Ionic Equilibrium

Part-01

According to conductivity substances are of two types

(1) Non-Conductor - Those substances which do not show the flow of current or electricity.
Ex. Non - metals, plastic, rubber, wood etc.
Exception – Graphite is a non-metal but show conductivity due to motion of free electrons.
(2) Conductors – Those substances which show conductivity or flow of current are called conductors and these are
of two types:
(a) Metallic conductor – Those conductors which show conductivity due to motion of free electrons.
Ex. All metals, Graphite

(b) Ionic conductors –

Those conductors which show conductivity due to movement
of free ions. Ions are in free state in the solutions of ionic
compounds. On passing electric current through the solution,
ions move towards oppositely charged electrodes, i.e., the
cation moves towards cathode (negative electrode) and the
anion moves towards anode (positive electrode). Due to this
reason, they are called cations and anions respectively. The
current flows through the solution due to the movement of
the ion.

According to strength, ionic conductors are of two types

(1) Strong electrolytes – Those ionic conductors which are almost completely ionized in aqueous solution are
called as strong electrolytes.
For strong electrolytes, the value of degree of ionisation is almost 100% i.e.  = 1
Ex.

(a) All Strong Acid : H2SO4, HCl, HNO3, HClO4, HBr, HI

(b) All Strong Base: KOH, NaOH, Ba(OH)2, CsOH, RbOH

(c) All Ionic Salts : NaCl, KCl, CuSO4

(2) Weak electrolytes – Those electrolytes which are partially ionized in aqueous solution are called as weak
electrolytes. For weak electrolytes the value of  is less than one.
 Ex.

(a) All Weak acids : HCN, CH3COOH, HCOOH, H2CO3, H3PO3, H3PO2, B(OH)3 or H3BO3, etc.
(b) All Weak bases : NH4OH, Cu(OH)2, Zn(OH)2, Fe(OH)3, Al(OH)3 etc.

Arrhenius Concept
(a) According to Arrhenius, when an electrolyte dissolves in water, it splits up into two oppositely charged particles
i.e. cation and anion.
(b) In an electrolytic solution (aqueous solution of electrolyte), total +ve charge = total –ve charge
i.e. solution is electrically neutral.
In an electrolytic solution number of +ve ions may or may not be equal to the number of negative ions.
(c) Properties of an electrolytic solution are defined by its ions.
Ex. Blue colour of CuSO 4 solution is due to Cu+2 ion (dark blue colour)
(d) When electric current is passed through aqueous solution of electrolyte then cation shows migration towards
cathode where as anion shows migration towards anode.
(e) When a weak electolyte is dissolved in water an equilibrium is set up between unionized species and ionized
species.
This condition of the reversible ionic reaction is known as ionic equilibrium. AB (aq.)  A + (aq.) + B– (aq.)

According to Law Of Mass Action.

K = Ionisation Constant

Illustration 1. No. of total ions and resultant total charge in A 2B3 electrolyte:
(1) Five and + 1 (2) Five and - 1 (3) 0 and 0 (4) None of them
Solution: (4)

Illustration 2. Assertion: H2SO4 is a strong acid.

Reason: H2SO4 is almost completely ionised in aqueous solution.
(1) A (2) B (3) C (4) D
Solution: (1)

Ostwald's Dilution Law

 Ostwald was the first to apply law of mass action to ionic equilibrium.
 Ostwald dilution law is applicable only for weak electrolytes.
Statement:

According to Ostwald's dilution law when solution of a weak electrolyte

is diluted then the degree of ionization of weak electrolyte is increases,
and at infinite dilution it remains 100% dissociated.

Let AB(aq) ⇌ A+ (aq) + B– (aq)

Initial concentration C 0 0

At Equilibrium (C – C) (C) (C)

 = Degree of Ionization

dilution   
At infinite dilution,  = 100%

Thus for weak electrolytes the degree of ionisation is directly proportional to square root of dilution or inversely
proportional to square root of concentration. This law is known as Ostwald Dilution Law.

➢ At infinite dilution the value of  becomes equal to one.

➢ The value of concentration should be in terms of normality for calculation of pH.

Limitation of Ostwald Dilution Law:

It is not applicable for strong electrolytes.
 Factors affecting the Value of Degree of ionisation

Temperature 1 3 Nature of electrolytes

Dilution 2 4 Nature of solvent

(1) Temperature → On increasing temperature, ionization increases so  increases because dissociation

is endothermic process.

(2) Dilution →   V so on dilution,  increases.

(3) Nature of electrolytes

(i) Strong electrolytes (ii) Weak electrolytes
 = 100%  < 100%

(4) Nature of solvent

If Dielectric constant  of solvent increases then the value of  increases.
H2O →  = 81
D2O →  = 79
C6H6 →  = 2.5
CCl4 →  = 0

Illustration 3. For which, dilution law is applicable:

(1) NaCl (SASB salt) (2) HCl (SA)
(3) CH3COONa (WASB salt) (4) None
Solution: (4)
 Ionic Equilibrium
Part-02

Introduction
Formulae:

(i) ln x = logex = 2.303 log10x = 2.303 log x

(ii) log (x × y) = log x + log y

x
(iii) log   = log x – log y
y
(iv) log xy = y log x

Ex. (i) log 6 = log (2 × 3)

= log 2 + log 3
= 0.3010 + 0.4771 = 0.7781
(ii) log 30= log (3 × 10)
= log 3 + log 10
= log 0.4771 + 1 = 1.4771
(iii) log 1000 = log 10 3
= 3 log 10 = 3 × 1 = 3

Some values of Log:

log 1 = 0
log 2 = 0.3010
log 3 = 0.4771
log 4 = 0.6020
log 5 = 0.6989
log 6 = 0.7781
log 7 = 0.8451
log 8 = 0.9030
log 9 = 0.9542
log 10 = 1
log 11 = 1.04
log 100 = 2
log 1000 = 3
log 10000 = 4
Some terms which are used in ionic equilibrium :
Antilog: Antilog (x) = 10x

antilog(0) = 100 = 1
antilog(0.3) = 100.3 = 2
antilog(0.48) = 100.48 = 3
antilog(0.6) = 100.6 = 4
antilog(0.7) = 100.7 = 5
antilog(0.78) = 100.78 = 6
antilog(0.85) = 100.85 = 7
antilog(0.9) = 100.9 = 8
antilog(0.95) = 100.95 = 9
antilog(1) = 101 = 10

Ex. Antilog (2) = 102 = 100

Antilog (0.3010) = 10.3010 = 2
Antilog [log (2)] = Antilog (0.3010) = 2
 Ionic Equilibrium
Part-03

pH - Scale: Given by – Sorenson

pH Scale is called Sorenson scale.
pH scale is a measuring scale used to measure strength of acid and base and its value is equal to –log[H +]

i.e. pH = –log [H+] = log

Ex. [H+] = 10–3

pH = – log 10–3 = + 3 log 10 = 3
Conclusion:
If pH = x then [H+] = 10–x or Vice versa
i.e. If [H+] = 10–x then pH = x
1
pOH → It is equal to – log [OH–] i.e. pOH = – log [OH–] = log
[OH – ]
a
Ex. If X = × 10–c, then find pX?
b
a 
Sol. pX = – log X = – log   10 − c 
 b 
 a 
pX = –  log + log10 − c  = – [ log a – log b – c]
 b 
pX = c + log b − log a

pH scale at 25ºC

Neutral
 5
Illustration 1. If [H+] = × 10–4 then find pH ?
3
5
−4 
Solution: pH = – log [H+] = – log   10 
3 
 5 −4 
= –  log + log10  = – [log 5 – log 3 – 4]
 3 
= – [ 0.699 – 0.4771 – 4] = – [ – 3.778] = 3.778
 Ionic Equilibrium
Part-04

Explanation of Water

a. Nature of water is neutral. [H+] = [OH–] =10–7M (At 25°C)

Nature of water is Neutral.

i.e.
At 25°C  pH = 7 & pOH = 7  pH = pOH

1000
b. No. of moles of H2O in 1 litre water = = 55.5 moles
18
c. Molar concentration of H 2O = 55.5 mol L–1

d. Number of H2O molecules in 1 litre water = 55.5 N A (NA= AVOGADRO'S NUMBER)

e. Concentration of H+ and OH– ions in 1 litre water

[H+] = 10–7 mol L–1 and [OH–] = 10–7 mol L–1
f. No. of H+ and OH– ions in 1 litre water
No. of H+ ions = 10–7NA and No. of OH– ions = 10–7 NA

g. In water (Number of H 2O molecules : Number of H + ions)

= 55.5 NA : 10–7 NA

= 55.5 × 107 : 1
i.e. one H+ ion is obtained from 55.5 × 10 7 H2O molecules

h. Degree of ionisation of water ():

Let H2O(aq) ⇌ H+(aq) + OH–(aq)

Initial concentration C 0 0

At Equilibrium (C – C) (C) (C)

 [H+] = C

 
Hence, water is a very weak electrolyte.
i. K (Ionisation constant of water):

H2O  H+ + OH–

j. Ionic product of water Kw:

H2O (aq) ⇌ H+ (aq) + OH– (aq)

 K × [H2O] = [H+] [OH–]

Since, dissociation takes place to a very small extent, [H2O] may be regarded as
constant.
Thus, the product gives another constant which is designated as Kw.

