10. Explain the concept of Bronsted acids and Bronsted bases.

Illustrate the answer with suitable

examples.
A. Bronsted  Lower theory :
According to Bronsted-Lowry theory,
“An acid is a chemical substance which shows a tendency to lose or donate a proton to an acceptor”.
i. e. Proton donor is an acid.
Ex: HCl  H2O  H 3O  Cl 
Here HCl donates a proton to water. So, HCl is a Bronsted-Lowry acid
“A base is a chemical substance that has a tendency to gain a proton from a donor”. i.e.,
Proton acceptor is a base.
Ex: NH 3  H 2O  NH 4   OH 
Here NH3 accepts a proton from water. So, NH3 is a Bronsted-Lowry base.
Neutralisation : The reaction between an acid and a base, which involves the transfer of a proton
from an acid to a base is called neutralisation.
 
Ex : HCl  NH 3  NH 4  Cl
Here proton is transferred from HCl to NH3
Conjugate acid-base pair: A pair of substances (an acid and a base) which differ by a proton is
known as conjugate acid-base pair.
Ex : HCl  NH 3  NH 4   Cl 
Acid1 Base2 Acid2 Base1

In the above reaction HCl and Cl is one conjugate acid-base pair. Similarly NH 4 and NH3
is another conjugate acid-base pair.
Advantages:
1. This theory explains the behaviour of acids and bases in both aqueous and non-aqueous
solvents.
2. It explains the behaviour of CO2, SO2 etc as acids and NH3, CaO etc as bases.
3. It is more generalised theory encompassing larger number of acids and bases than Arrhenius
theory.
Drawbacks:
1. A substance can be termed as an acid or a base only when it reacts with some other substance.
2. This theory could not explain the acidic nature of electron deficient molecules like BCl3, AlCl.3
etc.
11.I Explain Lewis acid-base theory with suitable example. Classify the following species into Lewis
acids and Lewis bases and show these act as Lewis acid/base.
II. a) OH b) F c) H+ d) BCl3
A. I) Lewis theory:
According to Lewis theory, an acid is a substance that can accept an electron pair to form a
co-ordinate covalent bond with the donor.
i.e., Electron pair acceptor is a Lewis acid.
Various examples of Lewis acids are listed below:
1. All transition metal cations and some cations of other metals.
Ex: Ag+, Cu2+, Zn2+, Fe2+, Mg2+, Ag+ etc
2. Proton and protonated species
Ex: H+, PH4+ etc.
3. All electron deficient molecules.
Ex: BF3, BCl3, AlCl3,FeCl3 etc.
4. Compounds in which central atom has vacant d-orbitals and may expand its octet.
Ex: SiF4, SF4, SnCl4, TeF4 etc.
 5. Non metallic oxides. They have multiple bonds between atoms of dissimilar electronegativity.
Ex: CO2, SO2, SO3, P4O10, Cl2O7 etc
6. Elements with an electron sextet.
Ex: O,S
According to Lewis theory, a base is a substance that can donate a lone pair of electrons to form
a co-ordinate covalent bond with the acceptor.
i.e., Electron pair donor is a Lewis base.
Various examples of Lewis bases are listed below:
1. All anions having at least one pair of electrons available for donation.
Ex: F  , Cl  , OH  , CN  etc.
2. Molecules having at least one or two lone pair of electrons on the central atom.

3. Unsaturated hydrocarbons have at least one ‘Pi()’ bond between two carbon atoms.
Ex: CH2 = CH2, CH  CH etc.
4. All metallic oxides.
Ex: Na2O, K2O, MgO, CaO etc.
Neutralisation : The reaction which involves the formation of a co-ordinate covalent bond between
an acid and a base is called neutralisation.
Ex:
1) Formation of BF3 and NH3 adduct : In the formation of ammonia-boron trifluoride, NH3
donates electron pair (base) and BF3 accepts electron pair (acid). Dative bond is formed from N
atom of NH3 to B atom of BF3.

2) Formation of hydronium (H3O+) ion: In the formation of H3O+ ion, oxygen of water molecule
donates electron pair and H+ acts as an electron pair acceptor. A dative bond is formed between
oxygen and H+ ion.

