UNIT – 8.

IONIC EQUILIBRIUM
 Write a note on Arrhenius Concept of acids and bases.
❖ An acid is a substance that dissociates to give H + ions in water.
HCl + H2 O ⇌ H3 O+ + Cl−
❖ A base is a substance that dissociates to give OH − in water.
NaOH + H2 O ⇌ Na+ + OH −
 What are Limitations of Arrhenius concept?
i. It does not explain the behavior of acids and bases in non-aqueous solvents such as
acetone, THF etc.,
ii. It does not explain for the basic nature of ammonia (NH3) which do not possess hydroxyl
group.
 Discuss the Lowery – Bronsted concept of acids and bases.
 An acid is as a substance that has a tendency to donate a proton to another substance.
i.e., Acid is a proton donor.
HCl + H2 O ⇌ H3 O+ + Cl−
 A base is a substance that has a tendency to accept a proton form other substance. i.e.,
Base is a proton acceptor.
NH3 + H2 O ⇌ NH4+ + OH −
 What is conjugate acid-base pairs? Explain with an example.
 According to Lowery- Bronsted concept of acids and bases an acid is a proton donor and a
base is a proton acceptor.
 The species that remains after the donation of a proton is a base (Base1) and, is called
the conjugate base of (Acid1).
 Chemical species that differ only by a proton are called conjugate acid – base pairs.
conjugate acid base pair

CH3COOH + H2O H3O+ + CH3COO-

Acid1 Base2 Acid2 Base1

conjugate acid base pair

 What are Lewis acids and bases? Give two examples for each.
 A species that accepts an electron pair is called a Lewis acid. It may a positive ion (or) an
electron deficient molecule. Examples: ,BF3, AlCl3,Fe2+, Cr3+,etc.,
 A species that donates a pair of electrons is called a Lewis base. It may be a negative ion
(or) a neutral molecule with a lone pair.
Examples: NH3, H2O, ROH, CN-, Cl- etc.,

Unit – 8 Ionic Equilibrium The Turning Point 1

 Write a balanced equation for the dissociation of the following in water and identify the
conjugate acid –base pairs.
i ) NH4+ ii ) H2SO4 iii ) CH3COOH.
i) conjugate acid base pair

NH4+ + H2O H3O+ + NH3

acid1 base2 acid2 base1

conjugate acid base pair

ii) conjugate acid base pair

H2SO4 + H2O H3O+ + HSO4-

acid1 base2 acid2 base1

conjugate acid base pair

 Differentiate between Lewis acids and Lewis bases.
s.n Lewis acids Lewis bases
They are Molecules with one (or)
They are electron deficient molecules
1 more lone pairs of electrons.
BF3, AlCl3,BeF2 etc.,
NH3,H2O,ROH,ROR, RNH2
All metal cations (or) atoms
2 2+ 3+ 3+ 2+ All anions F-,Cl-,CN- etc.,
Fe ,Fe ,Cr ,Cu etc.,
Molecules with polar double bond Molecules with C – C multiple bonds
3
SO2,CO2,SO3 etc., CH2 = CH2,CH  CH etc.,
Molecules in which the central atom can All metal oxides
4 expand its octet due to the availability of
CaO,MgO,Na2O etc.,
empty d – orbitals. Ex : SiF4 , FeCl3
5 Carbonium ions are Lewis acid (CH3 )3 C+ Carbanion are Lewis bases : CH3-
 What is auto ionisation of water?
The pure water itself has a little tendency to dissociate. i.e, one water molecule donates a
proton to another water molecule. This is known as auto ionisation of water.
H2O + H2O H3O+ + OH-
acid1 base2 acid2 base1

Unit – 8 Ionic Equilibrium The Turning Point 2

 Define ionic product of water. Give its value at room temperature.
For pure water
H2O + H2O H3O+ + OH-
acid1 base2 acid2 base1
The dissociation constant
H3O+  OH- 
K=  
2

H2O 
 
2
K H2O  = H3O+  OH- 

Kw = H3O+  OH- 
Here, K w represents the ionic product of water, the ionic product of water at 250 C is
Kw = 1  10-14 mol2L-2
 Derive an expression for Ostwald’s dilution law.
➢ Ostwald’s dilution law relates the dissociation constant of the weak acid ( Ka ) with its
degree of dissociation ( ) and the concentration (c).

degree of dssociation ( α ) =
( no ofmoles dissociated )
(Total number of moles)
CH3COOH CH3COO- H+
Initial number of moles 1 - -
Degree of dissociation of CH3COOH  - -
Number of moles at equilibrium (1 −  )  
Equilibrium concentration (1 −  ) C C C

CH3 𝐶𝑂𝑂𝐻 ⇌ 𝐶𝐻3 𝐶𝑂𝑂− + 𝐻 + α is so small for a weak acid and hence in the
CH3COO  H  - + denominator (1 - α) = 1.
Ka =   
Ka = α2C
CH3COOH 
 
Ka
Ka =
( αC)( αC) α=
C
(1-α) C When dilution increases, the degree of
2
αC dissociation of weak electrolyte also increases.
Ka =
(1-α) C This statement is known as Ostwald’s dilution
Law.