At 25°C : KW = 10–7 × 10–7 = 10–14

K[H2O] = KW  (always)

Various forms of KW
(1) KW = [H+] [OH–] for water [H+] = [OH–]
(2) KW = [H+]2
(3) KW = [OH–]2
(4) KW = [H3O+] [OH–]
(e) KW = [H3O+]2 {[H3O+] = [H+]}
Hydronium ion Proton
• Relation between pH and pOH :
KW = [H+] [OH–]
Taking –log on both sides
–log KW = – log [H+] – log [OH–]

pKw = pH + pOH
 • Nature of water is neutral so,
[pH = pOH]
pKW = pH + pH pKW = pOH + pOH
2pH = pKW 2 pOH = pKW
pK W pK W
pH = pOH =
2 2

At 25°C, KW = 10–14 or pKW = 14  pH + pOH = 14 or pH = pOH = 7

k. Effect of temperature:

+ –
H2O  H + OH H = +ve
Ionization of water is endothermic process so, on increasing
+ – + –
temperature  increases or [H ] and [OH ] increases or [H ] [OH ]
increase i.e. Kw increases means pH decreases or pOH decreases.
+ –
On increasing  T   Increases   [H ]  & [OH ]   Kw 
Kw   pKw   pH  & pOH 
–14
At 25C, Kw = 10
–12
At 90C, Kw = 10

At 25°C At 90°C
KW 10–14 10–12
pKw 14 12
pH = pOH 7 6
10–7 10–6
pH + pOH = pKW 14 12

Golden Key Points

• On increasing temperature, both [H +] and [OH–] increases equally so water remains neutral but pH changes from
7 to 6 at 90°C.

Illustration 1. Dissociation constant of water at 25° C is

(1) 10–14 × (55.5)–1 (2) 10–7 × (18)–1 (3) 10–14 × (18)–1 (4) 10–7 × (55.4)–1
Solution: (1)
Illustration 2. What should be the number of H + ions in 1 mL of distilled water, if the number of H + ions in
1 L is 6.023 × 1016?
6.023 1016
Solution: Number of H+ ions in 1 mL distilled water = = 6.023  1013
1000

Illustration 3. Calculate the sum of [H+] & [OH–] present in pure water at 25°C
Solution: At 25°C, pH =pOH =7 for pure water.
[H+] = 10–7M
[OH–] = 10–7M
[H+] + [OH–] = 10–7 + 10–7= 2 × 10–7M

Illustration 4. At a 25°C temperature, pH of pure water is found to be 4. Determine pK w at the same

temperature ?
Solution: For pure water
[H+] = 10–7M
pK w
pH = pOH =
2
 pKw = 2pH = 2 × 4 = 8
 Ionic Equilibrium
Part-05

C. Conjugate acid-base pair:

(i) If two species differ only by one H + ion then they form conjugate acid-base pair.
(ii) When an acid loses a proton, the residual part of it has a tendency to regain a proton. Therefore it behaves
as a base.
CH3 COOH  CH3 COO– + H+

Weak acid Conjugate strong base

(Ka = 1.85 × 10–5) or acceptor ion
NH4OH + H+  NH 4 OH +2 ⎯⎯⎯⎯→ NH4+ + H 2O

Weak base Conjugate strong acid

(Kb = 1.85 × 10–5) (acceptor ion)
HCl ⎯⎯⎯⎯→ H+ + Cl–
Strong acid Conjugate weak base (spectator ion)
(Ka ~ ) Accepting tendency of H + ~ 0
NaOH + H+ ⎯⎯⎯⎯→ NaOH2+ ⎯⎯⎯⎯→ Na+ + H 2O
Strong base Conjugate weak acid
(Kb ~ ) (spectator ion)
Note : Strong acids have weak conjugate bases while weak acids have strong conjugate bases. Similarly, strong
bases have weak conjugate acids while weak bases have strong conjugate acids.
D. Relation between conjugate acid-base pair :–
Example – CH3COOH  CH3COO– + H+

Acid conjugate base

+ –
NH4OH  NH4 + OH
Base conjugate acid
–
CH3COOH CH3COO
acid conjugate base
– + – –
CH3COOH + H2O  CH3COO +H3O CH3COO +H2O  CH3COOH + OH

[CH3COO – ] [H3O + ] [CH3COOH] [OH – ]

Ka = ...... (i) Kb = ..... (ii)
[CH3COOH] [CH3COO – ]
In both the reactions H 2O is in excess quantity so active mass of H 2O is one.
+ –
Now multiply the equation (i) and (ii) K a × Kb = [H ] [OH ]
+ –
we know [H ] × [OH ] = KW (Ionic product of water) Ka  Kb = Kw

Taking –log on both sides pK a + pK b = pK w

 –14
we know that for water at 25°C, KW = 10 or pKW = 14

So K a  K b = 10−14 or pK a + pK b = 14

Above relation is applicable only for conjugate acid-base pairs.

Illustration 1. Determine the ionisation constant of CH 3COOH if Kb for CH3COO– at 25°C is 5 × 10–10.
Solution: (K b )CH COO− = 5 × 10–10
3

(Ka )CH3COOH = ?
(K a )CH3COOH  (K b ) CH COO− = Kw
3

 Kw at 25oC = 10–14
10−14
(Ka )CH3COOH = = 0.2 × 10–4 = 2 × 10–5
5  10−10

Illustration 2. Calculate following values at 25 oC for given species:

(i) pKa of H3O+ (ii) pKb of OH–
Solution: (i) pKa of H3O  conjugate base of H3O+ is H2O
+

(K b )H2O = Ionisation constant of water

(K b )H2O = 1.8 × 10–16
(pKb )H2O = 16 – log 1.8 = 16 – 0.24 = 15.76
(pK a ) H O+ + (pKb )H2O = 14 at 25oC
3

 (pK a ) H O+ = 14 – 15.76 = –1.76

3

(ii) pKb of OH–  conjugate acid of OH – is H2O

(pKa )H2O + (pKb )OH− = 14 at 25oC
(pKb )OH− = 14 – 15.76 = –1.76
 Ionic Equilibrium
Part-06

Application of Ostwald's Dilution Law: K = C

2

Application of Ostwald's Dilution Law

(a) For mono basic (b) For mono acidic

weak acid (HA) weak base (BOH)

(a) For mono basic weak acid (HA)

(i) HA ⇌ H+ + A–
Initial Concentration C 0 0
At equilibrium C – C C C
Ionization constant (Ka)  is Degree of Dissociation

 <<<< 1  (1 –  ) ≈ 1  Ka = C2 

(ii) [H+] (Concentration of H +)

[H+] = C ........(1)
Ka
Ka = C2 or = .......(2)
C
Ka
from Eq. (1) and (2) [H+] = C ×
C
[H+] = Ka  C

(iii) pH = –log [H+]

put the value of [H+]
pH = – log ( K a  C ) = – log (Ka × C)1/2
1
pH = – [log Ka + log C]
2
1 1
pH = – log Ka – log C
2 2
1 1
pH = pKa – log C
2 2
 Summary:
1. Ka = C2

2. [H+] = C = Ka  C
3. pH = – log [H+]
1 1
or pH = pKa – log C
2 2

(b) For mono acidic weak base (BOH)

