pKa]

Eg: CH3COOH vs NaOH
15 mL 5.17
Half Equivalence Point (both
components of buffer in equal amounts)
Titration of Weak Acid vs Strong Base

Volume of NaOH added pH of solution

19 mL 6

20 mL 9.05

21 mL 12.09

30 mL 13

Equivalence point: Complete

Neutralization
Salt of WA & SB (CH3COONa = 0.25 M)
Titration of Weak Acid vs Strong Base

pH range of titration: 7 – 10

Common indicators that can be used are

Phenolphthalein & Phenol red.
 Titration of Strong Acid vs Weak Base

100 mL, 0.05 M NH4OH (pKb = 4.74) vs 0.1 M HCL

Volume of HCL added pH

Titration of Strong Acid
3
vs Weak Base 0 mL 10.98
10 mL 9.86

20 mL 9.43
Eg: HCl vs NH4OH
25 mL 9.26

Half Equivalence Point

(Maximum buffer capacity)
Titration of Strong Acid vs Weak Base

100 mL, 0.05 M NH4OH (pKb = 4.74) vs 0.1 M HCL

Volume of HCL added pH

40 mL 8.65

50 mL 5.37

60 mL 2.2

70 mL 1.93

Equivalence point
Titration of Strong Acid vs Weak Base

pH range of titration: 4 – 7

Common indicators that can be used

are Methyl orange, Methyl red & Phenol
red.
 Titration of Weak Acid vs Weak Base

Titration of Weak Acid vs

4
Weak Base
Titration of weak acid & weak base is
generally not carried out in laboratory
because of the very small pH range of this
titration (6.5 - 7.5).
Eg: CH3COOH vs NH4OH
Titration of Weak Acid vs Weak Base

Nor the rise of pH

In this particular case, encompasses an
neither the steep rise interval equal to the
of pH near the pH transition range of
equivalence point any of the indicators.
occurs

No common indicators can perform

appropriately in this small pH range.

However, if this titration is carried out,

then Phenol Red would be the best
indicator.
 Solubility

Maximum amount of solute

that can be dissolved in a
specified amount of solvent
at a specified temperature to
form a saturated solution.

Unit: mol/L
 Classification of Salts

Category I Soluble Solubility > 0.1 M

Category II Slightly soluble 0.01 M < Solubility < 0.1 M

Sparingly
Category III Solubility < 0.01 M
soluble

Solubility > 0.1 M 0.01 M < Solubility < 0.1 M Solubility < 0.01 M

Soluble Slightly soluble Sparingly soluble

 Solubility

An equilibrium is established between the

undissolved salt and its ions in the solution.

Considering BaSO4, a sparingly soluble salt, being added in water:

2–
BaSO4 (s) + H2O (l) ⇌ Ba2+ (aq) + SO4 (aq)

Dissolution

Precipitation
 Solubility Product

BaSO4 (s) + H2O (l) ⇌ Ba2+ (aq) + SO42– (aq)

2–
[Ba2+] [SO4 ]
Keq =
[BaSO4] Constant
 Solubility Product

Keq [BaSO4] = 2–
[Ba2+] [SO4 ]

Solubility 2–
product
Ksp = [Ba2+] [SO4 ]

Experimental value of
Ksp is 1.5 × 10-9
 Solubility Product

Ksp

Product of molar concentrations of ions

in the saturated solution raised to a power
equal to the coefficient of the ion

Ksp

Depends only on temperature

for a particular salt.
 Relation between K sp & Solubility

For a solid salt of the general formula MxXy with molar solubility S,

MxXy (s) ⇌ xMp+ (aq) + yXq- (aq)

Equilibrium
concentration ___ xs ys

Where, x × p = y × q
 Relation between K sp & Solubility

Ksp = [Mp+]x [Xq-]y = (xs)x (ys)y = xX yy s(x+y)

Ksp
s(x+y) =
xx yy

1
Ksp x+y
s =
xx.yy
 Ionic Product

Kip

For a solution of a salt at a specific

concentration, the product of the
concentrations of the ions, each
raised to the power equal to the
coefficient of the ions
 Solubility Product vs Ionic Product

Solubility product (Ksp) Ionic product (Kip)

Applicable to saturated
Applicable to only
as well as unsaturated
saturated solutions
solutions

Measures the maximum Measures the actual

amount of ions that the amount of ions in the
solution can dissolve solution
 Solubility Product vs Ionic Product

MxXy (s) ⇌ xMp+ (aq) + yXq- (aq)

If Kip < Ksp

Solution is More salt can No precipitate

unsaturated dissolve formation
Solubility Product vs Ionic Product

MxXy (s) ⇌ xMp+ (aq) + yXq- (aq)

If Kip = Ksp

Solution will become No precipitate

saturated formation
 Solubility Product vs Ionic Product

MxXy (s) ⇌ xMp+ (aq) + yXq- (aq)

If Kip > Ksp

Solution is holding more Precipitate formation

salt that it can dissolve takes place
 Conditions for Precipitation

Kip < Ksp Kip = Ksp Kip > Ksp

Unsaturated Saturated Precipitation

solution solution occurs
Solubility in the Presence
of a Common Ion
Effect of Common Ion on the Solubility of
Sparingly Soluble Salts

Presence of a common ion

in the solution decreases
the solubility of a given
sparingly soluble salt.
Solubility in the Presence of a Common Ion

Sparingly
soluble salt
AB AB (s) ⇌ A+ (aq) + B- (aq)

s + c1 s

Soluble salt AX AX (s) A+ (aq) + X- (aq)

c1 s + c1 c1
Solubility in the Presence of a Common Ion

Ksp = [A+ ] [B-]

Ksp = (s + c1) (s)

If s << c1 s + c1 ≈ c1

Ksp
s =
c1
 Effect of pH on Solubility
At lower pH

Solubility of salts
of weak acids like
phosphates increases

Due to its
At low pH, [Anion] Solubility of salt
protonation
 Simultaneous Solubility

Sum of Internal
When energy
two sparingly
soluble
and salts are
PV energy of aadded
systemin
water
undersimultaneously,
a given set of there
willconditions.
be simultaneous
equilibrium in the solution.