Unit – 8 Ionic Equilibrium The Turning Point 3

 Define pH.
pH of a solution is defined as the negative logarithm of, molar concentration of the
( )
hydronium H3O+ ions present in the solution.

PH = -log H3O+ 
Similarly POH can also be defined as
POH = -log OH- 
 Derive the relation between pH and POH .
Kw = H3O+  OH- 
take log on both sides
logKw = log H3O+  + log OH- 
multiply the whole equation by - sign
-logKw = -log H3O+  - log OH- 
PKw = PH + POH
At 250C Kw =1  10-14 PKw =14
PH + POH =14
 Explain common ion effect with an example.
 “The phenomenon of suppression of degree of dissociation of a weak acid or a weak base
by the addition of a strong electrolyte containing a common ion is called as common ion
effect.”
 Acetic acid is a weak acid. i.e., It is not completely dissociated in aqueous solution and the
following equilibrium exists.
CH3 𝐶𝑂𝑂𝐻 ⇌ 𝐶𝐻3 𝐶𝑂𝑂− + 𝐻 +
 If solid sodium acetate is added to the above solution, it undergoes complete dissociation
+
to produce Na and CH3COO- ions.
CH3 𝐶𝑂𝑂𝑁𝑎 → 𝐶𝐻3 𝐶𝑂𝑂− + 𝑁𝑎 +

 The concentration of CH3COO- ions increases in the equilibrium. According to Le

Chatlier’s principle, to maintain the equilibrium, the excess CH3COO- ions combines with
H+ ions to produce much more unionized CH3COOH i.e, the equilibrium will shifts
towards the left. In other words, the dissociation of CH3COOH is suppressed.


Unit – 8 Ionic Equilibrium The Turning Point 4

 What are buffer solutions? Give an example.
• A solution whose PH is resistant to addition of small amounts of strong acid or strong base
is called a buffer solution. Buffer solution is a mixture of a weak acid and its conjugate
base (or) a mixture of a weak base and its conjugate acid.
• Acidic buffer: a solution containing a weak acid and its salt.
Example: (CH3COOH + CH3COONa)
• Basic buffer: a solution containing a weak base and its salt.
Example: ( NH4OH + NH4Cl)
 Explain the buffer action in an acidic buffer containing equimolar acetic acid and sodium
acetate.
Let us explain the buffer action in a solution containing CH3COOH and CH3COONa .

The dissociation of the buffer components occurs as below.

CH3 𝐶𝑂𝑂𝐻 ⇌ 𝐶𝐻3 𝐶𝑂𝑂− + 𝐻 +
CH3 𝐶𝑂𝑂𝑁𝑎 → 𝐶𝐻3 𝐶𝑂𝑂− + 𝑁𝑎+
Addition of strong acid:

If a small amount of strong acid is added to this mixture, the added H+ ions will be

consumed by the conjugate base CH3COO- to form the undissociated weak acid thus, the

increase in the concentration of H+ does not reduce the pH significantly.

CH3 𝐶𝑂𝑂− + 𝐻 + ⇌ 𝐶𝐻3 𝐶𝑂𝑂𝐻
𝑎𝑑𝑑𝑒𝑑
Addition of strong base:
-
If a small amount of strong base is added to this mixture, the added OH ions will be

neutralized by the H3O+ ions. To maintain the equilibrium acetic acid is dissociated. Thus, the
-
increase in the concentration of OH does not increase the pH significantly.
𝐻3 𝑂+ + 𝑂𝐻 − ⇌ 2𝐻2 𝑂
𝑎𝑑𝑑𝑒𝑑
CH3 𝐶𝑂𝑂𝐻 ⇌ 𝐶𝐻3 𝐶𝑂𝑂− + 𝐻 +

Unit – 8 Ionic Equilibrium The Turning Point 5

 Derive Henderson-Hassel Balch equation.
In an acid buffer containing a weak acid and its salt,
HA ⇌ H + + 𝐴−
NaA ⎯⎯ → Na+ + A-
H3O+   A- 
Ka =   
HA 
 
HA 
H3O+  = Ka  
  A 
-
 

H3O+  = Ka
acid 
  conjugate base
The weak acid is dissociated only to a small extent. Moreover, due to common ion effect, the
dissociation is further suppressed and hence the equilibrium concentration of the acid is
nearly equal to the initial concentration of the unionized acid. Similarly, the concentration of
the conjugate base is nearly equal to the initial concentration of the added salt.