(i) BOH ⇌ B+ + OH–

Initial Concentration C 0 0
At equilibrium C – C C C
Ionization constant (Kb)  is Degree of Dissociation

 <<<< 1  (1 –  ) ≈ 1  Kb = C2 

(ii) [OH–] (Concentration of OH –)

[OH–] = C ........(1)
Kb
Kb = C2 or = .......(2)
C
Kb
from Eq. (1) and (2) [OH–] = C ×
C
[OH–] = Kb  C

(iii) pOH = –log [OH–]

put the value of [OH–]
pOH = – log ( K b  C ) = – log (Kb × C)1/2
1
pOH = – [log Kb + log C]
2
1 1
pOH = – log Kb – log C
2 2
1 1
pOH = pKb – log C
2 2
Summary:
1. Kb = C2

2. [OH–] = C = Kb  C
3. pOH = – log [H+]
1 1
or pOH = pKb – log C
2 2
Illustration 1. Find out the value of  of 10–2 M HCN solution if [H+] = 10–3.
Solution: [H+] = C
10−3
10–3 = 10–2  or  = = 10–1 or  = 0.1
10−2
% = 10%

Illustration 2. For 10 M CH3COOH solution if Ka = 10–5 then find out:

(i)  (ii) [H+] (iii) pH
Solution: (i) 
(Degree of ionisation) :– Ka = C2
105
10–5 = 102 or 2 = = 10–6 or  = 10–3
10
(ii) [H+] = C = 10 × 10–3 = 10–2
(iii) pH = – log [H+] = – log 10–2 = 2

Illustration 3. For 10–3 M H2CO3 if  = 10% then find out the value of pH ?
Solution: Normality = M × V.F. = 10 –3 × 2 = 2 × 10–3
[H+] = C = 2 × 10–3 × 0.1 = 2 × 10–4
pH = – log [H+] = – log (2 × 10–4) = – log 2 – log 10–4 = – 0.3010 + 4 = 3.7
 Ionic Equilibrium
Part-07

Mixing of ions
(a) Common ion effect (b) Odd ion effect
When a strong electrolyte having a When a strong electrolyte having
common ion, is mixed with weak an odd ion, is mixed with weak
electrolyte then the degree of electrolyte then the degree of
ionisation () of weak electrolyte is ionisation () of weak electrolyte is
decreased. This effect is called increased. This effect is called odd
common ion effect. ion effect.

Common ion: On mixing CH3COONa with CH3COOH solution

Initially CH3COOH  CH3COO– + H+

On mixing CH3 COONa → CH3 COO– + Na+

CH3 COOH  CH3 COO– + H+ [CH3COO–] increases So [H+]

decreases respectively
Odd ion: On mixing, NaOH with CH3COOH solution

Initially CH3 COOH  CH3COO– + H+

On mixing, NaOH → Na+ +

OH–
→ H2O (due to odd ion effect)
CH3COOH  CH3 COO– + H+

Illustration 1. Assertion : NaCl + HCl does not experience common ion effect.
Reason : Both NaCl and HCl are strong electrolytes.
(1) A (2) B (3) C (4) D
Solution: (1)
 Ionic Equilibrium
Part-08

pH of mixture of acid and base.

(a) pH of mixture of strong acids:

N1V1 + N2V2 + N3V3 + ................. = NV
V = Volume of final solution = V 1 + V2 + V3 + ..........
N = Normality of final solution = [H +] in final solution.
(b) pH of mixture of strong bases:
N1V1 + N2V2 + N3V3 + ................. = NV
V = Volume of final solution = V 1 + V2 + V3 + ..........
N = Normality of final solution = [OH –] in final solution.
 Ionic Equilibrium
Part-09

(c) pH of mixture of strong acids and strong bases :

For acid :
N1V1 + N2V2 + N3V3 + ................. = (NV)Acid
For base :
N1V1 + N2V2 + N3V3 + ................. = (NV)Base
(i) If (NV)Acid > (NV)Base then solution is acidic.
NV = (NV)Acid – (NV)Base and
[H+] = N
(ii) If (NV)Base > (NV)Acid then solution is basic.
NV = (NV)Base – (NV)Acid and
[OH–] =N
(iii) If, (NV)acid = (NV)base then solution is neutral.

Illustration 1. Calculate the pH of the following aqueous solutions at 25°C containing the mixture of -
(a) 2 mol H2SO4 and 1 mol HNO3 in 10 L aqueous solution
(b) 4 g NaOH and 5.6 g KOH are mixed in 20 L aqueous solution
2  2 + 11 1
Solution: (a) [H+] = 0.5 =
10 2
pH = –log 2–1 = 0.3
4 5.6
+
(b) [OH–] = 40 56 = 10−2
20
pOH = 2
pH = 12

Illustration 2. 4 L of 0.1 M Ba(OH) 2 and 6 L of 0.05 M NaOH are mixed. Determine the pH of the resultant
mixture at 25°C.
N1V1 + N 2 V2
Solution: [OH − ] =
V
0.1  2  4 + 0.05  6 0.8 + 0.3
= = = 1.1 × 10–1
10 10
pOH = – log (1.1 × 10 –1) = 1 – log 1.1  0.97
pH = 14 – 0.97 = 13.3
Illustration 3. Calculate the pH of mixture formed by mixing.
(a) 100 ml of 0.1M HNO3 + 900 ml of 0.1 M HCl.
(b) Equal volumes of 0.2M HCl, 0.1 M H 2SO4 & 0.2M HClO4.
0.1 0.1 + 0.9  0.1 10−2 + 9 10−2
Solution: (a) [H + ] = =
1 1
[H+] = 10–1 ; pH = –log(10–1) = 1
0.2  V + 0.1 2  V + 0.2  V 0.6  V
(b) [H + ] = = = 2 × 10–1
3V 3V
pH = –log (2 × 10–1) = 1 – 0.3 = 0.7

Illustration 4. 4 L of 0.2 M HNO3 and 6 L of 0.1 M NaOH are mixed at 25°C. Determine the pH of the resultant
mixture.
Solution: gm-eq. of HNO3 = M × VF × V(L)
= 0.2 × 1 × 4
= 0.8
gm-eq. of NaOH = M × VF × V (L)
= 0.1 × 1 × 6
= 0.6
gm-eq. of acid > gm. Eq. of base
0.8 − 0.6
 [H+] = = 0.02 = 2 × 10–2
10
 pH = –log (2 ×10–2) = 2 – log 2
= 2 – 0.3 = 1.7
 Ionic Equilibrium
Part-10

Salts, Types of Salt and Conjugate Theory

A. Salt: Salts are regarded as compounds made up of positive and negative ions. The positive part comes from a
base while negative part from an acid. Salts are ionic compounds.
i.e. A compound formed by the neutralization of acid and base is known as salt.
Acid + Base → Salt + Water; H = –ve
HCl + NaOH → NaCl (Salt) + H2O

B. Types of Salt

Normal/general Salts (a)

(b) Acid Salt

Basic Salt
(c)

(d)
Double Salt

Complex Salt (e)

(f)
Mixed Salt

(a) Normal/general salts: The salts formed by the loss of all possible protons of an acid and all hydroxide ions
of base are called normal salts. Such a salt does not contain either a replaceable hydrogen ion or a hydroxyl
(OH–) group.
Ex.: NaCl, NaNO3, K2SO4, Ca3(PO4)2, Na2HPO3, NaH2PO2 etc.
(b) Acid salts: Salts formed by incomplete neutralisation of poly basic acids are called acid salts. Such salts still
contain one or more replaceable hydrogen ions (H +).
Ex.: NaHCO3, NaHSO4, NaH2PO4, Na2HPO4 etc.
(c) Basic salts: Salts formed by incomplete neutralisation of poly acidic bases are called basic salts. Such salts
still contain one or more hydroxide ions.
Ex.: Zn(OH)Cl, Mg(OH)Cl, Fe(OH) 2Cl, Bi(OH)2Cl etc.
 (d) Double salts: The addition compounds formed by the combination of two simple salts are termed as
double salts. Such salts are stable in solid state only i.e. when dissolved in water they break into simple ions.
Ex.: FeSO4.(NH4)2SO4.6H2O, K2SO4 . Al2(SO4)3 . 24H2O etc.

(Ferrous ammonium sulphate) (Potash alum)

(e) Complex salts: These salts when dissolved in water give complex ions. Complex ions are stable in solid
state as well as in solutions.
Ex.: K4[Fe(CN)6], [Co(NH3)6]SO4, [Ag(NH3)2Cl etc.

