Chemistry Std XII [1] 03.

Ionic Equilibria

3. IONIC EQUILIBRIA Marks : 4 or 6

 Defination :
1) Electrolytes :-
The substances which in aqueous solution dissociate into cations and anions is
called as Electrolyte.
Ex. NaCl, HCl, CH3COOH etc.
There are two type of electrolyte:
a) Strong electrolyte :- The electrolyte which dissociate completely are called strong electrolyte
Ex. NaCl, HCl, H2SO4
b) Weak electrolyte :- The electrolyte which dissociate partially are called weak electrolyte.
Ex. CH3COOH, NH4OH
2) Ionic Equilibria :-
The equilibrium between ions and unionised molecules of an electrolyte in solution
is called as ionic equilibria.
CH3COOH(aq) CH3COO –(aq) + H +(aq)
3) Degree of dissociation :-
The fraction of total number of moles of an electrolyte that dissociate into its ions
at equilibrium is called as degree of dissociation .
It is denoted by  and represented by
 = number of moles dissociated / total number of moles of an electrolyte
Percentage dissociation =  x 100

 Arhenius theory of acids and bases :-[Ionic theory ]

Acid:- A substance which contains hydrogen and on dissolving in water produces hydrogen ions(H+)
is called as acid. Ex.HCl
HCl H+ + Cl-
Base :- A substance which contains OH group and on dissolving in water produces hydroxyl ions(OH-)
is called as base. Ex.NaOH
NaOH Na+ + OH-
Neutalisation :- The reaction between acid and base producing salt and water is called as
neutralisation.
HCl + NaOH  NaCl + HO
2

H+ + Cl- + Na+ + OH-  Na+ + Cl- + H2O

H+ + OH-  H O
2

Thus the reaction between hydrogen ion and hydroxyl ion forming unionised water molecules is
called as neutralisation .
Chemistry Std XII [2] 03. Ionic Equilibria
 Bronsted-Lowry theory of acids and bases :-[Protonic theory]
Acid : The substance that donate a proton (H+) to another substance is called as acid.
Base : The substance that accepts a proton (H+) from another substance is called as base.
For example, HCl + NH 3 NH4+ + Cl-
since HCl donates a proton it is an acid while NH3 accepts a proton it is a base.

◆ Conjugate acid - base pair :- A pair of an acid and a base differing by a proton is called a
conjugate acid base pair.
HCl + H2O H3O+ + Cl-
Acid 1 Base 2 Acid 2 Base 1
conjugate pair 2
conjugate acid base pair 1

Ques:- Mention a conjugate acid and a conjugate base for each of the following :
Ans :- Substance Conjugate acid Conjugate base
+
H2O H3O OH-
- -2
HSO4 H2SO4 SO4
- -2
H2PO4 H3PO4 HPO4
H2CO3 ---- HCO3-
+
NH4 ---- NH3
Br- HBr ----

 Lewis theory of acids and bases :[Electronic theory]

Acid:- Any species that can accept a pair of electron is called as acid.
Ex. Electron deficient species like cations(K+, Ag+,Ca+2) and molecule having
incomplete octet like BeF2, BF3, ZnCl2.
Base:- Any species that can donate a pair of electron is called as base.
Ex. Electron rich species like anions(Cl-, OH-, O-2) and molecule with lone
pair of electron like NH3, R-O-R, R-NH2

Since ammonia has a lone pair of electron to donate, it acts as a lewis base.While BF3
is a molecule with incomplete octet hence it is electron defecient and acts as a lewis acid.
Chemistry Std XII [3] 03. Ionic Equilibria

◆ Dissociation constant of weak acid:-

The equilibrium constant for dissociationequilibrium of a weak acid is called dissociation
constant of weak acid.
Consider an aqueous solution of a weak acid HA.
HA H+ + A-
[H+] x [A-]
The dissociation constant is represented as Ka =
[HA]

 Ostwald’s dilution law for weak electrolyte :-

Consider the dissociation of a weak electrolyte BA. Let V dm3 of a solution contain
one mole of the electrolyte. Let  be the degree of dissociation of weak electrolyte.Then
BA B+ + A-
Initial mole 1 0 0
Moles at equilibrium (1 -  )  
Conc. at equilibrium (1 -  )  
V V V
Applying law of mass action to this dissociation equilibrium, we have
[B+] x [A-]
K=
[BA]
 x 
V V
K=
 
V
As the electrolyte is very weak,  is very small as compared to unity,        

 K= V But C = 1/V where C is concentration in mol / dm3

 
 K= V or K= C

 = KV or  = K / C

= Kx V or  = K / C

  V or  1 / C
This is expression for Ostwald’s dilution law.

