PAWAN WAGH ACADEMY

Notes
Topic – IONIC EQUILIBRIA

 Ionic equilibria:-
The equilibrium between ions and unionized molecules in
the solutions is called as ionic Equilibria.

Unionized Ions
molecule
Ionic equilibria

Substance/Electrolyte

Strong Electrolyte Weak Electrolyte

The electrolytes which The electrolytes which do
ionizes completely in not ionizes or dissociates
aqueous solution are completely in aqueous
called as strong solution are called as weak
electrolytes. electrolytes.
Ex: - Strong Acid, Strong Ex: - Weak Acid, weak
Base Base

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 Degree of dissociation (α):-
The ratio of number of moles dissociated to the total
number of moles is called as degree of dissociation (α).

𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑑𝑖𝑠𝑠𝑜𝑐𝑖𝑎𝑡𝑒𝑑

α=
𝑇𝑜𝑡𝑎𝑙 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑙𝑦𝑡𝑒

 Percentage Dissociation (% α)
α% = αx100
 For solving, numerical, generally we use ‘α’ for calculations,
and not % α

 Various theory for Acids and Bases

Arrhenius Bronsted Lewis theory

Theory Lowry
Theory

 Arrhenius theory :-
Acid- Substance which gives H+ ions in aqueous solution.
Ex:- HCL Water H+ + Cl-

Base- Substance which gives OH- ions in aqueous solution.

Ex:-NaOH water Na+ + OH-

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 Bronsted- Lowry theory:-
Acid- Substance which donate H+ ion to other substance.
Base – Substance which accept H+ ion from other
substance.

Ex- HCl + NH3 Cl- + NH4(+)

Acid Base
donates accepts
H+ Ion H+ ion conjugate conjugate
Base Acid
Conjugate Base :- The base which is produced, when acid
donates H+ ion is called as Conjugated base.

Conjugate Acid
The acid which is produced, when base accept H+ ion is called
as Conjugated Acid.

Acid -H+ Conjugated Base

Base + H+ Conjugated Acid

 Lewis theory
Acid: - The species which accept shared electron pair.
Base: - The species which donate shared electron pair.
ex:

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  Amphoteric Nature
The nature in which, the substance shows both acidic as
well as basic behavior is called as amphoteric nature.

 Dissociation of strong acid and strong base and

weak acid and base weak Base
Strong Acid or Strong Base
(Represented By single Arrow)

Weak Acid or Weak Base

(Represented By double Arrow)

 Examples

Strong Acid Weak Acid Weak Base

Strong Base
HCl,HNO3, HF,HCOOH, Fe(OH)3,
NaOH,KOH
H2SO4,HBr,HI CH3COOH,H2S Cu(OH)2

[Product ]
 Constant =
[Reactant]

 A+B C+D Normal Reactions

 A+B C+D Dissociation Reactions
Reactants Products

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 Dissociation of

Weak Acid Weak Base

HA H+ + A- BOH B+ + OH-
(H+) (A−) (𝐵+)(𝑂𝐻−)
Ka= Kb =
(𝐻𝐴) (𝐵𝑂𝐻)

Ka = Dissociation constant Kb = Dissociation Constant

of acid of Base

Ostwald’s dilution Law

For weak Acid

HA H+ + A - For weak Base
Initial amount 1 0 0
BOH B+ OH-
Amount of equilib m
1-α α α
Initial amount 1 0 0
1−𝛼 𝛼 𝛼
Conc 𝑣 𝑣 𝑣 Amount at equilibm 1-α α α
1−𝛼 𝛼 𝛼
Concentration
𝑣 𝑣 𝑣
[𝐻+][𝐴−]
Ka = [𝑂𝐻−][𝐵+]
[𝐻𝐴] Ka =
[𝐵𝑂𝐻]
𝛼 𝛼
= ( )( ) ∝ ∝ 1−∝
𝑉 𝑉 =( )( )/
𝑉 𝑉 𝑉
1−𝛼
= ( ) =
∝2
𝑉 (1−∝)𝑉
𝛼2
= (1−𝛼 )𝑣
for dilute solution
=
∝2
for dilute soln (1-∝≅ 1)
1𝑥𝑣
𝛼
= [1-α≅] and also
Kb = ∝2C
1
=𝑐
𝑣(1)
𝑉
1
Ka = α2c =c or
𝑣

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 𝐾𝑏 ∝= √𝐾𝑏𝑥𝑣
𝑘𝑎
∝= √
α= √ α = √𝑘𝑎𝑋𝑉 𝐶
𝑐

Autoionization of water

H2O + H2O ⇌ H3O+ + OH-

[𝑃𝑟𝑜𝑑𝑢𝑐𝑡]
Equilibrium constant = Keq = = [H3O+][OH-] /[H2O]2
[𝑅𝑒𝑎𝑐𝑡𝑎𝑛𝑡]