(f) Mixed salts: The salts which furnish more than one type of cations or more than one type of anions when
dissolved in water are called mixed salts.
These are formed by the neutralisation of more than one acids and bases.
Ex.

H2SO4 + NaOH NaHSO4 + H2O

Acid Base Acid Salt
NaHSO4 + KOH NaKSO4 + H2O
Acid Salt Base Mixed Salt

OCl Na Na
Ca S NH4 PO4
Cl K H

(a) Types of general salts:

(i) SASB (ii) SAWB (iii) WASB (iv) WAWB

Illustration 1. Which salt is not an example of acidic salt:

(1) HCOONa (2) NaH2PO2 (3) NaHS (4) (1) and (2) both

Solution: (4)

Illustration 2. Calculate the no. of ions in Mohr's salt [FeSO 4.(NH4)2SO4.6H2O] or Ferrous Ammonium
Sulphate:
Solution: FeSO4. (NH4)2SO4 . 6H2O → Fe+2 + SO4–2 + 2NH4+ + SO4–2 + 6 H2O

Total number of ions = 5

Hydrolysis of Salts
Salt hydrolysis is defined as the process in which water reacts with cation or anion or both of a salt to change the
concentration of H+ and OH– ions of water.
Salt hydrolysis is reverse process of neutralization.
Water + Salt ⇌ Acid + Base ; H = +ve
 Hydrolysis of strong Hydrolysis of weak
acid and strong base A C acid and strong base
[SA – SB] types of salt [WA – SB] types of salt

Hydrolysis
of
Salts

Hydrolysis of strong Hydrolysis of weak

acid and weak base B D acid and weak base
[SA - WB] types of salt (WA – WB) type of salt

A. Hydrolysis of strong acid and strong base [SA – SB] types of salt –
Ex. NaCl, BaCl2, Na2SO4, KClO4, BaSO4, NaNO3, KBr, KCl etc.
Na+ + Cl– + H2O ⎯⎯→ Na+ + OH– + H+ + Cl–
H2O  H+ + OH– (It is not salt hydrolysis)

(i) Hydrolysis of salt of [SA – SB] is not possible as both cation and anion are not reactive.
(ii) Aqueous solution of these type of salt is neutral in nature. (pH = pOH = 7)
(iii) pH of the solution is 7.
(iv) No effect on litmus paper.
 Ionic Equilibrium
Part-11

B. Hydrolysis of strong acid and weak base [SA - WB] types of salt –
Ex. CaSO4, NH4Cl, (NH4)2SO4, Ca(NO3)2, ZnCl2, CuCl2, CaCl2 , AgCl, AgI, AgNO3 etc

NH4Cl + H2O NH4OH + HCl

WB SA

NH4++Cl– + H2O NH4OH + H+ + Cl–

NH4+ + H2O NH4OH + H+

(i) In this type of salt hydrolysis, cation reacts with H 2O therefore called as cationic hydrolysis. The cation of
the salt which has come from weak base is reactive.
(ii) Solution is acidic in nature as [H +] is increased.
(iii) pH of the solution is less than 7.
(iv) Solution turns blue litmus paper red.
Kh = Hydrolysis constant KW = Ionic product of water
Ka = Ionisation constant of acid Kb = Ionisation constant of base
C = Concentration of salt (concentration of ions) h = Degree of hydrolysis

(a) Relation between Kh, KW and Kb

B+ + H2O BOH + H+

NH4+ + H2O NH4OH + H+

Hydrolysis constant [Kh]
[NH 4 OH][H + ]
Kh = .......(1)
[NH +4 ]

For weak Base NH4OH NH4+ + OH–

 NH +4  OH − 
Kb =  ........(2)
 NH 4 OH 
For water H2O  H+ + OH–

KW = [H+] [OH–] ........(3)

Now multiplying Eq. (1) and (2) = Eq. (3)
NH4OH H+  NH+4  OH− 
   = [H+] [OH–]
×
NH+4  NH4OH
   
i.e. K h × Kb = KW

KW
Kh = ........(4)
Kb
 (b) Degree of hydrolysis – Represented by h

NH4+ + H2O NH4OH + H+

Initial concentration of salt C 0 0
C – Ch Ch Ch

 NH4OH  H +  Ch  Ch C2 h 2 Ch 2
Kh = = = =
 NH 
+
4
C − Ch C (1 − h ) (1 − h )

Since h <<<< 1 then (1 – h)  1

Kh = Ch 2
 ........(5)
 h
h2 = h  h= ........(6)
C C
KW
KW Kb
 Kh =  h=
Kb C
KW
h= …….(7)
Kb  C
(c) pH of the solution: pH = – log [H+]
KW KW  C
[H+] = Ch = C  [H+] ........(8)
Kb  C Kb
Taking – log on both sides
1

KW  C  KW  C 
2

– log [H+] = – log  pH = – log  

Kb  Kb 
1
pH = − [ log KW + logC – log Kb ]
2
1 1 1
pH = − logKW − logC − (–log Kb)
2 2 2
1 1 1
pH = pKw − log C – pKb
2 2 2
1 1
pH = 7 – pKb – log C ........(9)
2 2

C. Hydrolysis of weak acid and strong base [WA – SB] types of salt –
Ex. CH3 COONa, HCOONa, KCN, NaCN, K 2CO3, BaCO3, K3PO4 etc.
CH3 COONa + H2 O CH3  CH 3 COOH + NaOH
WA SB

CH3 COO– +Na+ + H2O  CH3 COOH +Na+ + OH–

CH3 COO– + H2O  CH3 COOH + OH–

(i) In this type of salt hydrolysis, anion reacts with water therefore called as anionic hydrolysis. The anion
of the salt which has come from weak acid is reactive.
(ii) Solution is basic in nature as [OH –] increases.
 (iii) pH of the solution is greater than 7.
(iv) Solution turns red litmus paper blue.
(a) Relation between Kh, KW and Ka
CH3 COO– + H2O  CH3COOH + OH–

CH3COOH  OH − 
Kh = ........(1)
CH3COO − 
For weak acid
CH3COOH  CH3COO– + H+

CH3COO−   H + 
Ka =  ........(2)
CH3COOH 
For water
H2O  H+ + OH–

KW = [H+] [OH–] ........(3)

Now multiply eq. (1) × eq. (2) = eq. (3)

CH3COOH OH −  CH3COO −   H + 

×  =[H+][OH–]
CH3COO−  CH3COOH 
K h × K a = KW

KW
Kh = ........(4)
Ka

(b) Degree of hydrolysis (h):

CH3COO– + H2O  CH3 COOH + OH–

Initial concentration of salt C 0 0

C – Ch Ch Ch

CH3COOH  OH −
 Ch  Ch Ch 2 2
Kh = = =
CH3COO  −
C − Ch C (1 − h )

Ch 2
Kh =
(1 − h )

Since h <<<< 1 then (1 – h)  1

Kh = Ch 2
 ........(5)
 h
h2 = h or h = ........(6)
C C

KW
h= ........(7)
Ka  C
 (c) pH of the solution
[OH–] = Ch

KW KW  C
[OH–] = C × or [OH–] = ........(8)
Ka  C Ka

taking – log on both sides

1
 K .C  2
– log [OH+] = – log  w 
 Ka 
1
pOH = − [log KW + logC – logKa]
2
1 1 1 1 1
pOH = pKW – pKa – logC or pOH = 7 – pKa – logC
2 2 2 2 2
 pH + pOH = 14

pH = 14 – pOH
1 1
 pH = 7 + pKa + logC ........(9)
2 2

Illustration 1. Which of the following solution has maximum degree of hydrolysis

(1) 0.1 M NH4Cl (2) 0.01 M NH4Cl
(3) 0.001 M NH4Cl (4) Same in all
Solution: NH4+ + H2O  NH4OH + H +

Kw Kh
Kh = h=
Kb C

Lower the conc., higher will be degree of hydrolysis.

Ans: (3)

Illustration 2. Which of the following solution has maximum pH?