Thus, The degree of dissociation of weak electrolyte is directly proportional to

the square root of volume of a solution or inversly proportional to square root of

concentration of solution.
Chemistry Std XII [4] 03. Ionic Equilibria

 Ostwald’s dilution law for weak acid :-

Consider the dissociation of a weak acid HA. Let V dm3 of a solution contain
one mole of weak acid HA . Let  be the degree of dissociation of weak acid HA .Then
HA H+ + A-
Initial mole 1 0 0
Moles at equilibrium (1 -  )  
Conc. at equilibrium (1 -  )  
V V V
Applying law of mass action to this dissociation equilibrium, we have
[H+] x [A-]
Ka =
[HA]
 x 
V V
Ka =
 
V
As the electrolyte is very weak,  is very small as compared to unity,        

 Ka = But C = 1/V where C is concentration in mol / dm3
V

 Ka = or Ka =  C
V
 = Ka V or  = Ka / C

=  Ka x V or  = Ka / C

  V or   1 / C

This is expression for Ostwald’s dilution law.

Thus, The degree of dissociation of weak acid is directly proportional to

the square root of volume of a solution or inversly proportional to square root of

concentration of solution.

 Ostwald’s dilution law for weak base :-

Consider the dissociation of a weak base BOH . Let V dm3 of a solution contain
one mole of weak base BOH . Let  be the degree of dissociation of weak base BOH .Then
BOH B+ + OH-
Initial mole 1 0 0
Moles at equilibrium (1 -  )  
Conc. at equilibrium (1 -  )  
V V V
Applying law of mass action to this dissociation equilibrium, we have
Chemistry Std XII [5] 03. Ionic Equilibria

[B+] x [OH-]
Kb=
[BOH]
 x 
V V
Kb =
 
V
As the electrolyte is very weak,  is very small as compared to unity,        
 
 Kb =  But C = 1/V where C is concentration in mol / dm3
V
 
 Kb = or Kb=  C
V
 = Kb V or  = Kb / C

=  Kb x V or  = Kb / C

  V or   1 / C

This is expression for Ostwald’s dilution law.

Thus, The degree of dissociation of weak base is directly proportional to

the square root of volume of a solution or inversly proportional to square root of

concentration of solution.

 Autoionisation of water
Pure water ionises to a very less extent. The ionisation equilibrium is represented as follows,
H2O + H2O H3O+ + OH-
The equilibrium constant K for the above equilibrium is represented as,
[H O+] x [OH-]
3
K=
[H2O]2
K x [H O]2 = [H O+] x [OH-]
2 3

Since K and conc. of pure water are constant therefore K x [H2O] = Kw

Kw= [H O3 +] x [OH-]

Where Kw is called ionic product of water.

At 25OC, Kw= 1 x 10-14

Defn:- The product of molar concentration of hydronium ions( or hydrogen ions) and hydroxyl ions at
equilibrium in pure water at constant temperature is called as ionic product of water.
It is represented as
Kw = [H 3O+] x [OH-]

At 25OC, Kw = 1 x 10-14
Chemistry Std XII [6] 03. Ionic Equilibria

 pH and pOH
1) pH :- The negative logarithum to the base 10 of the molar concentration of hydrogen ions
H+ is known as the pH of a solution
pH = - log 10[H+] or pH = - log 10[H3O+]
1) pOH :- The negative logarithum to the base 10 of the molar concentration of hydroxyl ions
OH- is known as the pOH of a solution
pOH = - log [OH -]
10

Ques : Derive the relation, pH + pOH = 14

Ans :- The ionic product of water is given by
Kw = [H 3O+] x [OH-]
At 25OC, Kw = 1 x 10-14

 [H3O+] x [OH-] = 1 X 10-14

Taking logarithum to base 10 of both sides, we get

log [H O+] + log [OH-] = - log 1 + log 10-14

10 3 10 10 10

Multiplying both side by -1,

(-log [H O+]) + ( -log [OH-] ) = (- log 1 ) + (-log 10-14)

