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Lets
 IONIC
EQUILIBRIUM
 Ionic Equilibrium

+ –
Ionic Associated with ions A B

Equilibrium State at which certain measurable properties such as pressure,

density, color, concentration etc. do not change with time .
Ionic Equilibrium

Definition :
It is the equilibrium which is established between the unionised
molecules and the ions in solution of weak electrolytes .
Classification of Electrolytes
Depending upon their nature
Strong Electrolytes :

The electrolytes which ionize completely or very nearly completely are

referred to as strong electrolytes.

Example

Strong acids ( HCl, H2SO4)

Strong soluble bases ( NaOH, KOH )
Soluble salts ( KCl, NaCl )
Weak Electrolytes

The electrolytes which dissociate only slightly in dilute aqueous solutions

are called weak electrolytes.

Example

Weak acids ( CH3COOH, HCOOH)

Weak bases ( NH4OH )
Depending upon their nature

Electrolyte

Acids Bases Salts

Citric Acid & Ascorbic Acid Base NaCl

Arrhenius theory of acids and bases
Limitations of Arrhenius Theory :

This theory is applicable only to aqueous solutions

It does not explain the acidic nature of substances
Which do not contain H
Example : CuSO4, FeSO4, SO2, CO2

It does not explain the basic nature of substances

Which do not contain OH groups
Example : NH3, Na2CO3
Bronsted & Lowry Theory
Example
Advantages & Limitations of Lowry – Bronsted theory
 Advantages of Lowry – Bronsted Theory

• This theory is more broader than Arrhenius Theory.

It explains acidic and basic behaviour in non aqueous medium also.

HCl (g) + NH3 (g) NH4Cl (s)

• It included many more substances as

acids and bases.

Acids – NH4+, H3O+ Bases – NH3 , H2O

 Limitations of Lowry – Bronsted Theory
● This Theory emphasized the presence of hydrogen in an acid like Arrhenius
Theory.
● Hence, it cannot explain the acidic behaviour of substances like CuSO4,
AlCl3 etc. which do not contain hydrogen.

• This Theory defines bases as proton acceptors,

But there are bases which do not accept proton like CaO, MgO etc.
Lewis Theory of Acids and Bases
 F H F H

F B + :N H F B N H

F H F H
Acid Base
Advantages of Lewis Theory
1) It explains the acidity of non - hydrogen compounds like BF3
and basicity of non - hydroxy compounds like NH3
2) It includes even all cations as acids NH4+ , H3O+
and all anions as bases. OH – , Cl –

3) It does not need the presence of a solvent

to exhibit acidic and basic properties.
Dissociation Constant Of Weak Acids And Weak Bases
 Dissociation Constant Of Weak Acids And Weak Bases

Let us consider a weak acid HA

HA(aq) H+(aq) + A– (aq)

As HA is a weak acid, it will not dissociate completely, it

will dissociate to a small extent
Applying Law of Mass Action, in the above equation, we get

[H+] [A–]
Ka = HA(aq) H+(aq) + A– (aq)
[HA]

Equilibrium constant
Also called as Acid – dissociation constant
Similarly, the dissociation constant of a weak base BOH in water is
represented by

BOH(aq) B+(aq) + OH– (aq)

The equilibrium constant called

Base – dissociation constant is

[B+] [OH–]
Kb =
[BOH]
Ionic Product of water
Relation between Kw & Temperature
Relation between Kw & Temperature
If temperature of solution is increased,
The value of Kw will also increase.

Kw = [H+][OH–]

Say for example

–12 0 H2O H+(aq) + OH–(aq)
Kw = 10 at temp > 25 c
As reaction in endothermic

(Due to increase in temperature, H2O will dissociate more,

producing more H+ & OH– ions )
Concept of pH
Relationship between pH & pOH
We can define power of any quantity ‘Q’ as
pQ = – log10Q
Based on this, we can define terms like
pH = – log10 [H+] pOH = – log10 [OH–]
pKa = – log10 Ka pKb = – log10Kb
pKw = – log10 Kw
Common ion Effect
Definition :

The common ion effect states that the ionization of a weak

electrolyte is suppressed in presence of a strong electrolyte
containing an ion common to the weak electrolyte.
The two types of solutions which most
frequently exhibit the common ion effect are :
1. Solution of a weak acid and its salt

2. Solution of a weak base and its salt

 1. Solution of a weak acid and its salt

CH3COOH(aq) CH3COO–(aq) + H+(aq) (Partial)

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

CH3COO– ions are obtained both from CH3COOH as well as CH3COONa, Complete
dissociation of CH3COONa provides a high concentration of CH3COO– ions.
 CH3COOH CH3COO– + H+
The reverse reaction is favoured

[H+] ↓ in the solution resulting in pH ↑

pH of solutions pH of solution containing

containing a weak
acid and its salt
> the same concentration
of weak acid alone
2. Solutions of a weak base and its salt
2. Solutions of a weak base and its salt

NH4OH(aq) NH4+(aq) + OH(–(aq) (Partial)

