TOPIC : EQULIBRIUM

SUB TOPIC : IONIC EQUILIBRIUM

PRESENTED BY : A.K.
MOHANTA
DAV PUBLIC SCHOOL,
ITPS BANHARPALI
 :Species which
dissociate into their ions on
dissolving in water are called
electrolytes
OR
Substances which conduct
electricity in their aqueous solution
are referred as electrolytes.
Types of electrolytes
 Strong Electrolyte:  Weak Electrolyte:
Substances which on Substances which on
dissolution, even at dissolution in water,
moderate dilution, ionize to a little extent
ionize almost completely  Example:-CH3COOH,
 Example:- NH4OH, AgCl etc.
HCl,HNO3,NaOH,NaCl,  Degree of ionization
CaCl2 etc. α ˂˂ 1
 Degree of ionization
α=1
Factors affecting Degree of Ionisation
Nature of Electrolyte
Nature of solvent
Temperature
Dilution
Common Ion Effect
Nature of electrolyte
 Strong electrolytes almost completely
dissociates into their ions and α = 1 .

 Weak electrolytes are only partially

ionised and α ˂˂ 1
Nature of solvent :
The degree of ionization of an
electrolyte increases with increase in
dielectric constant of the solvent in
which it is dissolved.
Temperature : Increase in temperature increases
the degree of ionization of electrolyte.

AB A + + B-

K = A + B- AB

With rise in temperature K increases thus degree of

ionization of electrolyte also increases.
 Dilution (Ostwald’s dilution law) :
Degree of ionisation of a weak electrolyte increases with dilution.

CH3COOH CH3COO- + H +
Initial conc. C 0 0
At equilibrium C-Cα Cα Cα

C. C. C2

K Ka 
C(1   ) (1  )

Since acetic acid is weak electrolyte, hence  << 1, 1 –   1

Hence, Ka = C2 and Ka

C
Common Ion Effect :
The suppression of degree of dissociation of
weak electrolyte in presence of a strong
electrolyte having common ion is called
common ion effect.
CH3COOH CH3COO- + H +

HCl H + + Cl-

Changu & Mangu

Q.No-1. Calculate the degree of ionization of CH3COOH in 0.1M
HCl solution . Given Ka (CH3COOH) = 1.8 x 10-5

Solution : CH3COOH CH3COO- + H +

Initial conc. C 0 0
At equilibrium C-Cα Cα Cα

HCl H+ + Cl-
0.1 M 0.1M 0.1M

[H+] Total = Cα + 0.1 M =0.1 M (As α ˂˂ 1)

[CH3COO-] [H+] Cα x 0.1

Ka = =
[CH3COOH] C(1-α )

Thus 1.8 x 10-5 = 0.1 α , α = 1.8 x 10-4

Concepts of acids/bases
(i) Arrhenius concept:
The substance furnishes H+ ions in aqueous solution are
known as acids and those which produce OH– ions in
aqueous solution are known as bases.
Example: HCl, H2SO4 , Mg(OH)2 , KOH etc

Note : B(OH)3 is not a base B(OH)3 + H2O B(OH)4- + OH-

Limitation of Arrhenius Concept :

 It defines acid and bases in aqueous

solutions only.
It can not explains acidic nature of HCl (g)
and basic nature of NH3 gas.
(ii) Bronsted-Lowry concept:

An acid donates proton (H+) to other substance and

base can accept proton from an acid.

For example,

NH3  H2 O 
 NH4  OH
Base Acid conjugate conjugate
Acid Base

HCl + H2O H3O+ + Cl-

Acid Base C.Acid C.Base

The stronger an acid weaker will be its conjugate base and vice versa.
Q. No.2 : Compare the basic nature of the following species

F-, Cl-, Br-, I-

Solution :

Acidic Strength : HF ˂ HCl ˂ HBr ˂ HI

Basic Strength : F- ˃ Cl- ˃ Br- ˃ I-

(iii) Lewis concept:
An acid can accept at least a pair of electrons (electron
deficient) and a base can donate at least one pair of
electrons (electron rich) to form a coordinate bond.