Simultaneous solubility of
Common ion effect exerted
each salt will be less than its
by ion coming from other salt
individual solubility because of
 Simultaneous Solubility

AgCl (s) + H2O (l) ⇌ Ag+ (aq) + Cl – (aq) Ksp

1

s1 + s2 s1

AgBr (s) + H2O (l) ⇌ Ag+ (aq) + Br – (aq) Ksp

2

s1 + s 2 s2

s1 Solubility of AgCl s2 Solubility of AgBr

 Simultaneous Solubility

Therefore, Ksp
1
= (s1 + s2) (s1) (i)

Ksp
2
= (s1 + s2) (s2) (ii)

Adding equation (i) & (ii)

K sp + K sp
1 2
= (s1 + s2)2
 Simultaneous Solubility

Therefore, s 1 + s2 = K sp + K sp
1 2

K sp
1
s1 =
K sp + K sp
1 2

K sp
2
s2 =
K sp + K sp
1 2
 Solubility Exchange

One precipitate is mixed with a solution of an ion to

get another precipitate and another ion in solution.

AgCl (s) + NaBr (aq) ⇌ AgBr (s) + NaCl (aq)

Ksp (AgCl) = [Ag+] [Cl– ]

Ksp (AgBr) = [Ag+] [Br– ]

 Selective Precipitation

If a single solution
The ion which requires
has two or more
less concentration of
ions both having the
ions of the reagent for
tendency to
precipitation will
precipitate with an
precipitate out first.
ion of a reagent
Solubility of Salts Involving Anion from Weak Acid

Consider a sparingly soluble salt ‘MA’ where

A – is the anion of weak acid ‘HA’

MA (s) ⇌ M+ (aq) + A– (aq) Ksp = s [A– ]

s

Kw
A (aq) + H2O (l)
–
⇌ –
HA (aq) + OH (aq) Kh =
Ka
Solubility of Salts Involving Anion from Weak Acid
–
Kw [HA] [OH ]
Kh = =
Ka [A– ]

Applying mole balance on ‘A’

s = [A– ]Total + [HA]Total (i)

[H+] [A–
HA (aq) ⇌ H+ (aq) + A– (aq) Ka = ]
[HA]
–
[H+] [A ]
[HA] =
Ka
Solubility of Salts Involving Anion from Weak Acid

Putting equation (ii) in equation (i) Ksp = s [A– ]

[H+] [A–
s
s = [A ]
–
+ ] s✕ [H+
Ka
Ksp =
1+ ]
Ka
s
[H+ [H+
[A ]
–
=
1+ ] s = Ksp 1+ ]
Ka Ka
Solubility of Salts Involving
Anion from Weak Acid in a
Buffer Solution
Solubility of Salts Involving Anion from Weak Acid

Let AgCN (s) be added to a buffer solution having H+ ([H+] = c)

AgCN (s) ⇌ Ag+ (aq) + CN– (aq) Keq = Ksp

s s-x

1
CN –(aq) + H+ (aq) ⇌ HCN (aq) Keq =
(Ka)HCN
s-x c x
Solubility of Salts Involving Anion from Weak Acid

Adding both equations, we get

Ksp
AgCN (s) + H+ (aq) ⇌ Ag+ (aq) + HCN (aq)
Ka

c s x

Ksp sx
= c
Ka
Solubility of Salts Involving Anion from Weak Acid

HCN is a weak acid. 1

is very high
So, Ka will be very small (Ka)HCN

s-x ≈ 0 ⇒ s ≈ x
Solubility of Salts Involving Anion from Weak Acid

Ksp s2
= c
Ka

c Ksp
s =
Ka
 Effect of Complex Formation on Solubility

Consider the solubility of AgCl in a solution of NH3 (where [NH3] = a)

AgCl (s) ⇌ Ag+ (aq) + Cl– (aq) (i)

x-y x

Ag+ (aq) + 2NH3 (aq) ⇌ [Ag(NH3)2]+ (aq) (ii)

x-y a - 2y y
Effect of Complex Formation on Solubility

Ksp (AgCl) = (x - y) x

y
Kf =
(x - y)(a - 2y)2

Formation constant
Kf
of [Ag(NH3)2]+
Effect of Complex Formation on Solubility

Adding equations (i) & (ii), we get

AgCl (s) + 2NH3 (aq) ⇌ [Ag(NH3)2]+ (aq) + Cl− (aq) K = Ksp × Kf

xy
Ksp × Kf = (a - 2y)2
Effect of Complex Formation on Solubility
If the complex is stable, then Kf will be
high

x-y ≈ 0 ⇒ x ≈ y

x2
Ksp × Kf =
(a - 2x)2

Due to the formation of

complex, solubility increases.