Advantages :
1. It explains the acidic nature of substances like BCl3, AlCl3, FeCl3 etc and also the acidic nature
of non metal oxides.
2. It explains the basic nature of the metallic oxides and also the basic nature of the unsaturated
hydrocarbons.
Drawbacks:
1. Lewis theory could not explain the relative strength of acids and bases.
2. It could not explain the catalytic activity of acids (H+).
3. It could not explain the neutralisation of simple acids and bases which donot involve co-ordinate
covalent bonds.
4. Generally acid-base reactions are fast. But Lewis acid-base reactions are slow.
II. a) Hydroxyl ion (OH-) is a Lewis base as it can donate an electron lone pair(:OH)
b) Flouride ion (F-) acts as a Lewis base as it can donate any one of its four electron lone pairs.
c) A proton (H+) is a Lewis acid as it can accept a lone pair of electrons from bases like hydroxyl
ion and fluoride ion.
d) BCl3 acts as a Lewis acid as it can accept a lone pair of electrons from species like ammonia or
amine molecules.
12. What is degree of ionization in respect of weak acids and weak bases? Derive the relationship
 between degree of ionization () and ionization constant (Ka) for the weak acid HX.
A. The extent of ionisation is the ratio of number of molecules ionised and the total number of
molecules of an acid or a base. It is denoted ‘’ (alpha). Extent of ionisation is usually expressed
interms of degree of dissociation.
Degree of dissociation,  = No.of molecules ionised
Total no.of moleculestaken
 is always less than one for weak electrolytes. But as the concentration of the solution
decreases or the dilution increases, the degree of ionisation increases and finally ‘’ tends to the
value of ‘1’ as concentration tends to ‘0’.
Let the concentration of a weak monoprotic acid (HA) is ‘c’ mol. lit1 and degree of
ionisation is ‘’. The equilibrium is
HA  H+ + A
c 0 0 (At start)
c(1 ) c c (At equilibrium)
The dissociation constant of the acid, HA is given as
 H    A  c .c c 2
Ka       
 HA c 1    1  
For a very weak acid ‘’ <<1.
Ka
Ka = c 2 (or) 2 = (or)  = Ka
c c
Similarly for a mono acidic weak base (BOH) in solutions, the equilibrium is
BOH  B+ + OH
c 0 0 (At start)
c(1 ) c c (At equilibrium)
The dissociation constant of the base, BOH is given as
Kb=  B  OH  = c .c  K  c
  2

 BOH  c 1    b
1   
Neglecting ‘’ for a very weak base Kb = c 2 (or) 2 = K b (or)  = Kb
c c
13. Define pH. What is buffer solution? Derive Henderson – Hasselbalch equation for calculating
the pH of an acid buffer solution.
A. a) The negative value of logarithm to the base 10 of hydrogen concentration expressed in mol-lit1
is called pH.
b) A solution which can resists any change in its pH value on dilution or on addition of small
amount of strong acid or strong base is called buffer solution.
c) Derivation of Henderson-Hasselbalch equation:
Calculation of the pH of a buffer solution: The pH of an acidic or basic buffer solution can be
calculated by the use of Henderson’s equation.
For acidic buffer: Let the acidic buffer solution consists of a weak acid HA and its salt NaA.
Their ionisations can be written as
HA  H     A
NaA  Na    A
The dissociation constant of weak acid is given as
  -
  
Ka=  H   A 
 HA
(or)