(1) 0.1 M NaCl (2) 0.1 M NH4Cl
(3) 0.001 M NH 4Cl (4) 0.01 M NH4Cl
Solution: Salt Salt type pH
NaCl SASB 7
NH4Cl SAWB <7

 1 
 pH = 7 − 2 (pK b + log C) 
 
NaCl solution has more pH than solution of NH 4Cl.
Ans: (1)
Illustration 3. Calculate pH of 10–2 M KCN solution if dissociation constant of HCN = 10 –10.
Solution: Ka = 10—10  pKa = 10
CN– + H2O  HCN + OH–
Kw
Kh =
Ka
pH = 7 + ½ (pKa + logC)
 pH = 7 + ½ (10 + log 10–2)
 pH = 11
 Ionic Equilibrium
Part-12

D. Hydrolysis of weak acid and weak base (WA – WB) type of salt :
Ex. CH3COONH4 , AgCN, NH4CN, CaCO3, [NH4]2CO3, ZnHPO3 etc.
CH3COONH4 + H2O  CH3 COOH + NH 4OH
WA WB

CH3 COO– + NH4+ + H2O  CH3COOH + NH4OH

* Maximum hydrolysis occurs of the salt of (WA – WB) as both the cation and anion are reactive.
* Solution is almost neutral but it may be acidic or basic depending upon the values of K a and Kb
* pH of the solution is near to 7.

For WA - WB types of salt

S.No. Ka > K b Kb > K a Ka = K b
1. Hydrolysis Cationic-anionic Anionic-cationic Neutral hydrolysis
2. Nature Acidic Basic Neutral
3. pH pH < 7 pH > 7 pH =7

(a) Relation between Kh, KW, Ka and Kb

CH3 COO– + NH4+ + H2O  CH3COOH + NH4OH

Kh =
CH3COOH  NH 4OH  ........(1)
CH3COO−   NH 4+ 
For weak base
NH4OH  NH4+ + OH–

 NH +4  OH − 
Kb =  ........(2)
 NH 4 OH 
For weak acid
CH3COOH  CH3 COO– +H+

CH3COO−   H + 
Ka =  ........(3)
CH3COOH
For water
H2O  H++ OH–

KW = [H+] [OH–] ........(4)

Multiply Eq. (1) × Eq. (2) × Eq. (3) = Eq. (4)
 CH3COOH  NH 4OH  ×  NH 4  OH 
+ −
CH3COO −   H + 
× = [H+] [OH–]
CH3COO−   NH +4   NH 4 OH  CH3COOH 
Kh × Kb × Ka = KW

KW
Kh = ........(5)
Ka  Kb

(b) Degree of hydrolysis (h) –

CH3 COO– + NH4+ + H2O  CH3COOH + NH4OH

Initial concentration of salt C C 0 0

C – Ch C – Ch Ch Ch

Kh =
CH3COOH  NH 4OH  = Ch  Ch
=
C2 h 2
CH3COO−   NH +4  ( C − Ch )( C − Ch ) C (1 − h )  C (1 − h )
Since h <<<< 1 then (1 – h)  1

 Kh = h2 .......(6)

KW KW
or h2 = or h = .......(7)
Ka  Kb Ka  Kb

(c) pH of the solution

From equation (3)
CH3COO−   H + 
Ka =
CH3COOH
K a  CH3COOH  K a  Ch K a  h
 H+  = = =
CH3COO  −
C − Ch 1− h

Since h <<<< 1 then (1 – h)  1

[H+] = Ka × h [Now put the value of h from eq. (5)]

KW
= Ka 
Ka  Kb

K W  Ka
 H +  = .......(8)
Kb
1
 KW  Ka 
2

Taking – log on both sides – log [H +] = – log  

 Kb 
1
pH = – [ log (Kw × Ka) – log Kb ]
2
1
pH = – [ log KW + log Ka – log Kb ]
2
 1 1 1
pH = – [ log KW] – [log Ka] – [ – log Kb ]
2 2 2
1 1 1
pH = + pKW + pKa – pKb
2 2 2
1 1
pH = 7 + pK a − pK b .......(9)
2 2

Illustration 1. What is the pH of 1 M CH 3COONa solution? K a of acetic acid = 1.8 × 10 –5, Kw=10–14 mol2 L–2
(1) 2.4 (2) 3.6 (3) 4.8 (4) 9.4
Solution: (4)

Illustration 2. Calculate the degree of hydrolysis of a mixture containing 0.1N NH 4OH and 0.1N HCN
If Ka = 10–5 and Kb = 10–5
Solution: Salt is [WA – WB]

KW 10−14
h= = = 10−14  10+10 = 10 −4 = 10–2
Ka  Kb 10 −5  10 −5

Illustration 3. Assertion : An aqueous solution of NH 4NO3 is acidic in characters.

Reason : NH4NO3 in an aqueous solution undergoes anionic hydrolysis.
(1) A (2) B (3) C (4) D
Ans. (3)
 Ionic Equilibrium
Part-14

Buffer Solution
Introduction
A. Definition: A solution which resists the change in pH and whose pH does not change significantly on addition of
small amount of strong acid or strong base is called buffer solution.
B. Properties of buffer solution:
(i) The pH of buffer solution does not change appreciably upon the addition of small amount of either strong
acid or strong base.
(ii) The pH of buffer solution does not depend on the volume of solution. Hence, solution can be diluted
without change in pH.
(iii) The pH of buffer solution remains constant even if it is kept for a long time.
Change in pH of a solution occurs due to change in concentration of free H + or OH– ions.

Types of
Buffer Solution

Simple Buffer Mixed Buffer

Solution Solution

Acidic Basic
Buffer Solution Buffer Solution

A. Simple buffer solution :- Aqueous solution of weak acid-weak base (WA – WB) types of salt.
Ex. CH3COONH4 , NH4CN, AgCN etc.
1 1
pH = 7 + pKa – pK [pH does not depend on concentration]
2 2 b
CH3COO– + + H2O  CH3COOH + NH4OH.

Case I Case II

When mixing of acid [H+] When mixing of base [OH–]

CH3 COO– + H+  CH3COOH NH4+ + OH– ⇌ NH4OH
CH3COOH + OH– ⇌ CH3COO– + H2O
NH4OH + H+ ⇌ NH4+ + H2O
B. Mixed buffer solution :
(i) Acidic buffer solution :- The solution in which weak acid and its conjugate base are present. or
Aqueous solution of mixture of weak acid and salt of same weak acid with any strong base is called acidic
buffer solution.
Ex. CH3COOH + CH3COONa
WA WASB
CH3 COOH  CH3 COO– + H+

CH3 COONa → CH3 COO– + Na+

 −
CH3COOH+ CH3COO  + Na (Spectator ion)
+

 WA C Base 

Buffer Action:
Case 1. Suppose that a small amount of strong acid is added to the buffer solution. The H + ions of the acid react
with the basic component, CH 3COO– ions in the buffer.
–
CH3COO(aq) + H+ CH3COOH (aq)
Most of the added H+ ions are consumed because the concentration of CH 3COO– in the buffer solution
is high. The reaction nearly goes to completion because CH 3COOH is a weak acid and its ions have
strong tendency to form nonionized CH 3COOH molecules. Due to the removal of most of the added H +
ions, there is no appreciable decrease in pH.

Case 2. If a small quantity of base is added to the buffer solution, the OH – ions are consumed by the acidic
component CH3COOH.
–
CH3COOH(aq) + OH(aq) –
CH3COO(aq) + H 2 O( )

The effect is the neutralization of most of the added OH – ions by CH3COOH. Therefore, there is no
appreciable change in pH.
(a) pH of acidic buffer solution :
CH3 COOH + CH3 COONa
Acid + Salt
CH3 COOH  CH3COO– + H+

CH3COONa → CH3COO– + Na+

CH3COO−   H + 
Ka = 
CH3COOH 
Ka[CH 3COOH] Ka[Acid]
or  H +  = −
=
[CH 3COO ] [Conjugate base]
Taking –log on both sides
[Acid] [Conjugate base]
pH = pKa – log or pH= pKa + log
[Conjugate base] [Acid]

Henderson's equation [Salt] Conjugate base

` pH= pKa + log or
[Acid]  Acid 
 • [Conjugate base]eq [Salt] because CH 3COO– mainly comes from salt since dissociation of CH 3COOH in
presence of CH 3COONa is appreciably decreased.
• [Acid]eq initial concentration of acid since it is almost unionised in presence of salt due to common ion
effect.