H3O+  = Ka
acid
  salt
Taking logarithm on both sides of the equation

log H3O+  = logKa +log

acid 
salt
reverse the sign on both sides

-log H3O+  = -logKa -log

acid 
salt
PH = PKa -log
acid 
salt
PH = PKa +log
salt
acid 
Similarly for base buffer

POH = PKb +log

salt
 base

Unit – 8 Ionic Equilibrium The Turning Point 6

 Define solubility product
The solubility product of a compound is defined as the product of the molar concentration of
the constituent ions, each raised to the power of its stoichiometric co – efficient in a
balanced equilibrium equation.
For a general salt X 𝑚 𝑌𝑛
H 2O
Xm Yn m X n+ + n Ym - -
[𝑋 𝑛+ ]𝑚 [𝑌 𝑚− ]𝑛
K=
[𝑋𝑚 𝑌𝑛 ]
In solubility equilibria, the equilibrium constant is referred as solubility product (Ksp). The
concentration of the solid is a constant and is omitted in the above expression.
K𝑆𝑃 = [𝑋 𝑛+ ]𝑚 [𝑌 𝑚− ]𝑛

• Ionic product > Ksp , solution is super saturated and precipitation will occur.
• Ionic product < Ksp , solution is unsaturated and no precipitation occurs.
• Ionic product = Ksp , solution is saturated, equilibrium exists.

EVALUATION
+
1. Concentration of the 𝐴𝑔 ions in a saturated solution of 𝐴𝑔2 𝐶2 𝑂4 is
2.24 × 10−4 𝑚𝑜𝑙 𝐿−1 solubility product of 𝐴𝑔2 𝐶2 𝑂4 is (NEET – 2017)
a) 2.42 × 10−8 𝑚𝑜𝑙3 𝐿−3 b) 2.66 × 10−12 𝑚𝑜𝑙3 𝐿−3
c) 4.5 × 10−11 𝑚𝑜𝑙3 𝐿−3 d) 𝟓. 𝟔𝟏𝟗 × 𝟏𝟎−𝟏𝟐 𝒎𝒐𝒍𝟑 𝑳−𝟑
2. Following solutions were prepared by mixing different volumes of NaOH with HCL of
different concentrations. (NEET – 2018)
i. 60 mL M/10 HCl + 40mL M/10/NaOH ii. 55 mL M/10 HCl + 45 mL M/10 NaOH
iii. 75 mL M/5 HCl + 25mL M/5NaOH iv. 100 mL M/10 HCl + 100 mL M/10 NaOH
Which one of them will have pH equal to 1?
a) iv b) i
c) ii d) iii
3. The solubility of BaSO4 in water is 2.42 × 10−3 𝑔 𝐿−1 at 298K. The value of its solubility
product (𝐾𝑆𝑃 ) ) will be (NEET -2018). (Given molar mass of BaSO4 = 233𝑔 𝑚𝑜𝑙 −1 )
a) 1.08 × 10−14 𝑚𝑜𝑙2 𝐿−2 b) 1.08 × 10−12 𝑚𝑜𝑙2 𝐿−2
c) 𝟏. 𝟎𝟖 × 𝟏𝟎−𝟏𝟎 𝒎𝒐𝒍𝟐 𝑳−𝟐 d) 1.08 × 10−8 𝑚𝑜𝑙2 𝐿−2
4. pH of a saturated solution of Ca(OH)2 is 9. The Solubility product (𝐾𝑆𝑃 ) of Ca(OH)2
a) 𝟎. 𝟓 × 𝟏𝟎−𝟏𝟓 b) 0.25 × 10−10
c) 0.125 × 10−15 d) 0.5 × 10−10