So [H3O+] [OH-] = keq x [H2O]2 ………….. [H2O]2 = K’’=constant

[H3O+] [OH+] = Keq x K’’

[H3O+] [OH-] = Kw

Kw = [H+] [OH-]
Or

Ionic product of water = Kw = [H+] [OH-] = 1x10-14

Some important Formula

1. PH = -log10 [H+]
2. POH = -log10 [OH-]
3. Kw = [H+] [OH-]= [H3O+] [OH] = 1x10-14
4. PH + POH = 14 (PH scale)

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 Types of solution

Acidic Neutral or Basic

Solution alkaline solution
solution

PH<7 PH=7 PH>7

[H+]>10-10 [H+]=[OH-]=10-7 [H+]<10-7

SA= strong acid

SB= Strong base
WA= Weak acid
Types of salt WB= weak base

SA+SB salt + H2O

WA+SB salt + H2O
HCl+NaOH NaCl +H2O
H2SO4+2NaOH Na2SO4+H2O CH3COOH+NaOH CH3COONa+H2O

HNO3+NaOH NaNO3+H2O HCN + KOH KCN+H2O

HCl + KOH KCl + H2O H2CO3+NaOH Na2CO3+H2O
HNO3 + KOH KNO3 + H2O

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SA+WB Salt + H2O

HCL+NH4OH NH4Cl+ H2O

H2SO4+Cu(OH)2 CuSO4+ H2O

HNO3 + NH4OH NH4NO3+ H2O

2HCl + Cu(OH)2 CuCl2 + H2O

WA+WB Salt + H2O

CH3COOH+NH4OH CH3COOH+H2O
HCN + NH4OH NH4CN + H2O

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  Hydrolysis Concept

Hydrolysis of salt
The reactions in which or anions or both ion of salt react
with ions of water is called as Hydrolysis of salt.

 Hydrolysis of salt of

Strong acid and Strong Acid And Weak acid and

strong base strong Base
Weak Base
HCl+NaOH NaCl+H2O CH3COOH+NaOH
H2SO4+Cu(OH)2 CuSO4+H2O CH3COONa+H2O

Weak acid and weak

Base

Ka>Kb Ka<Kb Ka=Kb

HF+NH4OH NH4F+H2O HCN+NH4OH CH3COOH+NH4OH
NH4CN+H2O CH3COONH4

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Steps involved while doing hydrolysis of any salt
Acid + Base Salt + H2O
Salt Cation + Anion
(C+) Cation + H2O C(OH) + H+ or H3O+
Base
H+ OH-

A-(Anion) + H2O AH + OH-

H+ OH- Acid

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I) Hydrolysis of salt of strong acid and strong base
HCl + NaOH NaCl + H2O
SA SB Salt

NaCl Na+ + Cl-

Here cation and anion formed are from strong acid

and strong base, so they do not undergoes hydrolysis
so [H3O+]=[OH-]
and nature of solution is neutral.

II) Hydrolysis of salt of strong acid and weak base

H2SO4 + Cu(OH)2 Cu(SO4)2 + H2O
SA WB salt

Cu(SO4)2 Cu+2 + 2 SO42-

Cu+2 (cation) is from Cu(OH)2

Cu(OH)2 is a weak base, so Cu+2 undergoes
hydrolysis

Cu+2 + H2O Cu(OH)2 + H3O+ or H+

As the acid is strong, so nature of solution is

acidic
So [H3O+]>[OH-]

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III) Hydrolysis of salt of weak acid and strong base

CH3COOH + NaOH CH3COONa + H2O

Weak acid Strong Salt Water
Base

CH3COONa CH3COO(-) + Na(+)

Anion cation

As CH3COO(-) anion comes from acid (CH3COOH)

As CH3COOH is a weak acid, so CH3COO- ion
undergoes hydrolysis

CH3COO- + H2O CH3COOH + OH-

In the solution base is strong, so the nature of solution
is basic
IV) Hydrolysis of salt of weak acid and weak base
In case of weak acid and weak base, the cation and
anion both undergoes hydrolysis as both acid and
bases are weak

3 cases

Ka>Kb Kb>Ka Ka=Kb

Ka= dissociation = constant for acid
Kb = Dissociation = constant for base

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Hydrolysis of weak acid and weak base

Kb= Ka

CH3COOH + NH4OH → CH3COONH4 + H2O

Acid Base Salt
- +
CH3COONH4 ⇌ CH3COO + NH4
Anion Cation
- -
CH3COO + H2O ⇌ CH3COOH + OH

+ +
NH4 + H2O ⇌ NH4OH + H3O
- + + -
CH3COO and NH4 ion hydrolysis to same extent, So H3O and OH are equally formed , So
solution is neutral and so Kb= Ka

