NOTE

C H E M I S T R Y

IONIC EQUILIBRIUM
BEGINNING OF HYDROLYSIS

What you already know

• Combining weak acid • Polyprotic weak acid

• Combining weak base

What you will learn

• Introduction to hydrolysis • Salt of a strong acid and a weak base

• Salt of a strong acid and a strong base • Salt of a weak acid and a strong base

BOARDS MAIN
Polyprotic Acid

Polyprotic acid: It is an acid that gives more than one H+ ion per molecule upon dissociation of
acids that have more than one ionisable H+ atom per molecule. Let C be the initial concentration of
H3PO4, where ‘x’ moles are being dissociated from it (as the volume is constant).
H3PO4(aq) ⇌ H+(aq) + H2PO4−(aq) H+  H2PO 4 −  H+  HP
C−x x+y+z x−y K a1 =    , K a2 =   
C(1 − 𝛼1) C𝛼1 + C𝛼1 𝛼2 + C𝛼1 𝛼2𝛼3 C𝛼1(1 − 𝛼2)
[H3PO4 ] H2PO

H2PO4−(aq) ⇌ H+(aq) + H+ 42−

HPO H(aq)
2PO 4 
−
H+  HPO 42−  H+  PO
K a1 =  , K a2 = , K a3 =
x−y x+y+z y[H− PO z ] H2PO 4 −  HPO 4 2
3 4
C𝛼1(1 − 𝛼2) C𝛼1 + C𝛼1 𝛼2 + C𝛼1 𝛼2𝛼3 C𝛼1 𝛼2(1 - 𝛼3)

HPO42−(aq) ⇌ H+H (aq)

+
H2PO 4 −  + PO
H4+ (aq)
3−
HPO 42−  H+  PO 4 3 − 
y−z K a1 = x+y+z , K a2 = z , K a3 =
[H3PO4 ] H2PO 4 −  HPO 42− 
C𝛼1 𝛼2(1 − 𝛼3) C𝛼1 + C𝛼1 𝛼2 + C𝛼1 𝛼2𝛼3 C𝛼1 𝛼2𝛼3

It can be seen that the higher order ionisation constants, Ka2 and Ka3 , are much smaller than the first
order ionisation constant, Ka1 . This is because of the ease of removing a proton from an uncharged
species than from a negatively charged one. It is very difficult to remove a proton from a doubly
charged HPO42− anion as compared to that from a singly charged H2PO4 – anion.

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O O
Ka1
H
O P H
O
⇌ H
+
+ H
O P
–
O
O H O H

O O
Ka2
H
O P
O
– ⇌ H
+
+ H
O P
O
–
O H O–

O O
Ka3
H
O P
O
– ⇌ H
+
+ –
O P
O
–
–
O O–
Fig. 1: Ionisation constants involved in each step of dissociation of H3PO4

If the values of Ka1, Ka2, Ka3, and C are such that the second and third dissociations are negligible,
then we can approximate:
• x−y≈x
• x+y+z≈x
• y−z≈y
So,
For finding the pH we can only consider the H+ ions coming from the first dissociation as the
successive ionisation constants are very small.
( x )( x ) ( x )( y ) ( x )( z )
K a1 = K a2 = K a3 =
C1 − x x y

Finding the concentration

Calculate [H2PO4–], [HPO42–], [PO43−], [H+] of a 0.1 M H3PO4 solution.

(Given, Ka1 = 7.5 × 10−3, Ka2 = 6.2 × 10–8, Ka3 = 4.2 × 10–13)

Solution

Here, Ka1 > 10–3, so (C − x) cannot be approximated to C. However, in the case of Ka2 and Ka3, degree
of dissociation can be neglected, as their values are less than 10–3.
H+  H2PO4 −  H+  HPO42−  H+  PO4 3− 
Ka1 = , Ka2 = , Ka3 =
[H3PO4 ] H2PO4 −  HPO42− 

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( x )( x ) ( x )( y ) ( x )( z ) 6.2 × 10−8 =
0.0238 × y
Ka1 = , Ka2 = , Ka3 =
C-x x y 0.0238
x.x Therefore, y = 6.2 × 10–8
Ka1 =
0.1 − x 0.0238 × z
4.2 × 10−13 =
x2 6.2 × 10−8
7.5 × 10-3 =
0.1 − x Therefore, z = 1.094 × 10–18
On solving the quadratic equation, we get, So,
x = 0.0238

• [H2PO4−] = [H+] = 0.0238 M • [HPO42−] = 6.2 × 10–8 M • [PO43−] = 1.094 × 10–18 M

BOARDS MAIN
Acid-Base Neutralisation

Reactions in which an acid and a base react quantitatively to form a neutral solution are known
as acid-base neutralisation reactions. Salt solutions are the products of acid-base neutralisation
reactions.
Example:
When aqueous solutions of hydrochloric acid (acid) and sodium hydroxide (base) are mixed in the
equimolar ratio, a neutralisation reaction takes place to form sodium chloride (salt) and water.
HCl ( aq ) + NaOH ( aq ) → NaCl ( aq ) + H2 O ( l )
Here, Na+ (cation) comes from NaOH (base) and Cl− (anion) from HCl (acid).