Unit – 8 Ionic Equilibrium The Turning Point 7

5. Conjugate base for bronsted acids H2 𝑂 and HF are
a) OH − 𝑎𝑛𝑑 𝐻2 𝐹𝐻 + respectively b) H3 O+ 𝑎𝑛𝑑 𝐹 − respectively
c) 𝐎𝐇 − 𝒂𝒏𝒅 𝑭− respectively d) H3 O+ 𝑎𝑛𝑑 𝐻2 𝐹 + , respectively
6. Which will make basic buffer?
a. 50 mL of 0.1M NaOH + 25mL of 0.1M CH3 COOH
b. 100 mL of 0.1M CH3 COOH + 100 mL of 0.1M NH4 OH
c. 𝟏𝟎𝟎 𝐦𝐋 𝐨𝐟 𝟎. 𝟏𝐌 𝐇𝐂𝐥 + 𝟐𝟎𝟎 𝐦𝐋 𝐨𝐟 𝟎. 𝟏𝐌 𝐍𝐇𝟒 𝐎𝐇
d. 100 mL of 0.1M HCl + 100 mL of 0.1M NaOH
7. Which of the following fluoro compounds is most likely to behave as a Lewis base?
a) 𝐵𝐹3 b) 𝑷𝑭𝟑
c) 𝐶𝐹4 d) 𝑆𝑖𝐹4
8. Which of these is not likely to act as lewis base?
a) 𝑩𝑭𝟑 b) 𝑃𝐹3
C) 𝐶𝑂 d) 𝐹 −
9. The percentage of pyridine (C5H5N) that forms pyridinium ion (C5H5NH) in a 0.10M aqueous
pyridine solution (𝐾𝑏 𝑓𝑜𝑟 𝐶5 𝐻5 𝑁 = 1.7 × 10−9 ) 𝑖𝑠
a) 0.006% b) 0.013%
c) 0.77% d) 1.6%
10. Equal volumes of three acid solutions of pH 1,2 and 3 are mixed in a vessel. What will be the
𝐻 + ion concentration in the mixture?
a) 𝟑. 𝟕 × 𝟏𝟎−𝟐 b) 10−6
c) 0.111 d) none of these
11. The solubility of AgCl (s) with solubility product 1.6 × 10−10 in 0.1M NaCl solution would be
a) 1.26 × 10−5 𝑀 b) 𝟏. 𝟔 × 𝟏𝟎−𝟗 𝑴
c) 1.6 × 10−11 𝑀 d) Zero
12. If the solubility product of lead iodide is 3.2 × 10−8 , its solubility will be
a) 𝟐 × 𝟏𝟎−𝟑 𝑴 b) 4 × 10−4 𝑀
c) 1.6 × 10−5 𝑀 d) 1.8 × 10−5 𝑀
13. 𝑀𝑌 𝑎𝑛𝑑 𝑁𝑌3 , are insoluble salts and have the same Ksp values of 6.2 × 10−13 at room
temperature. Which statement would be true with regard to 𝑀𝑌 𝑎𝑛𝑑 𝑁𝑌3 ?
a) The salts 𝑀𝑌 𝑎𝑛𝑑 𝑁𝑌3 are more soluble in 0.5M KY than in pure water
b) The addition of the salt of KY to the suspension of 𝑀𝑌 𝑎𝑛𝑑 𝑁𝑌3 will have no effect on
their solubilities.
c) The molar solubilities of 𝑀𝑌 𝑎𝑛𝑑 𝑁𝑌3 in water are identical
d) The molar solubility of MY in water is less than that of 𝑵𝒀𝟑
14. What is the pH of the resulting solution when equal volumes of 0.1M NaOH and 0.01M HCl
are mixed?
a) 2.0 b) 3 c) 7.0 d) 12.65
−3
15. The dissociation constant of a weak acid is 1 × 10 . In order to prepare a buffer solution
[𝐴𝑐𝑖𝑑]
with a pH = 4, the ratio should be
[𝑆𝑎𝑙𝑡]
a) 4:3 b) 3:4 c) 10:1 d) 1:10

Unit – 8 Ionic Equilibrium The Turning Point 8

16. The pH of 10−5 𝑀 KOH solution will be
a) 9 b) 5
c) 19 d) none of these
−
17. 𝐻2 𝑃𝑂4 is the conjugate base of
a) 𝑃𝑂43− b) 𝑃2 𝑂5
c) 𝑯𝟑 𝑷𝑶𝟒 d) 𝐻𝑃𝑂42−
18. Which of the following can act as lowery – Bronsted acid well as base?
a) HCl b) 𝑆𝑂42−
c) 𝑯𝑷𝑶𝟐− 𝟒 d) 𝐵𝑟 −
19. The pH of an aqueous solution is Zero. The solution is
a) slightly acidic b) strongly acidic
c) neutral d) basic
20. The hydrogen ion concentration of a buffer solution consisting of a weak acid and its salts is
given by
[𝒂𝒄𝒊𝒅]
a) [𝑯+ ] = 𝑲𝒂 b) [𝐻 + ] = 𝐾𝑎 [𝑠𝑎𝑙𝑡]
[𝒔𝒂𝒍𝒕]
[𝑠𝑎𝑙𝑡]
c) [𝐻 + ] = 𝐾𝑎 [𝑎𝑐𝑖𝑑] d) [𝐻 + ] = 𝐾𝑎
[𝑎𝑐𝑖𝑑]

Unit – 8 Ionic Equilibrium The Turning Point 9