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Modern Concepts of Acids & Bases

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27 views

Modern Concepts of Acids & Bases

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habeebullakhan069
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© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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MODERN CONCEPTS OF ACIDS AND BASES

INTRODUCTION
Theories of Acids and Bases
1. Arrhenius theory:
According to Arrhenius theory an acid is a substance, which gives hydrogen ions, and base is a
substance, which gives hydroxyl ions in water.
e.g. HCl H2O H+ + Cl-
(acid)

NaOH H2O Na+ + OH-


(base)

2. Bronsted-Lowry theory (Proton Transfer Theory):


According to Bronsted-Lowry theory, an acid is a proton (H+) donor and a base is a proton acceptor.
e.g. 1) HCl + H2O ⇋ Cl- + H3O+
acid base
In the above example HCl gives a proton (H+) to become Cl- and therefore HCl is an acid. H2O
accepts a proton to become H3O+ and therefore H2O is a base.
e.g. 2) NH3 + H2O ⇋ NH4+ + OH-
base acid

3. Lewis theory:
According to Lewis theory an acid is an electron pair acceptor and a base is an electron pair donor.
Lewis acids: It consists of all cations like H+, Na+, Ag+ etc. and molecules containing an atom of incomplete
octet or empty d-orbitals like BF3, SO3, AlCl3, SnCl4 etc.

Lewis bases: It consists of all anions like Cl-, OH-, CO32- etc. and molecules having lone pair of electrons
like NH3, H2O, CO etc.
e.g. NH3 + H+ → NH4+

MODERN CONCEPT OF ACIDS AND BASES


1. LUX-FLOOD CONCEPT
According this concept:
An acid is a substance which is an oxide ion acceptor and a base is a substance which is an oxide ion
donor.
General reaction: Base ⇌ O2- + Acid
e.g., Na2O ⇌ O2- + 2Na+
Base Acid

BaO ⇌ O2- + Ba2+


Base Acid

Based on the above definition, a few direct reactions between acidic and basic anhydrides in the absence
of hydrogen ions are water are given below

Base Acid Salt


BaO + CO2 BaCO3
CaO + SiO2 CaSiO3

1
Such reactions are in conformity with the following reactions:
BaO + H2O → Ba(OH)2 (Base)
CO2 + H2O → H2CO3 (Acid)

Limitation of Lux-Flood concept:


The concept is applicable to only one part of the general theories of Usanovich and Lewis.

2. SOLVENT SYSTEM CONCEPT


It is an extension of Bronsted-Lowry concept of acids and bases. It covers aqueous as well as non-aqueous
solvents. According to this theory:
An acid is a substance (solute) which either by direct dissociation or dissolution increases the
concentration of cations, characteristic of the solvent.
Base is a substance (solute) which either by direct dissociation or dissolution increases the concentration
of anions, characteristic of the solvent.
Following are the examples of some solvents and their characteristic cations and anions obtained.
H2SO4 + H2SO4 ⇌ H3SO4 + + HSO4-
H2O + H2 O ⇌ H3O+ + OH-
NH3 + NH3 ⇌ NH4+ + NH2-

e.g. Water as a solvent – According to this theory any substances that increases the concentration of H3O+
ions in water (solvent) is an acid while that increases the concentration of OH- ion in water is a base.

(i) HCl is an acid in water as it produces H3O+.


HCl + H2O ⇌ H3O+ + Cl-
Acid

(ii) NH3 is a base in water as it produces OH- ions


NH3 + H2O ⇌ NH4+ + OH-
Base

3. USANOVICH CONCEPT
According to this theory:
An acid is a substance which reacts with a base to from a salt or accepts electrons or anions and furnishes
cations.
A base is a substance which reacts with an acid to form salt or accepts cations and furnishes anions or
electrons.

e.g., Action of SO2 (acid) on Na2O (base) to form Na2SO3 (salt).


SO2 (acid) + Na2O (base) → Na2SO3 (salt) ----- (1)

Explanation: (i) Na2O → 2Na+ + O2- ------ (2)


Since Na2O furnishes O2- anion, it is a base.

(ii) SO2 + O2- → SO32- ------ (3)


Since SO2 has accepted the anion, O22-, it is an acid.

Adding equations (2) and (3)to get(1).


Na2O + SO2 → 2Na+ + O2- + SO2 → Na2SO3

2
PEARSON’S CONCEPT OF HARD AND SOFT ACIDS AND BASES
1. HARD ACIDS: They are Lewis acids which are small in size and having electron cloud which are not easily
polarizable. They are generally light metal ions with high oxidation states.
e.g. Li+, Na+, Mg2+, Al3+

2. SOFT ACIDS They are Lewis acids which are comparatively bigger in size and have electron cloud which are
easily polarizable. They are generally heavy metal ions with low oxidation states.
e.g. Cu+, Ag+, Au+, Hg+

3. HARD BASES: They are Lewis bases which prefer to coordinate with hard acids. They are anions or neutral
molecules which are not easily polarizable.
e.g. NH3, OH-, NO3-, F-

4. SOFT BASES: They are Lewis bases which prefer to coordinate with hard bases. They are anions or neutral
molecules which are easily polarizable.
e.g. CN-, SCN-, C6H6, CO

Theoretical Bases of Hardness and Softness


Two simple theories have been proposed to explain the preference of hard acids for hard bases and soft
acids for soft bases.
(1) Ionic and covalent bonding,
(2) Pi bonding theory.

(1) Ionic and Covalent bonding theory:


The interactions (or bonding) between hard acids and hard bases can be described primarily in terms of
electrostatic or dipole-dipole interactions. The reason is that hard acids and hard bases are small, compact,
highly charged and non-polarizable they are unable to share electrons. Smaller the size of the acceptor atom
and the donor atom of hard acids and hard bases, higher is the force of attraction between them.
Soft acids and soft bases are large, diffused and more polarizable than hard acids and hard basses,
therefore, they can share electrons. Thus, soft acid-soft base interactions are primarily covalent.

(2) The π-bonding theory: (by Chatt)


An important feature of soft acids is the presence of loosely held outer d-electrons which can form π bonds
by donation to suitable ligands. Such ligands have empty d or σ * or π * orbitals associated with the basic (or
donor) atom, such as P, As, S, CO and isonitriles. Thus, most of the soft bases are π acceptors and most of the
soft acids are π donors. By contrast, hard acids generally have empty orbitals and are π -electron acceptors and
hard bases with O, N or F basic atoms are π -electron donors.
The interaction between hard acid and soft bases is poor because of the repulsion between filled orbitals
on hard acids and soft bases. Similarly, interaction between soft acids and hard bases is poor because of the
repulsions between filled orbitals on soft acids and hard bases. The hydrogen bonding molecules and hard acids
such as BF3, do not fit in π -bonding concept.

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