Note

We are assuming that a salt solution is formed and nothing is deposited at the bottom of the vessel.

NaOH HCI Heat Salt Heat

released solution released
Fig. 2: Acid-base neutralization reaction

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Categories of salt
• Salt of a strong acid + Strong base
HCl ( aq) + NaOH ( aq) → NaCl ( aq) + H2O (l )
• Salt of a weak acid + Strong base
CH3COOH ( aq) + NaOH ( aq) → H2O (l) + CH3COONa ( aq)
• Salt of a strong acid + Weak base
HCl ( aq) + NH4OH ( aq) → H2O (l) + NH4CI ( aq)
• Salt of a weak acid + Weak base
CH3COOH ( aq) + NH4OH ( aq) → H2O (l ) + CH3COONH4 ( aq)

BOARDS MAIN
Salt Hydrolysis and the pH of their Solutions

If a salt BA dissolves in water, then,

BA(s) + H2O(l) ⟶ BA(aq) ⟶ B+(aq) + A–(aq)
Anionic hydrolysis
In some salts, if the anion is of weak acid then these react with water to produce OH– ions. Thus,
the solution becomes basic.
A − ( aq ) + H2 O ( l )  HA ( aq ) + OH− ( aq )

Example: CH3COO– (aq) + H2O ⇌ CH3COOH (aq) + OH– (aq)

Cationic hydrolysis
In some salts, if the cation is of weak base then these react with water to produce H3O+ ions. Thus,
the solution acquires an acidic nature.
B+ ( aq ) + 2H2 O ( l )  BOH ( aq ) + H3 O + ( aq )
Example: NH4+(aq) + H2O ⇌ NH4OH(aq) + H+(aq)
The cations/anions formed on the ionisation of salts either exist as hydrated ions in aqueous
solutions or interact with water to reform corresponding acids/bases, depending upon the nature
of the salts. In reaction with water, the cations produce H+ ions and the anions produce OH– ions.
The pH of the solution is affected by this interaction. The reaction of a cation, an anion, or both of
any salt with water is known as salt hydrolysis.
The salts of strong acids and bases only get hydrated but not hydrolysed. Therefore, the solutions
of salts formed from strong acids and bases are neutral, i.e., their pH is 7. However, the other
categories of salts undergo hydrolysis.

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pH of salt solutions

Generalised notations
Kh = Hydrolysis constant of the salt
h = Degree of hydrolysis
C = Concentration of the ion undergoing hydrolysis (Not the concentration of the salt)
Case 1: Salt of a strong acid and a strong base
The cations of the strong bases and the anions of the strong acids get hydrated but not hydrolysed.
So, the solution involves only the equilibrium of ionization of water.
Example: Na+(aq) + Cl–(aq) + H2O(l) ⇌ Na+(aq) + Cl–(aq) + H+(aq) + OH–(aq)
On cancelling the ions, Na+ and Cl–, on both the sides, we get.
H2O(l) ⇌ H+(aq) + OH–(aq)
Thus, the pH of the solution will be 7 (neutral solution at 25 °C).

NaCI

[Na+(aq)] [Na+ (aq)]

[CI–(aq)] – No effect on litmus paper
[CI (aq)]
[H3O+(aq)] [H3O+(aq)] (Neutral solution)
– –
[OH (aq)] [OH (aq)]
[H2O] [H2O]

Fig. 3: Dissolution of salt of strong acid and strong base in water (no hydrolysis)

Case 2: Salt of a strong acid and a weak base

Consider a strong acid (HCl) and a weak base (NH4OH) forming a salt (NH4Cl). NH4CI ionises in
water into the ions NH4+ and CI–.
NH4Cl(aq) → NH4+(aq) + Cl–(aq)
NH4+ reacts with water to form a weak base (NH4OH) and H+ ions.
NH4+(aq) + H2O(l) → NH4OH(aq) + H+(aq)
Only the cation will undergo hydrolysis and the solution will be acidic in nature due to the formation
of H+ ions. Thus, the pH of NH4Cl solution in water is less than 7 at 25 oC. So here, the cation is
responsible for the acidic nature of the solution.