For example,
..
N H3 + BF3 
 H3N : BF3 
(Adduct)

Here, NH3 is a Lewis base and BF3 is a Lewis acid.

Examples of Lewis Acids : BeCl2, BCl3, AlCl3 etc ( Incomplete octet)

Examples of Lewis Base : H2O , NH3 etc ( Having lone pair of

electrons )
Dissociation of water
Pure water is very weak electrolyte and dissociates to a small extent as
H2O H+ + OH-
[H ] [OH ]
K
H2O
Since the degree of dissociation of water ( α ) is very small.

K H2O  [H ] .[OH ]

Kw = [H+] . [OH- ]

where Kw = ionic product of water and Kw= 1 × 10–14 mol2 L–2 at 25° C

Since the dissociation of water is endothermic process, the value of Kw increases with
temperature.
The pH scale
pH = –log [H+]
and pOH = –log[OH– ]
At 25oC
For an acid solution [H+] > 10–7.

For a basic solution [H+] < 10–7.

[H+] [OH-] = 10-14
Also pKw =pH + pOH = 14

However Kw = [H+] [OH-] is valid for all temperature

and
pKw =pH + pOH
The pH scale
At 250C Kw= 14, Thus pH Scale ranges from 0 to 14
Neutral
Acidic Basic
0 7 14

At 620C Kw= 13, Thus pH Scale ranges from 0 to 13

Neutral
Acidic Basic
0 6.5 13

On increasing the temperature the pH scale shrinks

Q. What is the nature of water at 620C , if the pH of water is 6.5.

a) Acidic b) Basic c) Neutral d) Can not be predicted [Ans : c- Neutral]
 Calculation of pH of Strong Acids
Q. Calculate the pH of following solutions.
(i) 0.1M HCl (ii) 10-3 M HCl (iii) 10-7 M HCl (iv) 10-8 M HCl
Solution :
(i) HCl H+ + Cl-
[H+] Total = 10-7 + 10-7 = 2 x 10-7
0.1M 0.1 M 0.1M
pH = - log (2 x 10-7 )
[H+] = 0.1 M
= 7- 0.3010
pH = -log [H+] = -log 10-1 = 1
= 6.7
(ii) HCl H+ + Cl- (iv) 10-8 M HCl
10-3 M 10-3 M 10-3 M [H+] Total = 10-8 + 10-7
[H+] = 10-3 M = 0.1 x 10-7 + 10-7
pH = -log [10-3] = -log 10-3 = 3 = 1.1 x 10-7
pH = -log(1.1 x 10-7 )
(iii) HCl H+ + Cl- =7- 0.04
10-7 M 10-7 M 10-7 M = 6.96
H2O H+ + OH-
10-7 M 10-7 M 10-7 M

NOTE : When the concentration of strong electrolyte is less than 10-6 mol/L then,
we have to consider the [H+] from water.
Calculation of pH of diprotic acid
Q. Calculate the pH of 0.2 M H2SO4 solution.

Solution :
H2SO4 2H+ + SO42-
10-2 2 x 10-2 10-2

[H+] = 2 x 10-2 M
pH = - log (2 x 10-2)
= 2 – 0.3
=1.7
Calculation of pH of Strong Bases
Q. Calculate the pH of the following at 250C.
(i) 10-2 M NaOH (ii) 10-2 M Ca(OH)2 (iii) 10-7 M NaOH

Solution :
NaOH Na+ + OH-
10-2 10-2 10-2 Alternative Method :
pOH = -log 10-2= 2
[H+] [OH-]= 10-14
pH + pOH = 14
Thus [H+] = 10-14 / [OH-]
=10-14/10-2 Thus pH =14-pOH
= 10-12 = 14-2 =12
pH = -log 10-12= 12
(ii) 10-2 M Ca(OH)2

Solution :

Ca(OH)2 Ca2+ + 2OH-

10-2 2 x 10-2

pOH = - log (2x10-2)