NH4Cl(aq) NH4+(aq) + Cl–(aq) (Complete)

Complete dissociation of NH4Cl provides

a high concentration of NH4+ ions
NH4OH NH+4 + OH–

The reverse reaction is favoured

[OH–] ↓ in the solution resulting in pH ↓ causing less basicity.

pH solutions pH solutions containing

containing a weak
base and its salt
< the same concentration
of weak base alone
Relationship between Ka and Kb of a conjugate acid – base pair
Buffer solutions
 Buffers can be divided in three types
Types of Buffers

Acidic buffer Weak Acid and its salt with strong base furnishing its
conjugate base Ex: CH3COOH ,CH3COONa

Basic buffer Weak base and its salt with strong acid furnishing its
conjugate acid. Ex : NH4OH , NH4Cl

Mixed buffer Salt of a weak acid and weak base. Ex : CH3COONH4

Acidic buffer :

A buffer is most effective at the equimolar concentration of salt & acid

[Salt] = [Acid]
Acidic buffer :

Henderson Hazel batch Equation

[Salt]
pH = pKa + log
[Acid]

[Salt] = [Acid]

pH = pKa (∴ log 1 = 0)
Basic buffers
Basic buffer

NH4OH and NH4Cl also known as (NH3 – NH4Cl )

Henderson-Hazel batch equation for basic buffers will be….

[ salt ]
pOH = pKb + log
[ base ]

[ salt ] = [ base ]

pOH = pKb
Di &Polyprotic Acids and their analysis
 Polyprotic Acids
Acids which can furnished more than one H+ are called as polyprotic acid
Ex:- H2SO4, H3PO4 , H2CO3 , H2C2O4

Conjugate
Acid
base
H+ H+
Monoprotic Acid

Conjugate Conjugate
Acid
Base-1 Base-2
H+ H+
Polyprotic Acid
Analysis of a diprotic acid
 Analysis of a diprotic acid

H2CO3 H+ + HCO3– K1 = 4.5 × 10–7

HCO3– +
H + CO3–2 K2 = 4.7 × 10–11

Difference between values of K1 and K2 is very high

For a Polyprotic acids K1 > K2 >> K3 …..

It’s tougher to remove H+ from a negatively

charged ion so first dissociation is the major
source of ions out of all dissociations.
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Salt hydrolysis
The hydrolysis equilibrium can be written as,

Salt + Water Acid + Base

Applying law of mass action

[Acid] [Base]
K =
[Salt] [Water]

[Acid] [Base]
K × [Water] =
[Salt]
Since [Water] remains practically constant
during hydrolysis, we can write
 [Acid] [Base]
Kh =
[Salt]

where Kh Hydrolysis constant of the salt

Degree of hydrolysis :

The fraction of the total salt that is hydrolysed at equilibrium is

called degree of hydrolysis. It is denoted by ‘h’
Four types of salts :-
pH of solution of salt of Strong acid and weak base
 pH of solution of salt of Strong acid and weak base

NH4Cl(aq) NH4+(aq) + Cl–(aq)

HCl in water dissociates completely

NH4+ + H2O NH4OH + H+

1 1
pH = 7 – pKb– log10 C
2 2

This is the expression for pH of solution of salt of SA & WB

pH of solution of salt of Weak acid and Strong base
 pH of solution of salt of Weak acid and Strong base

CH3COONa (aq) CH3COO– (aq) + Na+(aq)

NaOH gets completely ionised in aqueous solution

CH3 COO– + H2O CH3 COOH + OH–

pOH = 7 – ½ pKa – ½ log10C

 pH = 14 – pOH

∴ pH = 14 – 7 – ½ pK – ½ log C
a 10

= 14 – 7 + ½ pKa + ½ log10C

pH = 7 + ½ pKa + ½ log10C
Solubility Product Constant
The constant KSP is known as the solubility
product constant or solubility product
Relation between Solubility and Solubility product
 Relation between Solubility and Solubility product
AgCl(s) Ag+(aq) + Cl–
(aq)
Initial SM 0 0 Solubility is ‘S’ moles/lit or S M
Equilibrium S S

The Equilibrium constant for the above equilibrium is

Ksp = [Ag+] [Cl–]

Ksp = S2

S = √ Ksp
Effect of common ion on solubility
Effect of common ion on solubility
Solubility decrease
CaF2 in NaF

CaF2(s) 2+ + 2F –
Ca(aq) (aq)

NaF Na+ + F–
Solubility will decrease

The solubility of a sparingly soluble ionic compound

decrease by the presence of a common ion in the
solution.
What is the solubility of AgCl in NaCl solution of concentration C M

AgCl(s) Ag+ + Cl– ‘S’ M be the solubility

(aq) (aq) of Ag Cl
‘S’ M ‘S’ M

NaCl Na+ + Cl–

CM CM
Total [Cl–] = (S + C) M
Ksp of AgCl = [Ag+] [Cl–]
= S (S + C)
Ksp = S.C. [If we assume S << C]

Ksp
S =
C

If S is not very small as compared to C

Then
Ksp = S(S + C)
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