(b) pH range of acidic buffer solution : It depends on pK a of acid and ratio of salt to acid concentrations.

[CH3 COOH] : [CH3 COONa]  pH = pKa + log

CH3COONa 
CH3COOH 
10
(i) If, 1 : 10  pH = pKa + log = pKa + 1
1
(ii) If, 10 : 1  pH = pKa –1
So pH range

pH = pKa ± 1

(c) Maximum buffer action condition of acidic buffer solution:

[CH3 COOH] : [CH3 COONa]

1
1 : 1  pH = pKa + log  
1
Or pH = pKa
(ii) Basic buffer solution :
Definition : The solution in which weak base and its conjugate acid are present. or
Aqueous solution of mixture of weak base and salt of same weak base with any strong acid is called basic
buffer solution.
Ex. NH4OH + NH4Cl

NH 4 OH NH 4+ + OH −
→ NH 4+ + Cl−
NH 4 Cl ⎯⎯
 + −
4 OH + NH 4  + Cl [Spectator ion]
 NHW.B. C.acid 

Buffer Action:
Case 1. If a small amount of the acid is added to the buffer solution, the H + ions are consumed by NH 4OH.
+ +
NH4 OH(aq) + H(aq) NH4(aq) + H 2 O( )

Thus, most of the added H + ions are neutralized by NH 4OH and there is no appreciable change in pH.
Case 2. When a small amount of base is added to the buffer solution, the OH – ions react with ions to produce
nonionized NH4OH molecules.

NH +4(aq) + OH (aq)
−
NH 4 OH( aq )
The concentration of ions is high in the buffer solution. Hence most of the added OH – ions are
consumed. The reaction goes nearly to completion because NH 4OH is a weak base and its ions have
 strong tendency to form nonionized NH 4OH molecules. Thus, there is no appreciable
increase in pH.
(a) pOH of basic buffer solution :
[ NH4OH + NH 4Cl]
Base Salt

NH4OH  NH +4 + OH −

→ NH 4+ + Cl−
NH 4 Cl ⎯⎯
 NH +4   OH −  K b  NH4 OH
Kb =  or [OH–] =
 NH 4 OH   NH+4 

 NH 4  +

taking –log on both sides pOH = pK b + log 

 NH 4OH 
Henderson's equation:

[Salt] Conjugateacid 
pOH = pK b + log or
[Base]  Base

(b) pOH range of basic buffer solution : It depends on pK b of base and ratio of salt to base concentrations.
NH4Cl
[NH4 OH] : [NH4 Cl]  pOH = pKb + log 
NH4OH

(i) If, 1 : 10  pOH = pKb + 1

(ii) If, 10 : 1  pOH = pKb – 1
So, pOH range : pOH = pKa  1

(c) Maximum buffer action condition of basic buffer solution :

1
NH4 OH : NH4 Cl pOH = pKb + log  
1
1 : 1 or pOH = pK b
 Ionic Equilibrium
Part-15

Buffer Capacity
Definition:
(i) It is defined as the number of moles of strong acid (or strong base) added to one litre of a buffer solution to
change its pH by one unit.
(ii) It measures the effectiveness of a buffer.
(iii) Larger the value of buffer capacity more resistant is the solution to pH change.
Number of moles of acid or base added per litre
Buffer capacity =
Change in pH of buffer solution

Illustration 1. When 2 moles of HCl is added to 1 L. of an acidic buffer solution, its pH changes from 3.9 to
3.4. Find its buffer capacity.
2
Solution: B.C. = =4
0.5

Illustration 2. 20 mg of NaOH is added into CH 3COOH solution in which 60 mg of CH 3COOH is present.

Calculate pH of solution if volume of final solution is 10 litre? [Given (pK a)CH3COOH = 4.74]

20  10−3 10−3
Solution: No. of moles of NaOH = = mol
40 2
60  10−3
No. of moles of CH3COOH = = 10–3 mol
60
CH3COOH + NaOH → CH3COONa + H2O
−3
10
t=0 10–3 mol mol – –
2
10−3 10−3
t = teq –
2 2
Buffer solution is obtained
[CH 3COONa]
pH = pKa + log
[CH 3COOH]
 10−3 10−3 
 pH = 4.74 + log  / 
 2  10 2  10 
 pH = 4.74

Illustration 3. Calculate volume of 0.1 M HCOONa solution that should be added into 50 ml of 0.05 M of
HCOOH solution to make a buffer solution of pH = 4. [Given: pK a = 3.7]
Solution: Suppose ‘V’ ml volume of HCOONa solution is added then final concentration would be as following:
0.1V
[HCOONa] = M
50 + V
0.05  50
[HCOOH] = M
50 + V
[HCOONa]
pH = pKa + log
[HCOOH]
0.1 V
 4 = 3.7 + log
0.05  50
V
 0.3 = log
25
V V
 log 2 = log  =2
25 25
 V = 50 ml

Illustration 4. For effectiveness of the buffer solution of CH 3COOH & CH3COONa determine its pH range.
(pKa for CH3COOH = 4.7)
Solution: pH range of acidic buffer  (pKa – 1 to pKa + 1)
= (4.7 – 1 to 4.7 + 1)
= 3.7 to 5.7
 Ionic Equilibrium
Part-17

Solubility and Solubility Product (Ksp)

A. Solubility
(a) Definition At constant temperature the maximum number of moles of solute which can be dissolved in a
solvent to obtain 1 litre of solution (i.e. saturated solution) is called solubility.

B. Solubility Product(Ksp):
When a sparingly soluble salt such as AgCl is put into water, a very small amount of AgCl dissolves in water and
most of the salt remains undissolved in its saturated solution.
• A solution which remains in contact with undissolved solute is said to be saturated.
• The salt AgCl is an electrolyte, its dissociation occurs in solution. Hence, the quantity of AgCl that dissolves in
water dissociates into Ag + and Cl– ions. Thus, in the saturated solution of AgCl an equilibrium exists between
undissolved solid AgCl and its ions, Ag + and Cl– ions.
Dissolution + −
AgCl(s) Pr ecipitation
Ag(aq) + Cl(aq)

 Ag +  . Cl− 
According to law of mass action K =
 AgCl
Since, the concentration of undissolved solid AgCl is constant. Thus, the product K.[AgCl] gives another constant
which is designated as Ksp.
So, K.[AgCl] = [Ag+].[Cl–]  Ksp = [Ag+] . [Cl–]

At constant temperature product of concentrations of ions in a saturated solution of substance is called solubility
product of that substance. (Saturated solution is that solution in which solid solute and the ions in solution remain in
equilibrium with each other.
• Ksp for CaCl2 CaCl2(s)  Ca+2(aq) + 2Cl–(aq)

Solubility product in terms of concentration of ions Ksp = [Ca +2 ] [Cl–]2

• Ksp for AlCl3 AlCl3(s)  Al+3(aq) + 3Cl–(aq)

Solubility product in terms of concentration of ions Ksp = [Al +3 ] [Cl–]3

• General form AxBy(s)  xA+y(aq) + yB–x(aq)

Ksp = [A+y ]x [B–x]y

Application of Solubility Product (Ksp)
(A) To find out the solubility (S) :
(i) Ksp of AB type salt
Ex. NaCl, BaSO4, CH3COONa, CaCO3, NaCN, KCN, NH4CN, NH4Cl etc.
AB(s)  A+(aq) + B–(aq)

a 0 0
(a–s) s s
Ksp = [A+] [B–]

Ksp = s2 or s = K sp

(ii) Ksp of AB2 or A2B type salt

Ex. CaCl2, CaBr2, K2S, (NH4)2SO4, K2SO4, K2CO3 etc.
AB2(s)  A+2(aq) + 2B–(aq)

a 0 0
a–s s 2s
Ksp = [A+2] [B–]2
Ksp = s × (2s)2 = s × 4s2 = 4s3
1
 K sp 
3

s=  
 4 

(iii) Ksp of AB3 or A3B type salt

Ex. FeCl3, AlCl3, K3PO4 etc.
AB3(s)  A+3(aq) + 3B–(aq)

a 0 0
a–s s 3s
− 3
Ksp =  A   B  = s × (3s)
+3 3
= 27s4

1
 K sp 
4

s = 
 27 

(iv) Ksp of A2B3 or A3B2 type salt

Ex. Al2(SO4)3, Ba3 (PO4 )2 etc.
A2B3(s)  2A+3(aq) + 3B–2(aq)

a 0 0
a–s 2s 3s
+3 2 −2 3
Ksp = A   B  = 2s × 2s × 3s × 3s × 3s = 108s 5

1
 K sp 
5

s= 
 108 
 (v) General form
AxBy(aq)  xA+y(aq)+ yB–x(aq)

a 0 0
a–s xs ys
Ksp = [A+y]x . [B–x]y

Ksp = (xs)x. (ys)y = Xx . Yy . (s)(x+y)

Illustration 1. Write the Ksp for the following salts.