= 2 – log2
=2- 0.3
= 1.7
pH = 14- pOH
=14-1.7
= 12.3
(iii) 10-7 NaOH

Solution :
NaOH Na+ + OH-
10-7 10-7 10-7

H2O H+ + OH-
10-7 10-7

[OH]Total = [OH]NaOH + [OH]H2O

= 10-7 + 10-7
= 2x 10-7
pOH = -log (2x 10-7)
= 7-0.3= 6.7
pH = 14-6.7
= 7.3
Ionization constant of weak acids:
HA (aq) + H2O (l) H3O+(aq) + A-(aq)
Initial conc. C 0 0

At equilibrium C-Cα Cα Cα

K= [H3O+] [A-] /[HA] [H2O]

Ka= K[H2O]= [H3O+][A-]/[HA]
= c2α2/c(1-α)= c α2/ 1- α

For a weak acid α˂˂ 1 and 1-α =1

Thus Ka= cα2 or, α = (Ka/c)1/2

Ionization constant of weak base:
BOH (aq) B+(aq) + OH-(aq)
Initial conc. C 0 0

At equilibrium C-Cα Cα Cα

Kb = [B+] [OH-] /[BOH]

= c2α2/c(1-α)= c α2/ 1- α

For a weak base α˂˂ 1 and 1-α =1

Thus Kb= cα2 or, α = (K/c)1/2

Relation between Ka, Kb and Kw

HA + H2O H3O+ + A-

Ka= [H3O+][A-]/ [HA] --------------- (1)

A- + H2O HA + OH-

Kb = [HA][OH-]/[A-] ---------------(2)

Eq-1 x Eq -2
Ka x Kb = [H3O+][OH-]=Kw
Solubility Equilibria and Solubility product.

When an ionic solid is dissolved in water in the saturated

condition there exist an equilibrium between the solid and the
ions present in the solution. This is called solubility equilibria.

BaSO4 (s) Ba2+(aq) + SO42-(aq)

K = [Ba2+] [SO42-]/ [BaSO4]

Ksp = K [BaSO4] =[Ba2+] [SO42-]

Ksp is constant for an electrolyte at a given temperature.

If s is the solubility of the salt

Ksp= s x s = s2 , Thus S =
 Solubility Equilibria and Solubility product.
CaF2 (s) Ca2+(aq) + 2F-(aq)

Ksp = [Ca2+] [F-]2

Let S be the solubility of CaF2

CaF2 (s) Ca2+(aq) + 2F-(aq)
At Equlibrium s 2s

Ksp= [Ca2+][F-]2
=s x (2s)2
= 4 s3

Thus solubility s = ( )1/3

 Solubility Equilibria and Solubility product.

A solid salt of general formula Mxp+Xyq- with molar solubility S

in equilibrium with its saturated solution may be represented
by
MxXy xMp+ + yXq-

And the solubility product constant is given by

Ksp= (xS)x. (yS)y
= Xx.Yy .S(x+y)
S(x+y) =( Ksp/Xx.Yy)
S = ( Ksp/Xx.Yy)1/(x+y)

Note: Ionic Product ˃ solubility product precipitation occurs.

Q . The value of Ksp of two sparingly soluble salts Ni(OH)2 and AgCN
are 2.0 x 10-15 and 6.0 x 10-17 respectively. Which salt is more soluble ?

Solution :
Ag CN Ag+ + CN-
Suppose the solubility AgCN is x mol L-1, so that
[Ag+] = x [CN-] = x

Ksp = [Ag+] [CN-]

= x . x = x2
x = (Ksp)1/2
= (6.0 X 10-17)1/2
= 7.75 X 10-9
 Ni(OH)2 Ni2+ + 2OH-

Let solubility of Ni(OH)2 is y mol L-1, so

[Ni2+] = y, [OH-] = 2x

Ksp = [Ni2+] [OH-]2

= y . (2y)2 = 4y3

Y=[ ]1/3

= ( ) 1/3

= (0.5 x 10-15) 1/3

= 7.93 x 10-5
Thus Ni(OH)2 is more soluble than AgCN.