10 3 10 10 10

But - log 10[H3O+] = pH and - log 10[OH-] = pOH

 pH + pOH = 0 + ( -14 x - log 10)

10

 pH + pOH = -14 x 1

 pH + pOH = 14
 pH Scale :-
The scale which represent the acidic, basic or neutral nature of the solution is called
as pH scale.
(a) For pure water or neutral solution, [H 3O+] = [OH-] = 1 x 10-7M
 pH = - log [H 10
O+3 ] = - log 101 x 10-7 = 7 or
 pOH = - log 10[OH-] = - log101 x 10-7 = 7

(b) For an acidic solution, [H3 O+] > [OH-] and hence
[H3O+] > 1 x 10-7M and [OH-] < 1 x 10-7M
 pH < 7 and pOH > 7

(c) For an basic solution, [H3 O+] < [OH-] and hence
[H3O+] < 1 x 10-7M and [OH-] >1 x 10-7M
 pH > 7 and pOH < 7
Chemistry Std XII [7] 03. Ionic Equilibria

 HYDROLYSIS OF SALT :-
Defn:- A reaction in which either cations or anions or both the ions of salt react with
water to produce acidity or basicity or neutrality is called hydrolysis.
 Types of salts :-
(1) Salt of strong acid and strong base: NaCl, KNO3, Na2SO4
(2) Salt of strong acid and weak base : NH4Cl, (NH4)2SO4
(3) Salt of weak acid and strong base : CH3COONa, KCN, HCOONa
(4) Salt of weak acid and weak base : CH3COONH4, NH4CN, (NH4)2CO3

Ques: Explain the Hydrolysis of Salt of strong acid and strong base.
Ans : Sodium chloride is a salt of strong acid HCl and strong base NaOH. When it is dissolved in water
it undergoes hydrolysis as follows:
NaCl + H2O NaOH + HCl
As both are strong, they dissociate completely to liberate H+ and OH- ions, respectively.

Na+ + Cl- + H2 O Na+ + OH- + H+ + Cl-

H2O H+ + OH-
Since the solution contain equal number of H and OH- ions , it is neutral.
+

Hence the Salt of strong acid and strong base does not undergoes hydrolysis.

Ques: Explain the Hydrolysis of Salt of strong acid and weak base.
A solution of CuSO4 is acidic . Explain.
Why it is necessary to add H2SO4 while preparing the solution of CuSO4.
Ans : Copper sulphate is a salt of strong acid H2SO4 and weak base Cu(OH)2. When it is dissolved
in water it undergoes hydrolysis as follows:
CuSO4 + 2H2O Cu(OH)2 + H2SO4
weak base strong acid
2+ 2-
Cu + SO + 2H O Cu(OH) + 2H+ + SO 2-
2+4 2 2 4
Cu + 2H O Cu(OH) + 2H+
2 2
Since the solution contain more number of H+ ions, the solution is acidic.
But Cu(OH)2 forms a precipitate and solution becomes turbid.
When H2SO4 is added, the hydrolysis equilibrium is shifted to the left hand side and Cu(OH)2
dissolves giving clear solution.

Ques: Explain the Hydrolysis of Salt of weak acid and strong base.
Ans : Sodium acetate is a salt of weak acid CH3COOH and strong base NaOH. When it is dissolved
in water it undergoes hydrolysis as follows:
CH3COONa + H2O CH3COOH + NaOH
Weak axid strong base
- +
CH COO + Na + H O CH COOH + Na+ + OH-
3 - 2 3
CH COO + H O CH COOH + OH-
3 2 3
Since the solution contain more number of OH- ions, the solution is basic.

Ques: Explain the Hydrolysis of Salt of weak acid and weak base.
Ans : (i) A salt of weak acid and weak base for which Ka = Kb :
Ammonium acetate is a salt of weak acid CH3COOH and weak base NH4OH. When it is dissolved
in water it undergoes hydrolysis as follows:
CH COO- + NH + + H O CH COOH + NH OH
3 4 2 3 4
weak acid weak base

Since Ka = Kb , weak acid CH3COOH and weak base NH4OH dissociate to the same extent.
Hence [H3 O+] = [OH-] and the solution becomes neutral after hydrolysis.
Chemistry Std XII [8] 03. Ionic Equilibria
(ii) A salt of weak acid and weak base for which Ka > Kb :
Ammonium Fluoride is a salt of weak acid HF and weak base NH4OH. When it is dissolved
in water it undergoes hydrolysis as follows:
NH + + F- + H O NH OH + HF
4 2 4
weak base weak acid

Since Ka for HF is greater than Kb for NH4OH, the acid dissociate partially more than the base .
Hence [H+] > [OH-] and the solution becomes acidic after hydrolysis.