[H+] = Ka
 HA .......(1)
 A1 
As the dissociation of weak acid is small, the equilibrium concentration of [HA] can be taken as
equal to the concentration of acid. [HA] = [Acid]
The salt (NaA) is almost completely ionised. The A– ions produced from the acid (HA) are
negligible when compared to those from the salt. Therefore equilibrium concentration of A– ions
can be taken as equal to the concentration of salt.
[ Acid ]
[A] = [Salt] [ H  ]  Ka
[salt ]
Taking ‘log’ on both sides
log[H+] =  log Ka log 
Acid   H
p = p Ka  log  Salt  (1)
 Salt   Acid 
(or)
N V 
p H  p Ka  log  salt salt 
 N acidVacid 
Where Vacid = Volume of weak acid, Nacid = Normality of weak acid
Vsalt and Nsalt are corresponding values for the salt.
14. Explain the term “Hydrolysis of salts” with examples. Discuss the pH of the following types of
salt solution.
i) Salts of weak acid and strong base.
ii) Salts of strong acid and weak base.
A. Salt hydrolysis : The phenomenon in which the anion or cation or both of a salt react with water
producing excess of OH ions or H+ ions or both in aqueous solution is called salt hydrolysis.
Salt hydrolysis may be cationic hydrolysis or anionic hydrolysis or both.
Cationic hydrolysis : If the cation in a salt is a strong conjugate acid, it reacts with water to give
excess H+ ions. As a result, the aqueous solution of such salt is acidic in nature. This is called
cationic hydrolysis.
M+ + H2O  MOH + H+
Cation Weak base
Anionic hydrolysis : If the anion in the salt is a strong conjugate base, it reacts with water to give
excess OH ions. As a result, the aqueous solution of such salt is basic in nature. This is called
anionic hydrolysis.
A + H2O  HA + OH
Anion Weak acid
b)
i) Salts of weak acid and strong base: When dissolved in water its anion reacts with water
forming excess of OH ions. Its solution is basic with pH > 7.
Ex: CH3COONa, Na2CO3, KCN, Na2S etc.
CH3COO + H2O  OH+CH3COOH (Weak acid)
CN + H2O  OH +HCN(Weak acid)
CO32 +2 H2O  2OH +H2CO3
 Weak acid
ii) Salt of a strong acid and weak base: When dissolved in water, its cation reacts with water
forming excess of H+ ions and the solution is acidic. Its pH is less than 7.
Ex:NH4Cl, CuSO4, NH4NO3, ZnSO4 etc
NH 4  H 2O  H   NH 4OH
Cu 2  2 H 2O  2 H   Cu  OH  2
15. What is solubility product? Explain the common ion effect on solubility of ionic salts.
A. Solubility product : The product of concentrations of cation and anion of salt in a saturated solution
is called solubility product (Ksp).
Ksp = [cation] [anion]
For example the Ksp expression for AgCl
AgCl  Ag+ + Cl
Ksp = [Ag+] [Cl]
Common ion effect : The phenomenon of suppression of ionization of an weak electrolyte in water
by the addition of another electrolyte which has one ion common with the electrolyte is called
common ion effect.
Common ion effect is due to the existence of two equilibria in a saturated solution and their
dynamic nature.
AB  AB  A+ + B
(solid) (soluble) ions
If A+ or B is added through another electrolyte Ax or yB both of equilibria shift towards left,
leading to decrease in the ionisation and consequently solubility decreases.
Ex 1 : CH3COOH ionises in aqueous solution as CH3COOH  CH3COO+ H+
Addition of CH3COO ions (common ion) in the form of CH3COONa diminishes the ionisation of
acetic acid. This is because of increase of CH3COO ions (common ion) in the form of CH3COONa
diminishes the ionisation of acetic acid. This is because of increase of CH3COO ions concentration
shifts the equilibrium to the left and more unionised acid is favoured.
CH3COOH  CH3COO + H+
CH3COONa  CH3 COO + Na+
Ex 2: The ionisation of NH4OH is diminished by the addition of NH4Cl due to the common NH4+ion.
NH4OH  NH4++ H
NH4Cl  NH4++ Cl
Applications:
1. Common ion effect is used in controlling the H+ ion concentration in buffer solution.
2. The concentration of S2in the 2nd group or OH in 3rd group qualitative analysis is controlled by
HCl and NH4OH on the basis of common ion effect.
16. Write notes on i) Common ion effect ii) The relation between Ksp and solubility (S) of a spaningly
soluble salt BaSO4.
A. Common ion effect: The phenomenon of suppression or ionization of an weak electrolyte in water
by the addition of another electrolyte which has one ion common with the electrolyte is called
common ion effect.
Common ion effect is due to the existence of two equilibria in a saturated solution and their
dynamic nature.
AB  AB  A+ + B
(solid) (soluble) ions
+ 
If A or B is added through another electrolyte Ax or or yB both of equilibria shift towards
left, leading to decrease in the ionisation and consequently solubility decreases.
Ex 1 : CH3COOH ionises in aqueous solution as CH3COOH  CH3COO+ H+
Addition of CH3COO ions (common ion) in the form of CH3COONa diminishes the ionisation of
acetic acid. This is because of increase of CH3COO ions concentration shifts the equilibrium to the
left and more unionised acid is favoured.
CH3 COOH   CH3 COO + H+
CH3 COONa  CH3 COO + Na+
Ex 2: The ionisation of NH4OH is diminished by the addition of NH4Cl due to the common
NH4+ion.
NH4OH  NH4++ OH
NH4Cl  NH4++ Cl
Applications:
1. Common ion effect is used in controlling the H+ ion concentration in buffer solution.
2. The concentration of S2 in the 2nd group or OH in 3rd group qualitative analysis is controlled by
HCl and NH4OH on the basis of common ion effect.
ii) Relation between Ksp and solubility (S) of sparingly soluble salt (BaSO4):
Consider a saturated solution of BaSO4. The following equilibrium exist.
BaSO4  BaSO4  Ba(aq2 )  SO4(2aq)
Undissolved Dissolved ions
Let the solubility of BaSO4 be S mole/litre. Then the [Ba+2] = S mole ions/litre
[SO42] = S mole ions/litre
This is because the dissolved salt completely dissociates into ions
The solubility product, Ksp = [Ba+2][SO42]
Ksp = S × S = S2; S = K sp
Thus the solubility of BaSO4 (binary electrolyte) is equal to square root of its solubility product.