Solution: (i) Al2 (SO4 )3(s)  2Al+3(aq) + 3SO4–2(aq)

Ksp = 22 × 33 × (S)2 + 3 = 4 × 27 × S 5 = 108 S5

(ii) Na2 KPO4(s)  2Na+(aq) + K+(aq) + PO4–3(aq)

Ksp = 22 × 11 × 11 (S)2+1+1 = 4S4

(iii) NaKRbPO 4(s)  Na+(aq) + K+(aq) + Rb+(aq) + PO4–3(aq)

Ksp = 11 × 11 × 11 × 11 × (S)1 + 1 + 1 + 1 = S4

Illustration 2. If solubility product of the base M(OH) 3 is 2.7 × 10–11, the concentration of OH – will be
(1) 3 × 10–3 (2) 3 × 10–4 (3) 10–3 (4) 10–1
Solution: (1)

Illustration 3. The solubility of BaSO4 in water is 1.07 × 10–5 mol dm–3. Estimate its solubility product.

Solution Solubility equilibrium for BaSO 4 is BaSO4(s)  Ba+2(aq) + SO4–2(aq)

The solubility product is, Ksp = [Ba2+] × [ SO42–]

It S is the solubility of BaSO 4. then Ksp = S2 because x and y = 1.
Now, S = 1.07 × 10–5 M.
Hence, Ksp = (1.07 × 10–5)2 = 1.145 × 10–10

Illustration 4. The solubility product of AgBr is 5.2 × 10 –13. Calculate its solubility in mol dm –3 and g
dm–3. (Molar mass of AgBr. = 187.8 g mol–1)

Solution: The solubility equilibrium of AgBr is AgBr(s)  Ag +(aq) + Br–(aq)

and Ksp = [Ag+] [Br–] = S2 because x = 1 = y.

The molar solubility S of AgBr is given by s = K sp = 5.2  10 –13

s = 7.2 × 10–7 × 187.8

= 1.35 × 10 –4 g dm–3
 Ionic Equilibrium
Part-18

(C) Common ion effect on solubility:

Important point:- Solubility of substances always decreases in the presence of common ion. According to
Le-Chatelier's principle on increasing common ion concentration equilibrium shifts in backward direction until the
equilibrium is re-established so, the solubility of substances decreases but K sp remains same because it is an
equilibrium constant which depends only on temperature.

Illustration 1. Find out the solubility of AgCl in the presence of C molar NaCl solution ?
Solution: AgCl  Ag+ + Cl–

S S S (Let solubility of AgCl is S mol L –1)

Ksp = [Ag+] [Cl–]
Ksp = S2
In NaCl solution
NaCl → Na+ + Cl–
C C C
Let solubility of AgCl in the presence of NaCl solution is S' mol L –1.
AgCl  Ag+ + Cl–

S' S' S'+C

According to L.M.A.
Ksp = [Ag+]' [Cl–]'
Ksp = S' (S' + C) = S' 2 + S'C (Neglecting the higher power terms of S')

K sp
Ksp = S' C S' =
C

Illustration 2. Find out the solubility of CaCl 2 solution in the presence of C molar NaCl solution ?
Solution: CaCl2  Ca+2 + 2Cl–

S S 2S [Let solubility of CaCl 2 is S mol L–1]

Ksp = [Ca+2] [ Cl–] 2 = 4S3
For NaCl solution
NaCl → Na+ + Cl–
C C C
Let solubility of CaCl2 in the presence of NaCl solution is S' mol L –1.
CaCl2  Ca+2 + 2Cl–

S' S' 2S'+C

 According to L.M.A.
Ksp = [Ca+2]' [Cl–]' 2
Ksp = S' (2S' + C)2 = S' (4S' 2 + 4S'C + C2) `
Ksp = 4S' 3 + 4S' 2 C + S'C2 (Neglecting the higher power terms of S')

K sp
S' =
C2

Illustration 3. Find out the solubility of NaCl in the presence of C molar CaCl 2 solution ?
Solution: CaCl2 → Ca+2 + 2Cl–
C C 2C
Let solubility of NaCl in the presence of CaCl 2 solution is S' mol L–1.
NaCl  Na+ + Cl–

S' S' S'+2C

According to L.M.A.
Ksp = [Na+]' [Cl–]'
Ksp = S' (S' + 2C) = S' 2 + 2S'C (Neglecting the higher power terms of S')

K sp
S' =
2C
 Ionic Equilibrium
Part-19

(B) Condition of precipitation /Ionic product (IP or Q sp):

• Ionic product (IP) of an electrolyte is defined in the same way as K sp. The only difference is that ionic product
expression contains the initial concentration of ions or the concentration at any time whereas the expression of
Ksp contains only equilibrium concentration. Thus, for AgCl.
Qsp = IP = [Ag+]i [Cl–]i and Ksp = [Ag+]eq.[Cl–]eq
• Ionic product changes with concentration but K sp does not. Ksp is applicable for saturated solution of the sparingly
soluble electrolyte.
• To decide whether an ionic compound will precipitate, its K sp is compared with the value of ionic product. The
following three cases arise:

(i) IP < Ksp : The solution is unsaturated and precipitation will not occur.
(ii) IP = Ksp : The solution is saturated and solubility equilibrium exists.
(iii) IP > Ksp : The solution is supersaturated and hence precipitation of the compound will occur.

Thus, a salt is precipitated when its ionic product exceeds the solubility product of the salt.

(D) Precipitation of soap and salt (NaCl)

(i) Precipitation of NaCl (common salt) :
For the precipitation of NaCl, HCl gas is passed in saturated solution of NaCl to increase the concentration
of Cl– ion by common ion, so ionic product of concentration of Na + and Cl– ion becomes more than K sp of
NaCl and NaCl gets easily precipitated.
Saturated solution of NaCl NaCl  Na+ + Cl–

Ksp = [Na+] [Cl–]

By passing HCl gas HCl → H+ + Cl–
due to common ion Ksp < [Na+] [Cl–] 

(ii) Precipitation of soap :

For precipitation of soap, NaCl is mixed in saturated solution of soap to increase the concentration of Na +
ion by common ion. So ionic product of concentration of Na + and stearate ions is more than K sp of soap
and soap gets easily precipitated.
Ex. C17H35COONa (Sodium stearate)
Saturated solution of C 17H35COONa C17H35COONa+  C17H35COO– + Na+

Ksp = [C17H35COO–] [Na+]

By mixing NaCl solution NaCl → Na+ + Cl–
due to common ion Ksp < [C17H35COO–] [Na+] 
Illustration 1. Solubility of CaCl 2 is 4 × 10–8, then find out its Ksp and its new solubility in the presence of
10–2 M Ca(OH)2.
Solution: CaCl2  Ca+2 + 2Cl–

1 s 2s (Initial solubility = s)
Ksp = 4s3 = 4(4 × 10–8)3 = 256 × 10–24 .......(i)
Ca(OH)2 → Ca+2 + 2OH–
C 0 0
0 C 2C
CaCl2  Ca+2 + 2Cl–

1 s' +C 2s' (New solubility = s')

Ksp = [Ca+2]' [Cl–]2 '
= [s' + C] [2s']2 = 4s'3 + 4s'2C (s'3 = negligible)
Ksp = 4s'2C .......(ii)
−24
Ksp 256  10
From equation (i) and (ii) s' 2 = = = 64 × 10–22
4C 4  10−2
s' = 8 × 10–11 mol L–1