(iii) A salt of weak acid and weak base for which Ka < Kb :
Ammonium cyanide is a salt of weak acid HCN and weak base NH4OH.When it is dissolved
in water it undergoes hydrolysis as follows:
NH + + CN- + H O NH OH + HCN
4 2 4
weak base weak acid

Since Ka for HCN is less than Kb for NH4OH, the base dissociate partially more than the acid .
Hence [H+] < [OH-] and the solution becomes basic after hydrolysis.

 BUFFER SOLUTION :-
Defn : A solution which resists the change in pH even after the addition of a small amount of a
strong acid or a strong base or on dilution or on addition of water is called as buffer solution.

Types of buffer solutions:

There are two types of buffer solutions :
(A) Acidic buffer solution : It is a solution containing a weak acid and its salt of strong base.
Ex. CH3COOH + CH3COONa
pH of an acidic buffer is given by following Henderson equation
pH = pK + log [Salt]
a 10
[Acid]
where pKa = - log10Ka Where Ka is dissociation constant of weak acid

(B) Basic buffer solution : It is a solution containing a weak base and its salt of strong acid.
Ex. NH4OH + NH4Cl
pOH of an basic buffer is given by following Henderson equation
pOH = pK +log [Salt]
b 10
[Base]
where pKb = - log10Kb Where Kb is dissociation constant of weak base

Properties of Buffer solution :-

i) The pH of buffer solution does not change by adding small of acid or base.
ii) On dilution with water , pH of the solution does not change.
iii) The pH of buffer solution does not change when it is kept for long time.

Ques:- Explain the mechanism of Buffer action of acidic buffer solution.

Ans :- An acidic buffer is a mixture of a weak acid and its salt with a strong base. Consider sodium
acetate - acetic acid buffer. Sodium acetate is a strong electrolyte which dissociate completely in
water producing large conc. of acetate ions.While acetate acid is weak acid, it remains
undissociate.
CH3COOH    undissociate
CH COONa CH COO- + Na+
3 3
i) When a small quantity of strong acid is added to this mixture , H+ ions combine with acetate
ions to form undissociated acetic acid. Thus addition of an acid does not change the pH of the buffer.
H+ + CH COO- CH COOH
3 3
This removal of added H+ is called reserved basicity
Chemistry Std XII [9] 03. Ionic Equilibria

ii) When a small quantity of strong base is added to this mixture , OH- ions combine with acetic acid to
form anions and water. Thus addition of an base does not change the pH of the buffer.
OH- + CH COOH CH COO- + H O
3 3 2
-
This removal of added OH is called reserved acidity.

 Applications of Buffer solution:-

(1) In biochemical system :- pH of the blood is maintained at 7.36 to 7.42 due to carbonate
buffer.[HCO - + H CO ]
3 2 3
(2) Medicine :- Penicillin is stabilized by addition of sodium citrate as buffer.
(3) Food Materials :- Sodium benzoate added to jams and jellies maintains the pH constant.
(4) Agriculture :- The soil gets buffered due to presence of salts such as carbonate, sulphate,
phosphates. Depending on pH the fertilizerts are selected.

 SOLUBILITY PRODUCT :-
1) Sparingly soluble salt :-
Salt which are less soluble in water are called as sparingly soluble salt.
Ex. AgCl, BaSO4, CaF2 etc
2) Saturated solution :-
The solution which contain maximum amount of solute in given amount of solvent at a
given temperature is called as saturated solution.
3) Solubility (S) :-
The number of moles of substance dissolve to give one litre of saturated solution is
called its molar solubility. Its unit is mol/litre.
4) Solubilty Product (Ksp) :-
The product of conc. of ions of sparingly soluble salt in its saturated solution raise
to some power at a given temperature is called as solubility product.
Consider a salt AxBy, its solubility equilibrium is given as
AxBy xAy+ + yBx-
Then its solubility product is
Ksp = [Ay+]x [Bx-]y
For examples :-
i. BaSO Ba2+ + SO 2- Ksp = [Ba2+] [SO 2-]
4 4 4
ii. CaF Ca2+ + 2F- Ksp = [Ca2+] [F-]2
2
iii. Bi S 2Bi3+ + 3S2- Ksp = [Bi3+]2 [S2-]3
23
iv. Ca (PO ) 3Ca2+ + 2PO 3- Ksp = [Ca2+]3 [PO 3-]2
3 4 2 4 4