Kb> Ka
HCN + NH4OH → NH4CN + H2O
Acid Base Salt
+ -
NH4CN ⇌ NH4 + CN
Cation anion
+
NH4+ + H2O ⇌ NH4OH + H3O

- -
CN + H2O ⇌ HCN + OH

- + -
CN hydrolysis to higher extent than NH4 , So more OH is formed , So solution is basic in
nature, So Kb>Ka

Ka>Kb
HF + NH4OH → NH4F + H2O
Acid Base salt
+ -
NH4F ⇌ NH4 + F

cation anion

+ +
NH4 + H2O ⇌ NH4OH + H3O

- -
F + H2O ⇌ HF + OH

+ - +
NH4 hydrolysis F higher than , So more H3O is formed , So solution
is acidic in nature , So Ka>Kb

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 Buffer
The solution which do not change its PH, when small
amount of strong acid or strong base is added to it,
is called as buffer solution.

Types of Buffer solution

Acidic buffer solution Basic buffer solution

A solution which A solution which contains
contains
Weak acid + salt of weak Weak base + salt of weak
acid and strong base base and strong acid

is called as acidic buffer solution is called as basic buffer solution

[𝑠𝑎𝑙𝑡] [𝑠𝑎𝑙𝑡]
pH=pKa + log10 pOH= pKb + log10
[𝑎𝑐𝑖𝑑] [𝐵𝑎𝑠𝑒]

pKa = -log10Ka pKb = -log10Kb

Properties of Buffer
pH do not change

By addition of By addition of By keeping it

strong acid or H2O(dilution) for long time
strong base

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 Application of buffer

In
Analytical
biochemical Agriculture Industry Medicine
chemistry
system

 Solubility equlibria:-
The equilibria that exist between the undissolved solid and
dissolved ions in solution is called as solubility equilibria.

Undissolved solid ⇌dissolved ions

 Sparingly soluble compounds

The compound that dissolve slightly in water, is called as
sparingly soluble compound

 Solubility product
The product of concentration of ions in a saturated
solution is called as solubility product (Ksp).
Ksp for AgCl = [Ag+][Cl-]

AxBy xAy+ + YBx-

Ex: BaSO4 1Ba+2 + 1SO42-…….Ksp= [Ba+2][SO42-]
Ex: CaF2 1Ca+2 + 2F1- …… Ksp= [Ca+2][F1-]2
Ex: Bi2S3 2Bi+3 + 3S2-……….Ksp= [Bi+3]2[S2-]3

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 Solubility:-
The ratio of amount of solute in grams per unit volume of
solution is called as solubility.
𝑔𝑟𝑎𝑚
Unit of solubility =
𝑙𝑖𝑡𝑟𝑒

 Molar solubility:-
The ratio of solubility in g/L per unit molar mass is
called as molar solubility
𝑚𝑜𝑙
Unit of molar solubility is
𝑙𝑖𝑡𝑟𝑒
 Imp Relation
/ (molecular mass)

Solubility molar solubility

𝑔 𝑚𝑜𝑙
( ) ( )
𝑙 𝑙

X (molecular mass)

Ksp=[Link]+y
In case of Bx Ay X B+y+ Y Ax-

So Ksp=[B+y]x[Ax-]y . Sx+y

Where S= Solubility

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For example
1. For AgBr
Ag1Br1 1Ag1+ + 1Br1-

So Ksp = (1)1 (1)1 S1+1= S2 = Ksp

2. For Pb I2
Pb I2 1Pb+2 + 2I1-

So ksp = (1)1(2)2 S1+2= 4S3=Ksp

3. For Al(OH)3
Al(OH)3 1Al+3 + 3(OH1-)

So Ksp = (1)1 (3)3. S1+3 = 27 S4 = Ksp

Condition of precipitation

IP=ksp IP>Ksp IP<Ksp

Solution is Solution is Solution is

saturated supersaturated unsaturated

Equilibrium Precipitation Precipitation do

exist occurs not occurs
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 Common ion effect:-
 Let CH3COOH be the weak acid.
 CH3COOH be the salt of weak acid and strong base.
 CH3COOH dissociates very less, as it is weak acid
 CH3COONa dissociates completely, as it is stronger
salt
 As below:-
CH3COOH CHCOO(-) + H(+) less CH3COO(-) ions
are formed

CH3COONa CH3COO(-) + Na(+) more CH3COO(-) ions

are formed

 So in overall, more CH3COO(-) (acetate ions are

formed) to the right side, as a result of which,
according to the Le-chateliers principle, the reaction
shifts towards the left side.
 Due to these shift of equilibrium to the left side, the
dissociation of CH3COOH is suppressed.
 The common ion in both the above reaction is
CH3COO(-) (acetate ion) and hence the effect
generated is termed as common ion effect.

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