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NH4Cl

[NH4+ (aq)] [NH4OH(aq)] Blue litmus turns red

[CI-(aq)] [NH4+ (aq)] (Acidic solution)
[H3O+ (aq)] [CI-(aq)]
[H2O] [H3O+(aq)]
[H2O]

Fig. 4: Nature of solution when salt of strong acid and weak base is hydrolysed

NH4+(aq) + H2O(l) ⇌ NH4OH(aq) + H+(aq)

Initially, C 0 0

At equilibrium, Ch × Ch Ch2
C − Ch KhCh
= ⇒Ch
Kh =
C ( 1 − h) ( 1 − h)
[NH4OH] H+ 
Kh = Kh Kw
NH4 +  h= =
C Kb C
( Ch) ...(1)
2

⇒ Kh = Kw
C ( 1 − h) H+=
 Ch
= C ×
Kb C
For the reaction,
K wC
NH4OH(aq) ⇌ NH4+(aq) + OH−(aq) H+  =
Kb
NH4 +  OH−  By taking logarithm on both the sides, we get,
Kb =
[NH4OH] 1 1 1
log H+  = log K w − log Kb + log C
Also, H2O(l) ⇌ H+(aq) + OH−(aq) 2 2 2
Kw = [H+][OH−] Multiplying −1 on both the side, we get
1 1 1
How is Kh related to Kb and Kw? − log H+  Multiplying
= − log K−w1 +on both b − side,
log Kthe logwe
C get
2 2 2
H+  OH−  NH4 OH H+  1 1 + 1 1 log K w + 1 log Kb − 1 log C
Kw
= =  pH = pK−wlog − HpK b=− − 2log C 2 2
Kb NH4 +  OH−  NH4 +  2 2 2
1 1 1 1
pH = [pKpH = pK pK − CpKb − log C
[NH4OH] w − 2b − log
w
2 ] 2
2
1
Thus, Kh =
Kw At 25 °C , pH = [pK w − pKb − log C ]
Kb 2
1 1
pH = 7 − AtpK 25 −
b °C , log C
From equation (1), we get, 2 2
1 1
pH = 7 − pK b − log C
Ch × Ch Ch2 2 2
Kh = ⇒ Kh =
C ( 1 − h) ( 1 − h)
If h << 1, then Kh = Ch2
Kh Kw
h= =
C Kb C
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Note

Kh
If h obtained from > 0.1 then solve the quadratic equation and get the value of h.
C

Case 3: Salt of a weak acid and a strong base

The solution of such a salt is basic in nature. The anion of the salt reacts with water to form a weak
acid and OH– ions. Consider CH3COOH (weak acid) and NaOH (strong base), forming the salt
CH3COONa. It ionizes in water to give CH3COO– and Na+ ions.
CH3COONa(aq) → CH3COO–(aq) + Na+(aq)
CH3COO− ions react with water to form OH− ions and a weak acid, CH3COOH.
CH3COO–(aq) + H2O(l) ⇌ CH3COOH(aq) + OH–(aq)
Only the anion undergoes hydrolysis and the solution will be alkaline in nature due to the OH– ions
formation. Hence, pH > 7 at 25 °C. Here, the anion is responsible for the alkaline nature of the salt
solution.

CH3COONa

[CH3COO–(aq)] [CH3COOH(aq)] Red litmus turns blue

[Na+ (aq)] [CH3COO–(aq)] (Basic solution)
[H3O+ (aq)] [Na+(aq)]
[OH–(aq)] [H3O+ (aq)]
–
[H2O] [OH (aq]
[H2O]

Fig. 5: Nature of solution when salt of weak acid and strong base is hydrolysed

CH3COO–(aq) + H2O(l) ⇌ CH3COOH(aq) + OH–(aq)

At t = 0, C 0 0

At t = teq, C − Ch Ch Ch

[CH3COOH] OH− 
Kh =
CH3COO− 

( Ch) ...(1)
2

⇒ Kh =
C ( 1 − h)

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For the reaction, If h << 1, then Kh = Ch2

CH3COOH(aq) ⇌ CH3COO−(aq) + H+(aq), Kh Kw
h= =
C K aC
CH3COO−  H+ 
Ka =  Kw
[CH3COOH] [OH−] = Ch = C ×
K aC
Also, H2O(l) ⇌ H+(aq) + OH−(aq),
K wC
Kw = [H+][OH−] OH−  =
Ka
How is Kh related to Ka and Kw?

Kw K wK a
Kw H+  OH−  [CH3COOH] OH−  =
H+  =
= = OH −
C
Ka CH3COO−  H+  CH3COO− 
By taking logarithm on both the sides, we get,
[CH3COOH]
1 1 1
log H+  = log K w + log Ka − log C
 OH 
−
[CH3COOH] OH  −
2 + 12 12 1
= log H  = log K + log Ka − log C
OO  H 
− +
CH3COO − On multiplying  − 
1 both2 side w
2 2
H3COOH] − log H+ On
1 1
log K w −−1 both
= −multiplying log Kside
1
Kw a + log C
Kh = 2 + 12 12 1
Ka 1 − log H  = − 2 log K w − 2 log Ka + 2 log C
pH = [pK w + pKa + log C ]
From equation (1), we get, 2 1
pH = [pK w + pKa + log C ]
Ch × Ch At 25 °C, 2
Kh =
C ( 1 − h) 1
pH = 7 + [pK a + log C ]
Ch2 2 1
Kh = pH = 7 + [pK a + log C ]
( 1 − h) 2

Note

Kh
If h obtained from > 0.1 then solve the quadratic equation and get the value of h.
C

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