 Relation between solubility and solubility product :-

Consider a salt AxBy, its solubility equilibrium is given as
AxBy xAy+ + yBx-
Then its solubility product is
Ksp = [Ay+]x [Bx-]y
If ‘S’ is molar solubility of compound, then Ksp = [xS]x [xS]y = xxyySx+y
For examples :-
i. AgBr Ag+ + Br- Here x = 1, y = 1  = S x S = S2
ii. PbI2
2+
Pb + 2I -
Here x = 1, y = 2 sp = (1)1(2)2S1+2 = 4S3
iii. Al(OH)3 Al3+ + 3OH- Here x = 1, y = 3 sp = (1)1(3)3S1+3 = 27S4

 Relation between Ionic product and solubility product :-CONDITION FOR PRECIPITATION
(i) If IP = Ksp ; the solution is saturated and solubility equilibrium exists.
(ii) If IP > Ksp ; the solution is supersaturated and precepitation of compound will occur.
(iii) If IP < Ksp ; The solution is unsaturated and precipitation will not occur.
Chemistry Std XII [10] 03. Ionic Equilibria
 COMMON ION EFFECT :-
The suppression of the degree of dissociation of a weak electrolyte by addition of
strong electrolyte having an ion in common with the weak electrolyte is called common ion
effect.
For Example. Consider a solution of weak acid CH3COOH and its salt CH3COONa
CH3COOH is a weak acid and hence it dissociate partially
CH COOH CH COO- + H+
3 3
CH3COONa being a strong electrolyte, dissociate completely
CH COONa CH COO- + Na+
3 3
The concentration of CH COO 3
-
in the solution increased, hence by Le Chatelier’s
principle the equilibrium of CH3COOH is shifted to the left hand side.Thus reverse reaction is
favoured in which CH3 COO- combines H+ to form unionised CH3 COOH. Hence dissociation
of CH COOH is suppressed due to presence of CH COONa containing Common CH COO-
3 3 3
ion.

 Common ion effect and Solubility :-

Th presence of a common ion also affects the solubility of a sparingly soluble salt.
Consider the solubility equilibrium of AgCl, AgCl Ag+ + Cl-
The solubility product of AgCl is Ksp = [Ag ] [Cl-]
+
+
Consider addition of a strong electrolyte AgNO3 with a common ion Ag .
+ -
AgNO3 Ag + NO 3
The concentration of Ag+ in the solution increased, hence by Le Chatelier’s principle the
equilibrium of AgCl is shifted to the left hand side.Thus in the presence of a common ion , the
solubility of a sparingly soluble salt is suppressed.

 Ques:- The dissociation of H2 S is suppressed in the presence of HCl. Explain.

   + 2-
Ans :- The weak acid H2S is dissociated as H2S 2H + S
When HCl is added, it increases the concentration of common ion H+
HCl H+ + Cl-
Hence by Le Chatelier’s principle , the equilibrium is shifted from right to left,
suppressing the dissociation of weak electrolyte H2S.

 Ques:- The ionisation of NH OH is suppressed by addition of NH Cl. Explain.

4 4
Ans :- The ionisation of NH4Cl is represented as +follows -
NH OH NH + OH
4 4
When strong electrolyte NH4Cl is added to its solution, it dissociate completely
NH Cl NH + + Cl-
4 4
Due to common ion NH 4
+
, by Le Chatelier’s principal, the equilibrium is shifted from
right to left, suppressing the ionisation of NH4OH

 Ques:- The dissociation of HCN is suppressed in the presence of HCl. Explain.

Note :- The hardness of water is due to presence of Ca2+ ions. Ca2+ ions can be removed by
adding more Ca2+ ions in the form of Ca(OH)2, to the hard water.The OH- ions of lime
react with HCO3- ions present in the hard water to form CO32- ions. Solubility product
of CaCO3 is very low.Addition of lime water results in the precipitation of CaCO3 and
thereby removal of hardness.

 THE END 