Illustration 2. Which of the following sets of concentration is responsible for the precipitation of PbI 2
(KSP = 1.2 × 10–13 M)
(1) [Pb2+] = 10–5 ; [I–] = 10–5 M
(2) [Pb2+] = 10–7 ; [I–] = 10–4 M
(3) [Pb2+] = 10–6 ; [I–] = 10–5 M
(4) [Pb2+] = 10–4 ; [I–] = 10–4 M
Solution: (4) For precipitation
IP > Ksp
Ksp = 1.2 × 10–13
(1) IP = [Pb+2] [I–]2 = 10–5 × (10–5)2 = 10–15
(2) IP = 10–7 × 10–8 = 10–15
(3) IP = 10–6 × 10–10 = 10–16
(4) IP = 10–4 × 10–8 = 10–12

Illustration 3. At what pH the precipitation of Zn(OH) 2 (KSP = 1 × 10–12 M3) will start from the aqueous solution
which is saturated with 0.001 M Zn 2+ ion.
Solution: (Ksp )Zn(OH)2 = 10–12
Qsp = Ksp = [Zn+2] [OH–]2
Qsp = 10–3 × [OH–]2 = 10–12
[OH–]2 = 10–9
2 pOH = 9
pOH = 4.5
 pH = 9.5
 Ionic Equilibrium
Part-20

Acid and Base

Introduction
The earliest classification of substances into acids and bases was based upon the characteristic properties
possessed by each one of them. For example,
Acid was defined as a substance whose aqueous solution possesses the following characteristic properties:
(i) conducts electricity.
(ii) reacts with active metals like zinc, magnesium etc. to give hydrogen.
(iii) turns blue litmus red.
(iv) has a sour taste.
(v) whose acidic properties disappear on reaction with a base.
Base was defined as a substance whose aqueous solution possessed the following characteristic properties:
(i) conducts electricity,
(ii) reacts with active metals like zinc, magnesium etc. to give hydrogen,
(iii) turns red litmus blue,
(iv) has a bitter taste
(v) whose basic properties are destroyed on reaction with an acid.
The above definitions of acids and bases are called operational definitions as they are based on certain operations
(i.e. tests) to be performed on the substances. However, these have been replaced by conceptual definitions (put
forward by Arrhenius, Bronsted-Lowry and Lewis) which go into the causes of the observed behavior, based upon
structure and composition of the substances.

(1) (2) (3)

Arrhenius Bronsted-Lowry Lewis

Concept Concept Concept
Arrhenius Concept (1884)
(a) Acid:- According to this concept, those substances which produce free H + ions in aqueous solution are called
acid.
Example HCl, HNO 3, H2SO4, H3PO4, H2CO3, H2S, CH3COOH etc.
HCl + H2O → H+(aq.) + Cl–(aq.)
H2SO4 + H2O → 2H+(aq.) + SO4–2(aq.)
CH3COOH + H2O  CH3COO–(aq.) + H+(aq.)

(b) Base:- Those substances which produce free OH – ions in aqueous solution are called base.
Example NaOH, KOH, Cs(OH), Rb(OH), NH 4OH, Ba(OH)2, Ca(OH)2, Al(OH)3 etc.
NaOH + H2O → Na+ (aq.) + OH– (aq.)
Ba(OH)2 + H2O → Ba+2 (aq.) + 2OH– (aq.)
(c) Nature of water:- According to this concept nature of water is neutral and act as a solvent.

(d) Neutralisation Reaction :- Those reactions in which acid and base react together to form water molecule
are called neutralisation reactions.
i.e. Na+ + OH– + H+ + Cl– → NaCl + H2O
H+ + OH– → H2O
(e) Strength of acids and bases:- This concept explains the strength of acids and bases depending upon the
basis of degree of ionisation.
Example For strong electrolytes  ~ 100%
For weak electrolytes  < 100%
(f) Advantage :- This concept explains the acids and bases practically. i.e. To find out the pH, ionisation constant,
hydrolysis constants, heat of neutralisation etc.
(g) Disadvantage :-
(i) It explains the behaviour of acids and bases only in aqueous (water) solvents.
(ii) It does not explain the stability of proton (H +).

Illustration 1. Gaseous hydrogen chloride is a very poor conductor of electricity but a solution of hydrogen chloride
in water is a good conductor. This is due to the fact that :-
(1) Water is a good conductor of electricity
(2) Hydrogen chloride ionises in water
(3) A gas cannot conduct electricity but a liquid can
(4) HCl does not obey Ohm's law where as the solution does
Solution: (2)

Illustration 2. Which is acid in the following pairs according to Arrhenius concept ?

(1) HCl(g) and HCl (aq) (2) CH3COOH(l) and CH 3COOH(aq)
Solution: (1) HCl(aq.) (2) CH3COOH(aq.)
Bronsted-Lowry Concept (1923)
It is based upon the exchange of proton.
(a) Acid :- According to this concept those substances which have tendency to donate proton (H +) by any
method in any solvent are called acids.
Example (i) HCl, HNO 3, H2SO4, H2CO3, H2S, CH3COOH, H3PO3 etc. (neutral molecules)
(ii) HS–, HCO3–, HSO4–, H2PO4–, HPO4–2 etc. (anions)
(iii) NH4+, H3O+, PH4+, CH3COOH2+ etc. (cations)
(iv) [Al(H2O)6]+3, [Ag(H2O)2]+1, [Fe(H2O)6]+3 etc.
(v) HCl (Acid) + H2O (Solvent) → H3O+ + Cl–
(vi) NH4+ (Acid) + H2O (Solvent) → NH3 + H3O+
(vii) [Al(H2O)6]+3 (Acid) + H2O (Solvent) → [Al(H2O)5OH]+2 + H3O+
(b) Base :- Those substances which have tendency to accept proton by any method in any solvent are called the
bases.
Example (i) NaOH, KOH, Rb(OH), Cs(OH), Ba(OH) 2, Ca(OH)2, NH4OH, Al(OH)3 etc.
(ii) HS–, HCO3–, HSO4–, H2PO4–, HPO4–2 etc.
(iii) NH3, RNH2, R2NH, R3N, C6H5NH2, C5H5N, H2N-NH2 etc.
(iv) O–2, SO4–2, CO3–2, Cl–, Br–, I–, CN– etc.
(v) NH3 (Base) + H2O (Solvent) → NH4+ + OH–
(vi) CO3–2(Base) + H2O (Solvent) → HCO3– + OH–
(c) Nature of water :- According to this concept nature of water is amphoteric or amphiprotic i.e. water can act
as both acid and base.
(i) HCl (Acid) + H2O (Base) → Cl– + H3O+
(ii) NH3 (Base) + H2O (Acid) → NH4+ + OH–
(d) Neutralisation Reaction :- According to this concept those reaction in which acid and base react together
and convert into their respective conjugate acid and base are called neutralisation reactions.
Example

– +
HCl + NH 3 Cl + NH 4
Acid Base Conjugate Conjugate
Base Acid

(e) Strength of acids and bases :- This concept explain the strength of acid and base depending upon the basis
of relative tendency to accept or donate the proton.
(i) HClO4 (ix) H3PO4 (xvii) C2H5 – OH
(ii) HI (x) HF (xviii) CH  CH
(iii) HBr (xi) CH3COOH (xix) NH3
(iv) H2SO4 (xii) H2CO3 (xx) R–NH2
(v) HCl (xiii) H2S (xxi) CH4
(vi) HNO3 (xiv) NH4+ (xxii) H2
(vii) H3O+ (xv) HCN
(viii) HSO4– (xvi) H – OH
 Example
(i) HCl + H2O  Cl– + H3O+

Strong acid Strong base Weak base Weak acid

(ii) HCl + CH3COOH  Cl– + CH3COOH2+

Weak acid Weak base Strong base Strong acid

(iii) HCl + C6H6 (Solvent)  HCl does not act as acid because

C6H6 is an aprotic solvent.

Illustration 3. Which of the following behave both as Bronsted acid as well as Bronsted bases ?
H2O, HCO3–, H2SO4, H3PO4, HS–, NH3
Solution: H2O, HCO3–, HS–, NH3

Illustration 4. Assertion : Cl– is weaker base than OC2H5.

Reason : Cl– is conjugate base of stronger acid, HCl.
Solution: (1)

Lewis Concept (1939)

(a) Lewis Acid:- According to this concept those species which have self tendency to accept the lone pair of
electrons are called acids. i.e. Lewis acid is an electron pair acceptor (electrophilic).
(b) Lewis Base:- Those species which have self tendency to donate the lone pair of electrons are called bases.
i.e. a base is an electron pair (lone pair) donor (nucleophile).